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1

Probing the surface structure of divalent transition metals using surface specific solid-state NMR spectroscopy.  

PubMed

Environmental and geochemical systems containing paramagnetic species could benefit by using nuclear magnetic resonance (NMR) spectroscopy due to the sensitivity of the spectral response to small amounts paramagnetic interactions. In this study, we apply commonly used solid-state NMR spectroscopic methods combined with chemometrics analysis to probe sorption behavior of the paramagnetic cations Cu(2+) and Ni(2+)at the amorphous silica surface. We exploit the unique properties of paramagnets to derive meaningful structural information in these systems at low, environmentally relevant cation surface loadings by comparing the NMR response of sorption samples to paramagnetic free samples. These data suggest that a simple sorption model where the cation sorbs as inner sphere complexes at negatively charged, deprotonated silanol sites is appropriate. These results help constrain sorption models that are used to describe metal fate and transport. PMID:22316095

Mason, Harris E; Harley, Stephen J; Maxwell, Robert S; Carroll, Susan A

2012-03-01

2

Probing Quadrupolar Nuclei by Solid-State NMR Spectroscopy: Recent Advances  

SciTech Connect

Solid-state nuclear magnetic resonance (NMR) of quadrupolar nuclei has recently undergone remarkable development of capabilities for obtaining structural and dynamic information at the molecular level. This review summarizes the key achievements attained during the last couple of decades in solid-state NMR of both integer spin and half-integer spin quadrupolar nuclei. We provide a concise description of the first- and second-order quadrupolar interactions, and their effect on the static and magic angle spinning (MAS) spectra. Methods are explained for efficient excitation of single- and multiple-quantum coherences, and acquisition of spectra under low- and high-resolution conditions. Most of all, we present a coherent, comparative description of the high-resolution methods for half-integer quadrupolar nuclei, including double rotation (DOR), dynamic angle spinning (DAS), multiple-quantum magic angle spinning (MQMAS), and satellite transition magic angle spinning (STMAS). Also highlighted are methods for processing and analysis of the spectra. Finally, we review methods for probing the heteronuclear and homonuclear correlations between the quadrupolar nuclei and their quadrupolar or spin-1/2 neighbors.

Fernandez, Christian; Pruski, Marek

2011-06-08

3

15N Solid-State NMR as a Probe of Flavin H-bonding  

PubMed Central

Flavins mediate a wide variety of different chemical reactions in biology. To learn how one cofactor can be made to execute different reactions in different enzymes, we are developing solid-state NMR (SSNMR) to probe the flavin electronic structure, via the 15N chemical shift tensor principal values (?ii). We find that SSNMR has superior responsiveness to H-bonds, compared to solution NMR. H-bonding to a model of the flavodoxin active site produced an increase of 10 ppm in the ?11 of N5 although none of the H-bonds directly engage N5, and solution NMR detected only a 4 ppm increase in the isotropic chemical shift (?iso). Moreover SSNMR responded differently to different H-bonding environments as H-bonding with water caused ?11 to decrease by 6 ppm whereas ?iso increased by less than 1 ppm. Our density functional theoretical (DFT) calculations reproduce the observations, validating the use of computed electronic structures to understand how H-bonds modulate the flavin’s reactivity. PMID:21619002

Cui, Dongtao; Koder, Ronald L.; Dutton, P. Leslie; Miller, Anne-Frances

2011-01-01

4

Solid-state NMR characterization of the acid sites in cubic mesoporous Al-MCM-48 materials using trimethylphosphine oxide as a 31P NMR probe  

Microsoft Academic Search

The acidic properties of Al-MCM-48 with Si\\/Al ratios ranging from 10 to 67, synthesized with Gemini surfactant as the template, have been characterized by a combination of multinuclear solid-state 1H, 23Na, 27Al, 29Si and 31P MAS (magic angle spinning) NMR and some double-resonance NMR methods using trimethylphosphine oxide (TMPO) as a probe molecule. XRD and 27Al MAS NMR results indicated

Hsien-Ming Kao; Pai-Ching Chang; Yun-Wen Liao; Lung-Ping Lee; Chu-Hua Chien

2008-01-01

5

Solid-State NMR Spectroscopy  

NASA Astrophysics Data System (ADS)

Due to the development of new techniques and further increase of magnetic field strength available for commercial applications, solid-state NMR spectroscopy became a routine method for the characterization of zeolites. As an important advantage, solid-state NMR spectroscopy allows the investigation of the local structure of nuclei in the solids under study. The specific behavior of zeolites often depends on local effects, such as framework defects, the substitution of framework atoms, guest compounds etc. Therefore, solid-state NMR spectroscopy is a widely applied analytical method for delivering structure data, which are complementary to those of diffraction methods suitable for investigating the long-range order. While early solid-state NMR spectroscopic studies often focused on the characterization of the zeolite framework in the as-synthesized and hydrated state, an increasing number of recent works is dealing with the investigation of the framework of dehydrated and calcined zeolites and of surface sites, i.e., on the determination of their concentration, strength, and accessibility. In all these applications, the advantage of solid-state NMR spectroscopy to be a quantitative method is utilized. The present chapter demonstrates the fundamentals, various techniques, and most important applications of solid-state NMR spectroscopy making this method to an important tool of research in zeolite science.

Hunger, Michael

6

Solid-state STRAFI NMR probe for material imaging of quadrupolar nuclei.  

PubMed

Stray field imaging (STRAFI) has provided an alternative imaging method to study solid materials that are typically difficult to obtain using conventional MRI methods. For small volume samples, image resolution is a challenge since extremely strong gradients are required to examine narrow slices. Here we present a STRAFI probe for imaging materials with quadrupolar nuclei. Experiments were performed on a 19.6 T magnet which has a fringe field gradient strength of 72 T/m, nearly 50 times stronger than commercial microimagers. We demonstrate the ability to acquire (7)Li 1D profiles of liquid and solid state lithium phantoms with clearly resolved features in the micrometer scale and as a practical example a Li ion battery electrode material is also examined. PMID:23151490

Tang, Joel A; Zhong, Guiming; Dugar, Sneha; Kitchen, Jason A; Yang, Yong; Fu, Riqiang

2012-12-01

7

Solid-state NMR imaging system  

DOEpatents

An apparatus for use with a solid-state NMR spectrometer includes a special imaging probe with linear, high-field strength gradient fields and high-power broadband RF coils using a back projection method for data acquisition and image reconstruction, and a real-time pulse programmer adaptable for use by a conventional computer for complex high speed pulse sequences.

Gopalsami, Nachappa (Naperville, IL); Dieckman, Stephen L. (Elmhurst, IL); Ellingson, William A. (Naperville, IL)

1992-01-01

8

Solid-state NMR spectroscopy to probe photoactivation in canonical phytochromes.  

PubMed

The photoreceptor phytochrome switches photochromically between two thermally stable states called Pr and Pfr. Here, we summarize recent solid-state magic-angle spinning (MAS) NMR work on this conversion process and interpret the functional mechanism in terms of a nano-machine. The process is initiated by a double-bond photoisomerization of the open-chain tetrapyrrole chromophore at the methine bridge connecting pyrrole rings C and D. The Pr-state chromophore and its surrounding pocket in canonical cyanobacterial and plant phytochromes has significantly less order, tends to form isoforms and is soft. Conversely, Pfr shows significantly harder chromophore-protein interactions, a well-defined protonic and charge distribution with a clear classical counterion for the positively charged tetrapyrrole system. The soft-to-hard/disorder-to-order transition involves the chromophore and its protein surroundings within a sphere of at least 5.5 Å. The relevance of this collective event for signaling is discussed. Measurement of the intermediates during the Pfr ? Pr back-reaction provides insight into the well-adjusted mechanics of a two-step transformation. As both Pr ? Pfr and Pfr ? Pr reaction pathways are different in ground and excited states, a photochemically controlled hyper-landscape is proposed allowing for ratchet-type reaction dynamics regulating signaling activity. PMID:23216105

Song, Chen; Rohmer, Thierry; Tiersch, Markus; Zaanen, Jan; Hughes, Jon; Matysik, Jörg

2013-01-01

9

Probing membrane protein structure using water polarization transfer solid-state NMR  

NASA Astrophysics Data System (ADS)

Water plays an essential role in the structure and function of proteins, lipid membranes and other biological macromolecules. Solid-state NMR heteronuclear-detected 1H polarization transfer from water to biomolecules is a versatile approach for studying water-protein, water-membrane, and water-carbohydrate interactions in biology. We review radiofrequency pulse sequences for measuring water polarization transfer to biomolecules, the mechanisms of polarization transfer, and the application of this method to various biological systems. Three polarization transfer mechanisms, chemical exchange, spin diffusion and NOE, manifest themselves at different temperatures, magic-angle-spinning frequencies, and pulse irradiations. Chemical exchange is ubiquitous in all systems examined so far, and spin diffusion plays the key role in polarization transfer within the macromolecule. Tightly bound water molecules with long residence times are rare in proteins at ambient temperature. The water polarization-transfer technique has been used to study the hydration of microcrystalline proteins, lipid membranes, and plant cell wall polysaccharides, and to derive atomic-resolution details of the kinetics and mechanism of ion conduction in channels and pumps. Using this approach, we have measured the water polarization transfer to the transmembrane domain of the influenza M2 protein to obtain information on the structure of this tetrameric proton channel. At short mixing times, the polarization transfer rates are site-specific and depend on the pH, labile protons, sidechain conformation, as well as the radial position of the residues in this four-helix bundle. Despite the multiple dependences, the initial transfer rates reflect the periodic nature of the residue positions from the water-filled pore, thus this technique provides a way of gleaning secondary structure information, helix tilt angle, and the oligomeric structure of membrane proteins.

Williams, Jonathan K.; Hong, Mei

2014-10-01

10

Probing membrane protein structure using water polarization transfer solid-state NMR.  

PubMed

Water plays an essential role in the structure and function of proteins, lipid membranes and other biological macromolecules. Solid-state NMR heteronuclear-detected (1)H polarization transfer from water to biomolecules is a versatile approach for studying water-protein, water-membrane, and water-carbohydrate interactions in biology. We review radiofrequency pulse sequences for measuring water polarization transfer to biomolecules, the mechanisms of polarization transfer, and the application of this method to various biological systems. Three polarization transfer mechanisms, chemical exchange, spin diffusion and NOE, manifest themselves at different temperatures, magic-angle-spinning frequencies, and pulse irradiations. Chemical exchange is ubiquitous in all systems examined so far, and spin diffusion plays the key role in polarization transfer within the macromolecule. Tightly bound water molecules with long residence times are rare in proteins at ambient temperature. The water polarization-transfer technique has been used to study the hydration of microcrystalline proteins, lipid membranes, and plant cell wall polysaccharides, and to derive atomic-resolution details of the kinetics and mechanism of ion conduction in channels and pumps. Using this approach, we have measured the water polarization transfer to the transmembrane domain of the influenza M2 protein to obtain information on the structure of this tetrameric proton channel. At short mixing times, the polarization transfer rates are site-specific and depend on the pH, labile protons, sidechain conformation, as well as the radial position of the residues in this four-helix bundle. Despite the multiple dependences, the initial transfer rates reflect the periodic nature of the residue positions from the water-filled pore, thus this technique provides a way of gleaning secondary structure information, helix tilt angle, and the oligomeric structure of membrane proteins. PMID:25228502

Williams, Jonathan K; Hong, Mei

2014-10-01

11

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area  

NASA Astrophysics Data System (ADS)

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q 3 groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the "Icelandic" samples and with duration of field weathering for both "Icelandic" and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q 3 sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative 19F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, 27Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.

Washton, Nancy M.; Brantley, Susan L.; Mueller, Karl T.

2008-12-01

12

DEVELOPMENT OF MULTIPLE SAMPLE SOLID-STATE NMR PROBES FOR ANALYSIS OF PHARMACEUTICAL COMPOUNDS AND FORMULATIONS  

E-print Network

. Compound 1H Frequency Delay (s) Delay at 9.4 T (s) Ref R.O.Y.* 300 40-70 70-125 4 Cimetidine 360 15 18 5 LY297802 400 5-10 5-10 6 Ephedrine 200 1.5 6 7 Aspirin 300 90 160 † Salicylic Acid 300 1000 1780 † Prednisolone t-Butylacetate 200 3 12 8...297802 Tartrate. J. Pharm. Sci., 1998. 87: p. 1568. 12. Schmidt, W.F. and I.L. Honigberg, Nuclear Magnetic Resonance (NMR) Spectroscopic Investigation of Interaction Energies of Ephedrine Steroisomers in Non Crystalline Solids and its Correlation...

Nelson, Benjamin Nels

2011-12-31

13

Chemical shift referencing in MAS solid state NMR  

Microsoft Academic Search

Solid state 13C magic angle spinning (MAS) NMR spectra are typically referenced externally using a probe which does not incorporate a field frequency lock. Solution NMR shifts on the other hand are more often determined with respect to an internal reference and using a deuterium based field frequency lock. Further differences arise in solution NMR of proteins and nucleic acids

Corey R Morcombe; Kurt W Zilm

2003-01-01

14

Probing Transient Conformational States of Proteins by Solid-State R1? Relaxation-Dispersion NMR Spectroscopy  

PubMed Central

Functionally relevant states of proteins are often only short-lived, and thus difficult to detect. It is shown that R1? relaxation-dispersion experiments in magic-angle spinning solid-state NMR provide access to such transient states. Information about the exchange kinetics and relative populations can be obtained, and also structural information about the short-lived state in terms of chemical shifts and bond vector orientations. PMID:24644028

Ma, Peixiang; Haller, Jens D.; Zajakala, Jeremy; Macek, Pavel; Sivertsen, Astrid C.; Willbold, Dieter; Boisbouvier, Jerome; Schanda, Paul

2014-01-01

15

Probing transient conformational states of proteins by solid-state R(1?) relaxation-dispersion NMR spectroscopy.  

PubMed

The function of proteins depends on their ability to sample a variety of states differing in structure and free energy. Deciphering how the various thermally accessible conformations are connected, and understanding their structures and relative energies is crucial in rationalizing protein function. Many biomolecular reactions take place within microseconds to milliseconds, and this timescale is therefore of central functional importance. Here we show that R1? relaxation dispersion experiments in magic-angle-spinning solid-state NMR spectroscopy make it possible to investigate the thermodynamics and kinetics of such exchange process, and gain insight into structural features of short-lived states. PMID:24644028

Ma, Peixiang; Haller, Jens D; Zajakala, Jérémy; Macek, Pavel; Sivertsen, Astrid C; Willbold, Dieter; Boisbouvier, Jérôme; Schanda, Paul

2014-04-22

16

A Modified Alderman-Grant Coil makes possible an efficient cross-coil probe for high field solid-state NMR of lossy biological samples  

NASA Astrophysics Data System (ADS)

The design, construction, and performance of a cross-coil double-resonance probe for solid-state NMR experiments on lossy biological samples at high magnetic fields are described. The outer coil is a Modified Alderman-Grant Coil (MAGC) tuned to the 1H frequency. The inner coil consists of a multi-turn solenoid coil that produces a B 1 field orthogonal to that of the outer coil. This results in a compact nested cross-coil pair with the inner solenoid coil tuned to the low frequency detection channel. This design has several advantages over multiple-tuned solenoid coil probes, since RF heating from the 1H channel is substantially reduced, it can be tuned for samples with a wide range of dielectric constants, and the simplified circuit design and high inductance inner coil provides excellent sensitivity. The utility of this probe is demonstrated on two electrically lossy samples of membrane proteins in phospholipid bilayers (bicelles) that are particularly difficult for conventional NMR probes. The 72-residue polypeptide embedding the transmembrane helices 3 and 4 of the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) (residues 194-241) requires a high salt concentration in order to be successfully reconstituted in phospholipid bicelles. A second application is to paramagnetic relaxation enhancement applied to the membrane-bound form of Pf1 coat protein in phospholipid bicelles where the resistance to sample heating enables high duty cycle solid-state NMR experiments to be performed.

Grant, Christopher V.; Yang, Yuan; Glibowicka, Mira; Wu, Chin H.; Park, Sang Ho; Deber, Charles M.; Opella, Stanley J.

2009-11-01

17

Probing physical and chemical changes in cortical bone due to osteoporosis and type 2 diabetes by solid-state NMR  

NASA Astrophysics Data System (ADS)

Approximately 1.5 million fractures occur each year in the U.S. due to osteoporosis, which is characterized by decreased bone mineral density and deterioration of bone micro-architecture. On the other hand, type 2 diabetes also significantly increases fracture risks, despite having a normal or even higher bone mineral density. Solid-state NMR has been applied to bone tissues from normal and disease-inflicted mouse models to study structural and chemical dynamics as the disease progresses. Proton relaxation experiments were performed to measure water populations in the bone matrix and pores. Collagen-bound water has strong influence on bone resilience, while water content in the pores reveals amount and size of pores from micro- to millimeter range. Other biochemical and atomic-scale structural alterations in the mineral and organic phases and their interface were investigated by proton, phosphorus, and carbon NMR spectroscopy. Experiments were designed to individually detect different types of phosphorus environments: near the mineral surface, similar to hydroxyapatite, and deficient of hydrogens due to substitution of the hydroxyl group by other ions. A new method was also developed for accurate quantification of each phosphorus species.

Zhou, Donghua; Taylor, Amanda; Rendina, Beth; Smith, Brenda

2013-03-01

18

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area  

Microsoft Academic Search

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due

Nancy M. Washton; Susan L. Brantley; Karl T. Mueller

2008-01-01

19

Distortional binding of transition state analogs to human purine nucleoside phosphorylase probed by magic angle spinning solid-state NMR  

PubMed Central

Transition state analogs mimic the geometry and electronics of the transition state of enzymatic reactions. These molecules bind to the active site of the enzyme much tighter than substrate and are powerful noncovalent inhibitors. Immucillin-H (ImmH) and 4?-deaza-1?-aza-2?-deoxy-9-methylene Immucillin-H (DADMe-ImmH) are picomolar inhibitors of human purine nucleoside phosphorylase (hPNP). Although both molecules are electronically similar to the oxocarbenium-like dissociative hPNP transition state, DADMe-ImmH is more potent than ImmH. DADMe-ImmH captures more of the transition state binding energy by virtue of being a closer geometric match to the hPNP transition state than ImmH. A consequence of these similarities is that the active site of hPNP exerts greater distortional forces on ImmH than on DADMe-ImmH to “achieve” the hPNP transition state geometry. By using magic angle spinning solid-state NMR to investigate stable isotope-labeled ImmH and DADMe-ImmH, we have explored the difference in distortional binding of these two inhibitors to hPNP. High-precision determinations of internuclear distances from NMR recoupling techniques, rotational echo double resonance, and rotational resonance, have provided unprecedented atomistic insight into the geometric changes that occur upon binding of transition state analogs. We conclude that hPNP stabilizes conformations of these chemically distinct analogs having distances between the cation and leaving groups resembling those of the known transition state. PMID:24043827

Vetticatt, Mathew J.; Itin, Boris; Evans, Gary B.; Schramm, Vern L.

2013-01-01

20

Solid-State NMR for Bacterial Biofilms  

PubMed Central

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 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 E. coli biofilm and transform 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. PMID:24976646

Reichhardt, Courtney; Cegelski, Lynette

2014-01-01

21

Dynamic nuclear polarization in biomolecular solid state NMR : methods and applications in peptides and membrane proteins  

E-print Network

Solid state NMR can probe structure and dynamics on length scales from the atomic to the supramolecular. However, low sensitivity limits its application in macromolecules. NMR sensitivity can be improved by dynamic nuclear ...

Bajaj, Vikram Singh

2007-01-01

22

Ligand-Induced Conformational Changes of the Multidrug Resistance Transporter EmrE Probed by Oriented Solid-State NMR Spectroscopy  

PubMed Central

We used oriented solid-state NMR spectroscopy and biochemical cross-linking experiments to demonstrate that the ligand-free membrane protein transporter EmrE forms anti-parallel dimers with different monomer tilt angles relative to the lipid bilayer. Our results also show the subtle conformational changes efflux pumps experience in response to drug binding and emphasize the importance of studying membrane proteins in a fluid bilayer environment. PMID:23939862

Gayen, Anindita; Banigan, James R.

2013-01-01

23

Solid-state NMR crystallography through paramagnetic restraints.  

PubMed

Pseudocontact shifts (PCSs) measured by solid-state NMR spectroscopy (SS-NMR) on microcrystalline powders of a paramagnetic metalloprotein permit NMR crystallography. Along with other restraints for SS-NMR experiments, the protein molecular structure as well as the correct crystal packing are obtained. PMID:22393876

Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico; Rinaldelli, Mauro

2012-03-21

24

Solid-state NMR of proteins sedimented by ultracentrifugation  

PubMed Central

Relatively large proteins in solution, spun in NMR rotors for solid samples at typical ultracentrifugation speeds, sediment at the rotor wall. The sedimented proteins provide high-quality solid-state-like NMR spectra suitable for structural investigation. The proteins fully revert to the native solution state when spinning is stopped, allowing one to study them in both conditions. Transiently sedimented proteins can be considered a novel phase as far as NMR is concerned. NMR of transiently sedimented molecules under fast magic angle spinning has the advantage of overcoming protein size limitations of solution NMR without the need of sample crystallization/precipitation required by solid-state NMR. PMID:21670262

Bertini, Ivano; Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico; Reif, Bernd; Turano, Paola

2011-01-01

25

Solid-state NMR of proteins sedimented by ultracentrifugation.  

PubMed

Relatively large proteins in solution, spun in NMR rotors for solid samples at typical ultracentrifugation speeds, sediment at the rotor wall. The sedimented proteins provide high-quality solid-state-like NMR spectra suitable for structural investigation. The proteins fully revert to the native solution state when spinning is stopped, allowing one to study them in both conditions. Transiently sedimented proteins can be considered a novel phase as far as NMR is concerned. NMR of transiently sedimented molecules under fast magic angle spinning has the advantage of overcoming protein size limitations of solution NMR without the need of sample crystallization/precipitation required by solid-state NMR. PMID:21670262

Bertini, Ivano; Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico; Reif, Bernd; Turano, Paola

2011-06-28

26

Solid state NMR — a powerful tool for the investigation of surface hydroxyl groups in zeolites and their interactions with adsorbed probe molecules  

NASA Astrophysics Data System (ADS)

Recent developments in the NMR spectroscopic investigation of surface hydroxyl groups in zeolites are reviewed in the present paper. The composition and porous structure of zeolites are briefly described. The structure and basic properties of surface hydroxyl groups (especially of bridging hydroxyl groups) in zeolites are explained. The influence of the magic angle spinning (MAS) technique on the 1H NMR spectrum of activated zeolites is described in detail. Different NMR spectroscopic methods which allow the measurement of the H?Al distance rH?Al between the protons and the 27Al nuclei in bridging hydroxyl groups are compared. The limitations of spectral resolution of the 1H MAS NMR spectra are discussed quantitatively on the basis of extended quantum chemical calculations. It is shown that the 1H NMR chemical shift ?H allows the measurement of the deprotonation energy of free surface hydroxyl groups in zeolites. The influence of electrostatic interactions upon ?H is discussed and a correlation between the 1H NMR chemical shift and the wavenumber of the stretching vibration of surface hydroxyl groups is stated. Further, 1H MAS NMR and IR spectroscopy are compared especially with respect to concentration measurements. Applications of low-temperature 1H MAS NMR spectroscopy to the investigation of the interaction between surface hydroxyl groups and adsorbed probe molecules are demonstrated. Finally, the present paper reviews recent NMR spectroscopic studies of probe molecules under the influence of bridging hydroxyl groups.

Brunner, Eike

1995-08-01

27

Probing the structural disorder of basalts and slab-driven andesite melts: Insights from high-resolution solid-state NMR study  

NASA Astrophysics Data System (ADS)

Whereas the structure of multi-component silicate melts has strong implication for the properties of natural silicate melts and relevant magmatic processes in Earth's mantle and crust, little is known about their atomic structures due to lack of suitable experimental probes of multi-component amorphous oxides. Although most of the progress in melt structure has been made for relatively simple binary and ternary silicate glasses, recent advances in high-resolution solid-state NMR (nuclear magnetic resonance) unveil previously unknown structural details of multi-component silicate melts (Lee, S. K. and Sung, S., Chem. Geol., 2008, 256, 326; Lee et al., P. Natl. Acad. Sci. USA., 2011, 108, 6847; Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125). In this study we report experimental results on the effects of composition. atomic structure of CaO-MgO-Al_{2} O_{3} -SiO_{2} (CMAS) glasses in diopside (CaMgSi_{2}O_{6}) and Ca-tschermakite (CaAl_{2}SiO_{6}) join and glass in the diopside-anorthite eutectic composition (Di_{64}An_{36})—model systems for basaltic melts—using solid-state NMR. We also report the first high-resolution experimental results on the atomic structure of CaO-MgO-Na_{2}O-Al_{2}O_{3}-SiO_{2} (CMNAS) glasses in diopside and jadeite (NaAlSi_{2}O_{6}) join, and glass in the natural phonolite composition (CaO: MgO: Na_{2}O: K_{2}O: Al_{2}O_{3}: SiO_{2}= 1.4: 8.0: 9.0: 3.8: 13: 64 mol%), a model system for slab driven andesite melts. The Al-27 3QMAS (triple quantum magic angle spinning) NMR spectra of CMAS glasses in diopside-Ca-tschermakite join show predominant ^{[4]}Al and a non-negligible fraction of ^{[5]}Al. Approximately 3.3% of ^{[5]}Al is observed for Di_{64}An_{36} glass. The Al-27 3QMAS NMR spectra of CMNAS glasses in diopside and jadeite join show mostly ^{[4]}Al and a non-negligible fraction of ^{[5]}Al (X_{Diopside}=0.75, the mole fraction of diopside content). While the C_{q} (quadrupolar coupling constant) of ^{[4]}Al for glasses in diopside-Ca-tschermakite join decreases, that of ^{[4]}Al in diopside-jadeite increases with increasing X_{Diopside}. The Al-27 3QMAS NMR spectrum of phonolite glass shows only ^{[4]}Al species. The C_{q} of ^{[4]}Al ( 4.6 MHz) in phonolite glass is smaller than that of Di_{64}An_{36} eutectic glass ( 6.0 MHz) indicating larger deviation from perfect tetrahedral symmetry around ^{[4]}Al in basaltic melt than that of natural andesitic melt. The fraction of ^{[5]}Al, the degree of configurational disorder, increases with increasing X_{Ca+Mg} (the fraction of high field strength cations, X_{Ca+Mg}=[Ca+Mg]/[Ca+Mg+Na]) and thus the average cation field strength of non- framework cations (the average value of cation field strength normalized by mole fraction of each cations). The fraction of ^{[5]}Al is negligible from X_{Ca+Mg} =0 to X_{Ca+Mg} =0.08, and then it abruptly increases from 1.6 % for X_{Ca+Mg}=0.11 to 3.5% for X_{Ca+Mg}=0.13. This result indicates that there is a threshold composition (X_{Ca+Mg} 0.1) of silicate glasses and melts for increasing fraction of ^{[5]}Al. The abrupt changes of the fraction of ^{[5]}Al multi-component silicate glasses and melts can provide insight into drastic changes of macroscopic properties (entropy, viscosity, diffusivity, etc.) with varying composition of melt (i.e., basalt and andesite melts in this study).

Park, S.; Lee, S.

2012-12-01

28

Solid-State NMR Studies of Amyloid Fibril Structure  

NASA Astrophysics Data System (ADS)

Current interest in amyloid fibrils stems from their involvement in neurodegenerative and other diseases and from their role as an alternative structural state for many peptides and proteins. Solid-state nuclear magnetic resonance (NMR) methods have the unique capability of providing detailed structural constraints for amyloid fibrils, sufficient for the development of full molecular models. In this article, recent progress in the application of solid-state NMR to fibrils associated with Alzheimer's disease, prion fibrils, and related systems is reviewed, along with relevant developments in solid-state NMR techniques and technology.

Tycko, Robert

2011-05-01

29

Structural studies of amyloid fibrils using solid-state NMR  

E-print Network

he development of solid-state NMR techniques and application to amyloid fibrils are presented. In addition, a new method of selective inversion based on chemical shift anisotropy is presented. An improved method for highly ...

Caporini, Marc Anthony

2008-01-01

30

Probing silicon and aluminium chemical environments in silicate and aluminosilicate glasses by solid state NMR spectroscopy and accurate first-principles calculations  

NASA Astrophysics Data System (ADS)

Silicon and aluminium chemical environments in silicate and aluminosilicate glasses with compositions 60SiO2·20Na2O·20CaO (CSN), 60SiO2·20Al2O3·20CaO (CAS), 78SiO2·11Al2O3·11Na2O (NAS) and 60SiO2·10Al2O3·10Na2O·20CaO (CASN) have been investigated by 27Al and 29Si solid state magic angle spinning (MAS) and multiple quantum MAS (MQMAS) nuclear magnetic resonance (NMR) experiments. To interpret the NMR data, first-principles calculations using density functional theory were performed on structural models of these glasses. These models were generated by Shell-model molecular dynamics (MD) simulations. The theoretical NMR parameters and spectra were computed using the gauge including projected augmented wave (GIPAW) method and spin-effective Hamiltonians, respectively. This synergetic computational-experimental approach offers a clear structural characterization of these glasses, particularly in terms of network polymerization, chemical disorder (i.e. Si and Al distribution in second coordination sphere) and modifier cation distributions. The relationships between the local structural environments and the 29Si and 27Al NMR parameters are highlighted, and show that: (i) the isotropic chemical shift of both 29Si and 27Al increases of about +5 ppm for each Al added in the second sphere and (ii) both the 27Al and 29Si isotropic chemical shifts linearly decrease with the reduction of the average Si/Al-O-T bond angle. Conversely, 27Al and 29Si NMR parameters are much less sensitive to the connectivity with triple bridging oxygen atoms, precluding their indirect detection from 27Al and 29Si NMR.

Gambuzzi, Elisa; Pedone, Alfonso; Menziani, Maria Cristina; Angeli, Frédéric; Caurant, Daniel; Charpentier, Thibault

2014-01-01

31

Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: applications to nanoporous solids.  

PubMed

A five-channel ((1)H, (19)F, (31)P, (27)Al, (13)C) 2.5 mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T1 relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time. PMID:24011557

Martineau, Charlotte; Decker, Frank; Engelke, Frank; Taulelle, Francis

2013-01-01

32

Probing the Transmembrane Structure and Topology of Microsomal Cytochrome-P450 by Solid-State NMR on Temperature-Resistant Bicelles  

PubMed Central

Though the importance of high-resolution structure and dynamics of membrane proteins has been well recognized, optimizing sample conditions to retain the native-like folding and function of membrane proteins for Nuclear Magnetic Resonance (NMR) or X-ray measurements has been a major challenge. While bicelles have been shown to stabilize the function of membrane proteins and are increasingly utilized as model membranes, the loss of their magnetic-alignment at low temperatures makes them unsuitable to study heat-sensitive membrane proteins like cytochrome-P450 and protein-protein complexes. In this study, we report temperature resistant bicelles that can magnetically-align for a broad range of temperatures and demonstrate their advantages in the structural studies of full-length microsomal cytochrome-P450 and cytochrome-b5 by solid-state NMR spectroscopy. Our results reveal that the N-terminal region of rabbit cytochromeP4502B4, that is usually cleaved off to obtain crystal structures, is helical and has a transmembrane orientation with ~17° tilt from the lipid bilayer normal. PMID:23989972

Yamamoto, Kazutoshi; Gildenberg, Melissa; Ahuja, Shivani; Im, Sang-Choul; Pearcy, Paige; Waskell, Lucy; Ramamoorthy, Ayyalusamy

2013-01-01

33

Probing the Transmembrane Structure and Topology of Microsomal Cytochrome-P450 by Solid-State NMR on Temperature-Resistant Bicelles  

NASA Astrophysics Data System (ADS)

Though the importance of high-resolution structure and dynamics of membrane proteins has been well recognized, optimizing sample conditions to retain the native-like folding and function of membrane proteins for Nuclear Magnetic Resonance (NMR) or X-ray measurements has been a major challenge. While bicelles have been shown to stabilize the function of membrane proteins and are increasingly utilized as model membranes, the loss of their magnetic-alignment at low temperatures makes them unsuitable to study heat-sensitive membrane proteins like cytochrome-P450 and protein-protein complexes. In this study, we report temperature resistant bicelles that can magnetically-align for a broad range of temperatures and demonstrate their advantages in the structural studies of full-length microsomal cytochrome-P450 and cytochrome-b5 by solid-state NMR spectroscopy. Our results reveal that the N-terminal region of rabbit cytochromeP4502B4, that is usually cleaved off to obtain crystal structures, is helical and has a transmembrane orientation with ~17° tilt from the lipid bilayer normal.

Yamamoto, Kazutoshi; Gildenberg, Melissa; Ahuja, Shivani; Im, Sang-Choul; Pearcy, Paige; Waskell, Lucy; Ramamoorthy, Ayyalusamy

2013-08-01

34

Solid state NMR and protein-protein interactions in membranes.  

PubMed

Solid state NMR spectroscopy has evolved rapidly in recent years into an excellent tool for the characterization of membrane proteins and their complexes. In the past few years it has also become clear that the structure of membrane proteins, especially helical membrane proteins is determined, in part, by the membrane environment. Therefore, the modeling of this environment by a liquid crystalline lipid bilayer for solid state NMR has generated a unique tool for the characterization of native conformational states, local and global dynamics, and high-resolution structure for these proteins. Protein-protein interactions can also benefit from this solid state NMR capability to characterize membrane proteins in a native-like environment. These complexes take the form of oligomeric structures and hetero-protein interactions both with water-soluble proteins and other membrane proteins. PMID:24034903

Miao, Yimin; Cross, Timothy A

2013-12-01

35

Pure-Exchange Solid-State NMR  

NASA Astrophysics Data System (ADS)

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield 13C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration ?, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing ? and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s).

deAzevedo, Eduardo R.; Bonagamba, Tito J.; Schmidt-Rohr, Klaus

2000-01-01

36

Pure-exchange solid-state NMR.  

PubMed

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield (13)C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration tau, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing tau and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s). PMID:10617438

deAzevedo, E R; Bonagamba, T J; Schmidt-Rohr, K

2000-01-01

37

Kubo-Anderson oscillator and NMR of solid state.  

PubMed

The analytical solution for the Kubo-Anderson oscillator with a fluctuating frequency omega for arbitrary distribution function p(omega) has been obtained. The obtained theoretical expression has been applied to consideration of some dynamical problems of solid state NMR, namely (1) dynamical transformation of NMR line shape and spin-echo signal and (2) the temperature transformation of the second moment of NMR line for the case, when the potential barrier for the mobility of magnetic nuclei is a stochastic function of time. PMID:18783926

Sergeev, N A; Olszewski, M

2008-10-01

38

Solid-State NMR Characterization of Aluminum Oxide Nanofibers  

SciTech Connect

Aluminum oxide nanofibers have been generated by an electrospinning process, creating fibers with diameters on the nanometer scale and aspect ratios greater than a thousand. These nanofibers have the potential of providing enhanced catalytic properties, due to their large surface area and controllable compositions. Solid-state NMR is being used to investigate both the bulk and surface properties of these materials. 27Al NMR has shown that no chemistry occurs during the electrospinning process, even though potentials in excess of 20 kV are applied to the sample. Thermal treatment of the fibers to convert them to alumina results in the formation of different phases, with the phases identified by the relative populations of 4-, 5-, and 6-coordinate alumina sites. Heating to 525°C or 1200°C produces a species similar to the catalytically active gamma-phase or conversion of the nanofibers into the thermodynamically stable ?-alumina phase, respectively. 1H-27Al CP/MAS has shown that the ?-alumina phase has a low population of surface hydroxyls, whereas the “gamma-alumina” form has a much higher fraction of 5-coordinate sites, compared to materials synthesized by traditional techniques. Organophosphates are being used as molecular probes in the characterization of the nanofiber surfaces. 31P CP/MAS data has revealed the presence of mono-, bi- and tri-denate bound phosphate groups on the surface, with the onset of surface alumina dissolution with sample heating. The application of 1H-31P HETCOR shows that the three different types of bound organophosphates are intermixed, rather than there being separate domains for each type. 31P-27Al CP is also being used to distinguish the types of surface alumina sites bound to the phosphate species.

Cross, Jennifer L.; Tuttle, Ricky W.; Ramsier, Rex D.; Espe, Mathew

2006-07-24

39

Solid state NMR of porous materials : zeolites and related materials.  

PubMed

Solid state NMR spectroscopy applied to the science of crystalline micro- and mesoporous silica materials over the past 10 years is reviewed. A survey is provided of framework structure and connectivity analyses from chemical shift effects of various elements in zeolites including heteroatom substitutions, framework defects and pentacoordinated silicon for zeolites containing fluoride ions. New developments in the field of NMR crystallography are included. Spatial host-guest ordering and confinement effects of zeolite-sorbate complexes are outlined, with special emphasis on NMR applications utilizing the heteronuclear dipolar interaction. The characterization of zeolite acid sites and in situ NMR on catalytic conversions is also included. Finally, the motion of extra-framework cations is investigated in two tutorial cases of sodium hopping in sodalite and cancrinite. PMID:21452082

Koller, Hubert; Weiss, Mark

2012-01-01

40

Magic-angle spinning solid-state multinuclear NMR on low-field instrumentation.  

PubMed

Mobile and cost-effective NMR spectroscopy exploiting low-field permanent magnets is a field of tremendous development with obvious applications for arrayed large scale analysis, field work, and industrial screening. So far such demonstrations have concentrated on relaxation measurements and lately high-resolution liquid-state NMR applications. With high-resolution solid-state NMR spectroscopy being increasingly important in a broad variety of applications, we here introduce low-field magic-angle spinning (MAS) solid-state multinuclear NMR based on a commercial ACT 0.45 T 62 mm bore Halbach magnet along with a homebuilt FPGA digital NMR console, amplifiers, and a modified standard 45 mm wide MAS probe for 7 mm rotors. To illustrate the performance of the instrument and address cases where the low magnetic field may offer complementarity to high-field NMR experiments, we demonstrate applications for (23)Na MAS NMR with enhanced second-order quadrupolar coupling effects and (31)P MAS NMR where reduced influence from chemical shift anisotropy at low field may facilitate determination of heteronuclear dipole-dipole couplings. PMID:24291330

Sørensen, Morten K; Bakharev, Oleg; Jensen, Ole; Jakobsen, Hans J; Skibsted, Jørgen; Nielsen, Niels Chr

2014-01-01

41

Magic-angle spinning solid-state multinuclear NMR on low-field instrumentation  

NASA Astrophysics Data System (ADS)

Mobile and cost-effective NMR spectroscopy exploiting low-field permanent magnets is a field of tremendous development with obvious applications for arrayed large scale analysis, field work, and industrial screening. So far such demonstrations have concentrated on relaxation measurements and lately high-resolution liquid-state NMR applications. With high-resolution solid-state NMR spectroscopy being increasingly important in a broad variety of applications, we here introduce low-field magic-angle spinning (MAS) solid-state multinuclear NMR based on a commercial ACT 0.45 T 62 mm bore Halbach magnet along with a homebuilt FPGA digital NMR console, amplifiers, and a modified standard 45 mm wide MAS probe for 7 mm rotors. To illustrate the performance of the instrument and address cases where the low magnetic field may offer complementarity to high-field NMR experiments, we demonstrate applications for 23Na MAS NMR with enhanced second-order quadrupolar coupling effects and 31P MAS NMR where reduced influence from chemical shift anisotropy at low field may facilitate determination of heteronuclear dipole-dipole couplings.

Sørensen, Morten K.; Bakharev, Oleg; Jensen, Ole; Jakobsen, Hans J.; Skibsted, Jørgen; Nielsen, Niels Chr.

2014-01-01

42

Microcoils and microsamples in solid-state NMR.  

PubMed

Recent reports on microcoils are reviewed. The first part of the review includes a discussion of how the geometries of the sample and coil affect the NMR signal intensity. In addition to derivation of the well-known result that the signal intensity increases as the coil size decreases, the prediction that dilution of a small sample with magnetically inert matter leads to better sensitivity if a tiny coil is not available is given. The second part of the review focuses on the issues specific to solid-state NMR. They include realization of magic-angle spinning (MAS) using a microcoil and harnessing of such strong pulses that are feasible only with a microcoil. Two strategies for microcoil MAS, the piggyback method and magic-angle coil spinning (MACS), are reviewed. In addition, MAS of flat, disk-shaped samples is discussed in the context of solid-state NMR of small-volume samples. Strong RF irradiation, which has been exploited in wide-line spectral excitation, multiple-quantum MAS (MQMAS), and dipolar decoupling experiments, has been accompanied by new challenges regarding the Bloch-Siegert effect, the minimum time resolution of the spectrometer, and the time scale of pulse transient effects. For a possible solution to the latter problem, recent reports on active compensation of pulse transients are described. PMID:23083521

Takeda, Kazuyuki

2012-01-01

43

Dynamics of amyloid ? fibrils revealed by solid-state NMR.  

PubMed

We have investigated the site-specific backbone dynamics of mature amyloid ? (A?) fibrils using solid-state NMR spectroscopy. Overall, the known ?-sheet segments and the turn linking these two ?-strands exhibit high order parameters between 0.8 and 0.95, suggesting low conformational flexibility. The first approximately eight N-terminal and the last C-terminal residues exhibit lower order parameters between ?0.4 and 0.8. Interestingly, the order parameters increase again for the first two residues, Asp(1) and Ala(2), suggesting that the N terminus could carry some structural importance. PMID:22130659

Scheidt, Holger A; Morgado, Isabel; Rothemund, Sven; Huster, Daniel

2012-01-13

44

Solid-state NMR relaxation studies of Australian spider silks.  

PubMed

Solid-state NMR techniques were used to study two different types of spider silk from two Australian orb-web spider species, Nephila edulis and Argiope keyserlingi. A comparison of (13)C-T(1) and (1)H-T(1rho) solid-state NMR relaxation data of the Ala Calpha, Ala Cbeta, Gly Calpha, and carbonyl resonances revealed subtle differences between dragline and cocoon silk. (13)C-T(1rho) and (1)H-T(1) relaxation experiments showed significant differences between silks of the two species with possible structural variations. Comparison of our data to previous (13)C-T(1) relaxation studies of silk from Nephila clavipes (A. Simmons et al., Macromolecules, 1994, Vol. 27, pp. 5235-5237) also supports the finding that differences in molecular mobility of dragline silk exist between species. Interspecies differences in silk structure may be due to different functional properties. Relaxation studies performed on wet (supercontracted) and dry silks showed that the degree of hydration affects relaxation properties, and hence changes in molecular mobility are correlated with functional properties of silk. PMID:12115143

Kishore, A I; Herberstein, M E; Craig, C L; Separovic, F

45

Solid-state NMR characterization of Mowry Formation shales  

SciTech Connect

Solid-state {sup 13}C and {sup 29}Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS {sup 13}C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of {sup 29}Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The {sup 29}Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

Miknis, F.P.

1992-04-01

46

Solid-state NMR characterization of Mowry Formation shales  

SciTech Connect

Solid-state [sup 13]C and [sup 29]Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS [sup 13]C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of [sup 29]Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The [sup 29]Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

Miknis, F.P.

1992-04-01

47

Solid-state NMR spectroscopy of Pb-rich apatite.  

PubMed

Pb-containing hydroxylapatite phases synthesized under aqueous conditions were investigated by X-ray diffraction and solid-state nuclear magnetic resonance (NMR) techniques to determine the Pb, Ca distribution. 31P and 1H magic-angle spinning (MAS) NMR results indicate slight shifts of the isotropic chemical shift with increased Ca content and complex lineshapes at compositions with near equal amounts of Ca and Pb. 31P{207Pb} and 1H{207Pb} rotational-echo double resonance (REDOR) results for intermediate compositions show that resolved spectral features cannot be assigned simply in terms of local Ca, Pb configurations or coexisting phases. 207Pb MAS NMR spectra are easily obtained for these materials and contain well-resolved resonances for crystallographically unique A1 and A2 Pb sites. Splitting of the A1 and A2 207Pb resonances for pure hydroxyl-pyromorphite (Pb10(PO4)6(OH)2) compared to natural pyromorphite (Pb5(PO4)3Cl) suggests symmetry reduced from hexagonal. We find that 207Pb{1H} CP/MAS NMR is impractical in Pb-rich hydroxylapatites due to fast 207Pb relaxation. PMID:19821466

Mason, Harris E; Hirner, Joshua J; Xu, Wenqian; Parise, John B; Phillips, Brian L

2009-12-01

48

Solid State NMR Studies of the Aluminum Hydride Phases  

NASA Technical Reports Server (NTRS)

Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

2006-01-01

49

Solid state NMR study of nanodiamond surface chemistry.  

PubMed

Solid state NMR measurements using 13C, 1H and 19F nuclei (MAS, CP-MAS) underline the surface chemistry of nanodiamonds from different synthesis (detonation, high pressure high temperature and shock compression). The comparison of the spin-lattice relaxation times T1 and physicochemical characterization (spin densities of dangling bonds, specific surface area and Raman and infrared spectroscopies) for the various samples, as synthesized, chemically purified and fluorinated allows the nature and the location of the various groups, mainly C-OH, C-H and C-F to be investigated. C-OH groups are located only on the surface whereas C-H and dangling bonds seem to be distributed in the whole volume. Fluorination was studied as a chemical treatment for purification and change of the hydrophobicity through the conversion of the C-OH groups into covalent C-F bonds. PMID:22119523

Dubois, Marc; Guérin, Katia; Batisse, Nicolas; Petit, Elodie; Hamwi, André; Komatsu, Naoki; Kharbache, Hayat; Pirotte, Pascal; Masin, Francis

2011-11-01

50

Molecular structure of humin and melanoidin via solid state NMR.  

PubMed

Sugar-derived humins and melanoidins figure significantly in food chemistry, agricultural chemistry, biochemistry, and prebiotic chemistry. Despite wide interest and significant experimental attention, the amorphous and insoluble nature of the polymers has made them resistant to conventional structural characterization. Here we make use of solid-state NMR methods, including selective (13)C substitution, (1)H-dephasing, and double quantum filtration. The spectra, and their interpretation, are simplified by relying exclusively on hydronium for catalysis. The results for polymers derived from ribose, deoxyribose, and fructose indicate diverse pathways to furans, suggest a simple route to pyrroles in the presence of amines, and reveal a heterogeneous network-type polymer in which sugar molecules cross-link the heterocycles. PMID:21456563

Herzfeld, Judith; Rand, Danielle; Matsuki, Yoh; Daviso, Eugenio; Mak-Jurkauskas, Melody; Mamajanov, Irena

2011-05-19

51

Recent advances in solid-state NMR spectroscopy of quadrupolar nuclei.  

PubMed

Nuclear magnetic resonance (NMR) spectroscopy of quadrupolar nuclei (i.e., those with a spin quantum number I > 1/2) has always been viewed as "difficult" owing to the presence of an anisotropic broadening arising from the interaction of the nuclear electric quadrupole moment with the electric field gradient. This quadrupolar interaction can be considerable, resulting in broadening of the spectral resonances often over many MHz. Furthermore, magic-angle spinning (MAS), a conventional approach for increasing the resolution in solid-state NMR, is often unable to remove the broadening completely and high-resolution spectra are generally not obtained. Despite the vast amount of information contained in the anisotropic linewidths and lineshapes, the resolution and sensitivity challenges have, until recently, somewhat limited the application of solid-state NMR for quadrupolar nuclei. In general, structural information, such as that obtained through recoupling techniques or from two-dimensional correlation spectroscopy, is much more difficult to extract easily and accurately. However, recent advances in magnet design, probe hardware and pulse sequence development have significantly improved the ease with which quadrupolar spins can be studied and high-resolution spectra can be obtained, and recent applications are beginning to exploit the wealth of information available. In this discussion, we highlight just a few of the recent developments in this area, including new state-of-the art correlation experiments, the expanding study of nuclei with low gyromagnetic ratio, gamma, the increasing application of first-principles calculations in the solid state, and methods which exploit the quadrupolar broadening to provide information on dynamics. Whilst not a complete review, it is hoped that this brief overview of some of the more exciting recent developments can provide insight into the challenges, and the rewards, involved in the NMR study of quadrupolar nuclei. PMID:19652823

Ashbrook, Sharon E

2009-08-28

52

Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses  

SciTech Connect

Solid-state NMR is a powerful tool for probing the role and significance of alteration layers in determining the kinetics for the corrosion of nuclear waste glass. NMR methods are used to probe the chemical structure of the alteration layers to elucidate information about their chemical complexity, leading to increased insight into the mechanism of altered layer formation. Two glass compositions were examined in this study: a glass preliminarily designed for nuclear waste immobilization (called AFCI) and a simplified version of this AFCI glass (which we call SA1R). Powdered glasses with controlled and known particles sizes were corroded at 90 °C for periods of one and five months with a surface-area to solution-volume ratio of 100,000 m-1. 1H-29Si CP-CPMG MAS NMR, 1H-27Al CP-MAS NMR, 1H-11B CP-MAS NMR, and 1H-23Na CP-MAS NMR experiments provide isolated structural information about the alteration layers, which differ in structure from that of the pristine glass. Both glasses studied here develop alteration layers composed primarily of [IV]Si species. Aluminum is also retained in the alteration layers, perhaps facilitated by the observed increase in coordination from [IV]Al to [VI]Al, which correlates with a loss of charge balancing cations. 1H-11B CP-MAS NMR observations indicated a retention of boron in hydrated glass layers, which has not been characterized by previous work. For the AFCI glass, secondary phase formation begins during the corrosion times considered here, and these neophases are detected within the alteration layers. We identify precursor phases as crystalline sodium metasilicates. An important finding is that layer thickness depends on the length of the initial alteration stages and varies only with respect to silicon species during the residual rate regime.

Murphy, Kelly A. [Penn State Univ., State College, PA (United States). Dept. of Chemistry; Washton, Nancy M. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Science Lab.; Ryan, Joseph V. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Pantano, Carlo G. [Penn State Univ., State College, PA (United States). Dept. of Materials Science and Engineering; Mueller, Karl T. [Penn State Univ., State College, PA (United States). Dept. of Chemistry; Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Science Lab.

2013-06-01

53

Ultrafast Solid-State 2D NMR Experiments via Orientational Encoding Rangeet Bhattacharyya and Lucio Frydman*  

E-print Network

Ultrafast Solid-State 2D NMR Experiments via Orientational Encoding Rangeet Bhattacharyya and Lucio October 6, 2006; E-mail: lucio.frydman@weizmann.ac.il 2D NMR1 enables the characterization of a wide by sensitivity constraints. Proposals for accelerating 2D NMR include among others non-FT schemes3 as well

Frydman, Lucio

54

Solid-state NMR studies of biomineralization peptides and proteins.  

PubMed

Nature has evolved sophisticated strategies for engineering hard tissues through the interaction of proteins, and ultimately cells, with inorganic mineral phases. This process, called biomineralization, is how living organisms transform inorganic materials such as hydroxyapatite, calcite, and silica into highly intricate and organized structures. The remarkable material properties of shell, bone, and teeth come from the activities of proteins that function at the organic-inorganic interface. A better understanding of the biomolecular mechanisms used to promote or retard the formation of mineral-based structures could provide important design principles for the development of calcification inhibitors and promoters in orthopedics, cardiology, urology, and dentistry. With the knowledge of the structural basis for control of hard tissue growth by proteins, scientists could potentially develop materials using biomimetic principles with applications in catalysis, biosensors, electronic devices, and chromatographic separations, to name a few. Additionally, biomineralization also has potential applications in electronics, catalysis, magnetism, sensory devices, and mechanical design. Where man-made hard materials require the use of extreme temperatures, high pressure, and pH, biological organisms can accomplish these feats at ambient temperature and at physiological pH. Despite the fact that many researchers want to identify and control the structure of proteins at material and biomineral interfaces, there is a decided lack of molecular-level structure information available for proteins at biomaterial interfaces in general. In particular, this holds for mammalian proteins that directly control calcification processes in hard tissue. The most fundamental questions regarding the secondary and tertiary structures of proteins adsorbed to material surfaces, how proteins catalyze the formation of biomineral composites, or how proteins interact at biomaterial interfaces remain unanswered. This is largely due to a lack of methods capable of providing high-resolution structural information for proteins adsorbed to material surfaces under physiologically relevant conditions. In this Account, we highlight recent work that is providing insight into the structure and crystal recognition mechanisms of a salivary protein model system, as well as the structure and interactions of a peptide that catalyzes the formation of biosilica composites. To develop a better understanding of the structure and interactions of proteins in biomaterials, we have used solid-state NMR techniques to determine the molecular structure and dynamics of proteins and peptides adsorbed onto inorganic crystal surfaces and embedded within biomineral composites. This work adds to the understanding of the structure and crystal recognition mechanisms of an acidic human salivary phosphoprotein, statherin. PMID:23932180

Roehrich, Adrienne; Drobny, Gary

2013-09-17

55

Methodology and applications of high resolution solid-state NMR to structure determination of proteins  

E-print Network

A number of methodological developments and applications of solid-state NMR for assignment and high resolution structure determination of microcrystalline proteins and amyloid fibrils are presented. Magic angle spinning ...

Lewandowski, Józef Romuald

2008-01-01

56

Dipolar recoupling in solid state NMR by phase alternating pulse sequences  

E-print Network

We describe some new developments in the methodology of making heteronuclear and homonuclear recoupling experiments in solid state NMR insensitive to rf-inhomogeneity by phase alternating the irradiation on the spin system ...

Lin, J.

57

Analysis of trivalent cation complexation to functionalized mesoporous silica using solid-state NMR spectroscopy.  

PubMed

Functionalized mesoporous silica has applications in separations science, catalysis, and sensors. In this work, we studied the fundamental interactions of trivalent cations with functionalized mesoporous silica. We contacted trivalent cations of varying ionic radii with N-[5-(trimethoxysilyl)-2-aza-1-oxopentyl]caprolactam functionalized mesoporous silica with the aim of probing the binding mechanism of the metal to the surface of the solid. We studied the functionalized silica using solid-state nuclear magnetic resonance (NMR) spectroscopy before and after contact with the metals of interest. We collected NMR spectra of the various metals, as well as of (29)Si and (13)C to probe the silica substrate and the ligand properties, respectively. The NMR spectra indicate that the metals bind to the functionalized silica via two mechanisms. Aluminum sorbed to both the silica and the ligand, but with different coordination for each. Scandium also sorbed to both the silica and the ligand, and unlike the aluminum, had the same coordination number. Additionally, the functionalized silica was susceptible to acid hydrolysis and two primary mechanisms of degradation were observed: detachment from the silica surface and opening of the seven-membered ring in the ligand. Opening of the seven-membered ring may be beneficial in that it decreases steric hindrance of the molecule for binding. PMID:25265419

Shusterman, Jennifer; Mason, Harris; Bruchet, Anthony; Zavarin, Mavrik; Kersting, Annie B; Nitsche, Heino

2014-10-22

58

SedNMR: on the edge between solution and solid-state NMR.  

PubMed

Solid-state NMR (SS-NMR) of proteins requires that those molecules be immobilized, usually by crystallization, freezing, or lyophilization. However, self-crowding can also slow molecular rotation sufficiently to prevent the nuclear interactions from averaging. To achieve self-crowding, researchers can use a centrifugal field to create a concentration gradient or use regular ultracentrifugation to produce highly concentrated, gel-like solutions. Thus sedimented solute NMR (SedNMR) provides a simple method to prepare biological samples for SS-NMR experiments with minimal perturbation. This method may also give researchers a way to investigate species that are not otherwise accessible by NMR. We induce the sedimentation in one of two ways: (1) by the extreme centrifugal force exerted during magic angle spinning (MAS-induced sedimentation or in situ) or (2) by an ultracentrifuge (UC-induced sedimentation or ex situ). Sedimentation is particularly useful in situations where it is difficult to obtain protein crystals. Furthermore, because the proteins remain in a largely hydrated state, the sedimented samples may provide SS-NMR spectra that have better resolution than the spectra from frozen solutions or lyophilized powders. If sedimentation is induced in situ, the same protein sample can be used for both solution and SS-NMR studies. Finally, we show that in situ SedNMR can be used to detect the NMR signals of large molecular adducts that have binding constants that are too weak to allow for the selective isolation and crystallization of the complexed species. We can selectively induce sedimentation for the heaviest molecular species. Because the complexed molecules are subtracted from the bulk solution, the reaction proceeds further toward the formation of complexes. PMID:23470055

Bertini, Ivano; Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico

2013-09-17

59

Solid-state NMR approaches to internal dynamics of proteins: from picoseconds to microseconds and seconds.  

PubMed

Solid-state nuclear magnetic resonance (NMR) spectroscopy has matured to the point that it is possible to determine the structure of proteins in immobilized states, such as within microcrystals or embedded in membranes. Currently, researchers continue to develop and apply NMR techniques that can deliver site-resolved dynamic information toward the goal of understanding protein function at the atomic scale. As a widely-used, natural approach, researchers have mostly measured longitudinal (T1) relaxation times, which, like in solution-state NMR, are sensitive to picosecond and nanosecond motions, and motionally averaged dipolar couplings, which provide an integral amplitude of all motions with a correlation time of up to a few microseconds. While overall Brownian tumbling in solution mostly precludes access to slower internal dynamics, dedicated solid-state NMR approaches are now emerging as powerful new options. In this Account, we give an overview of the classes of solid-state NMR experiments that have expanded the accessible range correlation times from microseconds to many milliseconds. The measurement of relaxation times in the rotating frame, T1?, now allows researchers to access the microsecond range. Using our recent theoretical work, researchers can now quantitatively analyze this data to distinguish relaxation due to chemical-shift anisotropy (CSA) from that due to dipole-dipole couplings. Off-resonance irradiation allows researchers to extend the frequency range of such experiments. We have built multidimensional analogues of T2-type or line shape experiments using variants of the dipolar-chemical shift correlation (DIPSHIFT) experiment that are particularly suited to extract intermediate time scale motions in the millisecond range. In addition, we have continuously improved variants of exchange experiments, mostly relying on the recoupling of anisotropic interactions to address ultraslow motions in the ms to s ranges. The NH dipolar coupling offers a useful probe of local dynamics, especially with proton-depleted samples that suppress the adverse effect of strong proton dipolar couplings. We demonstrate how these techniques have provided a concise picture of the internal dynamics in a popular model system, the SH3 domain of ?-spectrin. T1-based methods have shown that large-amplitude bond orientation fluctuations in the picosecond range and slower 10 ns low-amplitude motions coexist in these structures. When we include T1? data, we observe that many residues undergo low amplitude motions slower than 100 ns. On the millisecond to second scale, mostly localized but potentially cooperative motions occur. Comparing different exchange experiments, we found that terminal NH2 groups in side chains can even undergo a combination of ultraslow large-angle two-site jumps accompanied by small-angle fluctuations that occur 10 times more quickly. PMID:23875699

Krushelnitsky, Alexey; Reichert, Detlef; Saalwächter, Kay

2013-09-17

60

Solid state NMR: The essential technology for helical membrane protein structural characterization.  

PubMed

NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed - neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins. PMID:24412099

Cross, Timothy A; Ekanayake, Vindana; Paulino, Joana; Wright, Anna

2014-02-01

61

Solid state NMR and LVSEM studies on the hardening of latex modified tile mortar systems  

SciTech Connect

Construction mortars contain a broad variety of both inorganic and organic additives beside the cement powder. Here we present a study of tile mortar systems based on portland cement, quartz, methyl cellulose and different latex additives. As known, the methyl cellulose stabilizes the freshly prepared cement paste, the latex additive enhances final hydrophobicity, flexibility and adhesion. Measurements were performed by solid state nuclear magnetic resonance (NMR) and low voltage scanning electron microscopy (LVSEM) to probe the influence of the latex additives on the hydration, hardening and the final tile mortar properties. While solid state NMR enables monitoring of the bulk composition, scanning electron microscopy affords visualization of particles and textures with respect to their shape and the distribution of the different phases. Within the alkaline cement paste, the poly(vinyl acetate) (VAc)-based latex dispersions stabilized by poly(vinyl alcohol) (PVA) were found to be relatively stable against hydrolysis. The influence of the combined organic additives methyl cellulose, poly(vinyl alcohol) and latexes stabilized by poly(vinyl alcohol) on the final silicate structure of the cement hydration products is small. But even small amounts of additives result in an increased ratio of ettringite to monosulfate within the final hydrated tile mortar as monitored by {sup 27}Al NMR. The latex was found to be adsorbed to the inorganic surfaces, acting as glue to the inorganic components. For similar latex water interfaces built up by poly(vinyl alcohol), a variation in the latex polymer composition results in modified organic textures. In addition to the networks of the inorganic cement and of the latex, there is a weak network build up by thin polymer fibers, most probably originating from poly(vinyl alcohol). Besides the weak network, polymer fibers form well-ordered textures covering inorganic crystals such as portlandite.

Rottstegge, J. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany); Arnold, M. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany); Herschke, L. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany); Glasser, G. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany); Wilhelm, M. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany); Spiess, H.W. [Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz (Germany)]. E-mail: spiess@mpip-mainz.mpg.de; Hergeth, W.D. [Wacker Polymer Systems GmbH and Co. KG, Johannes Hess Strasse 24, D-84483 Burghausen (Germany)

2005-12-15

62

Solid-State NMR Studies of Pharmaceutical Systems  

Microsoft Academic Search

High?and low?resolution solid?state nuclear magnetic resonance (SSNMR) applications to the study of pharmaceuticals are reviewed. Examples are shown involving the use of mono?and bidimensional SSNMR techniques based on different nuclear interactions and the measurement of several nuclear parameters, such as chemical shifts, line widths, and relaxation times (T1, T2, T1?). The systems investigated include pure active pharmaceutical ingredients (APIs), substances

Marco Geppi; Giulia Mollica; Silvia Borsacchi; Carlo Alberto Veracini

2008-01-01

63

Direct detection of discharge products in lithium-oxygen batteries by solid-state NMR spectroscopy.  

PubMed

A closer look: Solid-state (7) Li and (17) O NMR spectroscopy is a valuable tool in the characterization of products formed in the lithium-oxygen battery, a necessary step in the development of a viable cell. Since lithium peroxide, the desired discharge product, has a unique (17) O NMR signature, it can be clearly identified. PMID:22786802

Leskes, Michal; Drewett, Nicholas E; Hardwick, Laurence J; Bruce, Peter G; Goward, Gillian R; Grey, Clare P

2012-08-20

64

Heat Management Strategies for Solid-state NMR of Functional Proteins  

PubMed Central

Modern solid-state NMR methods can acquire high-resolution protein spectra for structure determination. However, these methods use rapid sample spinning and intense decoupling fields that can heat and denature the protein being studied. Here we present a strategy to avoid destroying valuable samples. We advocate first creating a sacrificial sample, which contains unlabeled protein (or no protein) in buffer conditions similar to the intended sample. This sample is then doped with the chemical shift thermometer Sm2Sn2O7. We introduce a pulse scheme called TCUP (for Temperature Calibration Under Pulseload) that can characterize the heating of this sacrificial sample rapidly, under a variety of experimental conditions, and with high temporal resolution. Sample heating is discussed with respect to different instrumental variables such as spinning speed, decoupling strength and duration, and cooling gas flow rate. The effects of different sample preparation variables are also discussed, including ionic strength, the inclusion of cryoprotectants, and the physical state of the sample (i.e. liquid, solid, or slurry). Lastly, we discuss probe detuning as a measure of sample thawing that does not require retuning the probe or using chemical shift thermometer compounds. Use of detuning tests and chemical shift thermometers with representative sample conditions makes it possible to maximize the efficiency of the NMR experiment while retaining a functional sample. PMID:22868258

Fowler, Daniel J.; Harris, Michael J.; Thompson, Lynmarie K.

2012-01-01

65

Spinning-rate encoded chemical shift correlations from rotational resonance solid-state NMR experiments  

PubMed Central

Structural measurements in magic-angle-spinning (MAS) solid-state NMR rely heavily on 13C-13C distance measurements. Broadbanded recoupling methods are used to generate many cross-peaks, but have complex polarization transfer mechanisms that limit the precision of distance constraints and can suffer from weak intensities for distant peaks due to relaxation, the broad distribution of polarization, as well as dipolar truncation. Frequency-selective methods that feature narrow-banded recoupling can reduce these effects. Indeed, rotational resonance (R2) experiments have found application in many different biological systems, where they have afforded improved precision and accuracy. Unfortunately, a highly selective transfer mechanism also leads to few cross-peaks in the resulting spectra, which complicates the extraction of multiple constraints. R2-width (R2W) measurements that scan a range of MAS rates to probe the R2 matching conditions of one or more sites can improve precision, and also permit multiple simultaneous distance measurements. Unfortunately, multidimensional R2W can be very time-consuming. Here, we present an approach that facilitates the acquisition of 2D-like spectra based on a series of 1D R2W experiments, by taking advantage of the chemical shift information encoded in the MAS rates where matching occurs. This yields a more time-efficient experiment with many of the benefits of more conventional multidimensional R2W measurements. The obtained spectra reveal long-distance 13C-13C cross-peaks resulting from R2-mediated polarization transfer. This experiment also enables the efficient setup and targeted implementation of traditional R2 or R2W experiments. Analogous applications may extend to other variable-MAS and frequency-selective solid-state NMR experiments. PMID:23475055

Li, Jun; van der Wel, Patrick C. A.

2013-01-01

66

Solid-State NMR on Polymers under Mechanical Stress  

NASA Astrophysics Data System (ADS)

Low-field NMR in a Halbach magnet has been used for the in-situ investigation of polymers under mechanical stress. Low-field NMR at a Larmor frequency of 32 MHz is particularly suited for the investigation of magnetic resonance relaxation and residual dipolar couplings. The method has been demonstrated on an elastomer and has subsequently been applied to a semicrystalline polymer. Under uniaxial load the transverse relaxation T2 becomes faster and residual dipolar couplings are getting stronger. The effect on the elastomer is completely reversible, while in the semicrystalline polymer an irreversible rearrangement is observed.

Böhme, Ute; Gelfert, Karsten; Scheler, Ulrich

2011-03-01

67

Solid state NMR studies of materials for energy technology  

NASA Astrophysics Data System (ADS)

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.

Nambukara Kodiweera Arachchilage, Chandana K.

68

Solid-state /sup 13/C NMR and X-ray diffraction of dermatan sulfate  

SciTech Connect

Dermatan sulfate in the solid state has been studied by /sup 13/C CP/MAS nmr and X-ray diffraction in order to establish the ring conformation of the L-iduronate moiety. The solid state nmr spectrum is similar to the solution spectrum obtained previously, indicating that a ring conformation at least approximating to /sup 1/C/sub 4/ predominates in the solid state. X-ray powder diffraction data from the same sample indicate the presence of the 8-fold helix form previously observed by fiber diffraction, and interpreted in terms of a /sup 4/C/sub 1/ ring form. A likely explanation of the results is that a distorted /sup 1/C/sub 4/ L-iduronate ring conformation, not considered in the initial X-ray analysis, may emerge to provide a satisfactory interpretation of all available physical-chemical data.

Winter, W.T.; Taylor, M.G.; Stevens, E.S.; Morris, E.R.; Rees, D.A.

1986-05-29

69

SOLID STATE NMR STUDY SUPPORTING THE LITHIUM VACANCY DEFECT MODEL IN CONGRUENT LITHIUM  

E-print Network

@ Pergamon SOLID STATE NMR STUDY SUPPORTING THE LITHIUM VACANCY DEFECT MODEL IN CONGRUENT LITHIUM performed on powdered and single crystal lithium niobate of defectivecongruent composition (48.4%LirO;51.6% NbrOr) using a magnetic field strength of 7.05 Tesla with the aim to distinguish between a lithium

Bluemel, Janet

70

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

E-print Network

growth process, plants use expansins to induce wall stress relaxation, which creates the driving force-stimulated growth of plant cells (2). Auxin, the classical plant growth hormone, rapidly stim- ulates growth in partSensitivity-enhanced solid-state NMR detection of expansin's target in plant cell walls Tuo Wanga

Hong, Mei

71

High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound  

ERIC Educational Resources Information Center

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…

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

2014-01-01

72

Solid-State 25Mg NMR of a Magnesium(II) Adensosine 5-Triphosphate Complex  

E-print Network

Solid-State 25Mg NMR of a Magnesium(II) Adensosine 5-Triphosphate Complex Christopher V. Grant interacting with RNA, such as magnesium- (II) binding sites within ribozymes, has become a topic of intense such as magnesium(II). X-ray crystallography has been most useful at providing structural information about

Frydman, Lucio

73

DHA and EPA Interaction with Raft Domains Observed With Solid-State 2 H NMR Spectroscopy  

E-print Network

DHA and EPA Interaction with Raft Domains Observed With Solid-State 2 H NMR Spectroscopy Jacob J phospholipids and modify the structure and organization of lipid rafts, thus affecting cell signaling. We used-eicosapentaenoylphosphatidylcholine (PEPC) and 1-palmitoyl- 2-docosahexaenoylphosphatidylcholine (PDPC) with the raft

Zhou, Yaoqi

74

Two-dimensional solid state NMR characterization of physisorbed siloxane polymer (OV-225) on silica  

Microsoft Academic Search

Physisorbed cyanopropyl methyl phenyl methyl siloxane polymer on a silica surface was characterized by one- and two-dimensional solid state NMR techniques including heteronuclear proton silicon correlation spectroscopy. Spin lattice relaxations of protons of the siloxane polymer exhibited only small changes upon anchoring to the silica surface indicating somewhat altered molecular dynamics of proton moieties that contribute to the relaxation process.

Anima B. Bose; Mahinda Gangoda; Mietek Jaroniec; Roger K. Gilpin; Rathindra N. Bose

2006-01-01

75

Solid-State NMR Spectroscopic Study of Phosphate Sorption Mechanisms on Aluminum (Hydr)oxides  

E-print Network

Information ABSTRACT: Sorption reactions occurring at mineral/water interfaces are of fundamental importanceSolid-State NMR Spectroscopic Study of Phosphate Sorption Mechanisms on Aluminum (Hydr)oxides Wei. To advance the understanding of sorption reactions, development of new methodology is required. In this study

Sparks, Donald L.

76

Two-dimensional correlation of solid state and liquid state NMR using a laser temperature jump  

Microsoft Academic Search

Solid state nuclear magnetic resonance (NMR) spectra and the corresponding liquid state spectra have been interrelated through two-dimensional experiments with a fast temperature jump during the mixing time. This jump must, as a minimum requirement, be shorter than the relevant spin lattice relaxation times, and was implemented using a CO2 laser heater. As the first demonstration of this experiment we

David B. Ferguson; Thomas R. Krawietz; James F. Haw

1994-01-01

77

Low-E probe for 19 F- 1 H NMR of dilute biological solids  

Microsoft Academic Search

Sample heating induced by radio frequency (RF) irradiation presents a significant challenge to solid state NMR experiments in pro- teins and other biological systems, causing the sample to dehydrate which may result in distorted spectra and a damaged sample. In this work we describe a large volume, low-E 19 F- 1 H solid state NMR probe, which we developed for

Peter L. Gor; Raiker Witter; Eduard Y. Chekmenev; Farhod Nozirov; Riqiang Fu; William W. Brey

2007-01-01

78

Solid state 13C NMR in conducting polymers F. Devreux (*), G. Bidan (**), A. A. Syed(**,+) and C. Tsintavis (**)  

E-print Network

1595 Solid state 13C NMR in conducting polymers F. Devreux (*), G. Bidan (**), A. A. Syed al. [1], the so-called solid-state high-resolution 13C NMR (CMR) could be a promis- ing way material for battery appli- cations. 2. Experimental High resolution CMR is achieved in solids by averag

Paris-Sud XI, Université de

79

Orientation and Dynamics of an Antimicrobial Peptide in the Lipid Bilayer by Solid-State NMR Spectroscopy  

E-print Network

the molecular mechanisms of the antimicrobial activities of natural and synthetic peptides, it is importantOrientation and Dynamics of an Antimicrobial Peptide in the Lipid Bilayer by Solid-State NMR and dynamics of an 18-residue antimicrobial peptide, ovispirin, has been investigated using solid-state NMR

Hong, Mei

80

Understanding the leaching properties of heterogenized catalysts: a combined solid-state and PHIP NMR study.  

PubMed

Para-hydrogen induced polarization (PHIP) NMR in solution, combined with solid-state NMR, can be efficiently employed for the highly sensitive in-situ detection of the leaching properties of immobilized catalysts. The knowledge of this property is important for possible applications of PHIP experiments in medicine, biology or industry, where leached catalysts poison the solution of hyperpolarized products. As experimental example Wilkinson's catalyst RhCl(PPh(3))(3) (1) immobilized on mesoporous silica is chosen. As model reaction the hydrogenation of styrene in solvents with different polarities (methanol-d(4), acetone-d(6) and benzene-d(6)) is used. A (31)P solid-state MAS-NMR study reveals that there are two different species of catalysts on the silica, namely coordinatively bound catalysts and physisorbed catalyst. Only the second species exhibits substantial leaching, which is visible in a strong PHIP enhancement of the reaction product. PMID:21435842

Gutmann, Torsten; Ratajczyk, Tomasz; Xu, Yeping; Breitzke, Hergen; Grünberg, Anna; Dillenberger, Sonja; Bommerich, Ute; Trantzschel, Thomas; Bernarding, Johannes; Buntkowsky, Gerd

2010-11-01

81

Characterization of covalent protein conjugates using solid-state sup 13 C NMR spectroscopy  

SciTech Connect

Cross-polarization magic-angle spinning (CPMAS) {sup 13}C NMR spectroscopy has been used to characterize covalent conjugates of alachlor, an {alpha}-chloroacetamide hapten, with glutathione (GSH) and bovine serum albumin (BSA). The solid-state NMR method demonstrates definitively the covalent nature of these conjugates and can also be used to characterize the sites of hapten attachment to proteins. Three different sites of alachlor binding are observed in the BSA system. Accurate quantitation of the amount of hapten covalently bound to GSH and BSA is reported. The solid-state {sup 13}C NMR technique can easily be generalized to study other small molecule/protein conjugates and can be used to assist the development and refinement of synthetic methods needed for the successful formation of such protein alkylation products.

Garbow, J.R.; Fujiwara, Hideji; Sharp, C.R.; Logusch, E.W. (Monsanto Co., St. Louis, MO (United States))

1991-07-23

82

Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.  

PubMed

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. PMID:25194346

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

2014-11-01

83

Analysis of RF heating and sample stability in aligned static solid-state NMR spectroscopy.  

PubMed

Sample instability during solid-state NMR experiments frequently arises due to RF heating in aligned samples of hydrated lipid bilayers. A new, simple approach for estimating sample temperature is used to show that, at 9.4 T, sample heating depends mostly on (1)H decoupling power rather than on (15)N irradiation in PISEMA experiments. Such heating for different sample preparations, including lipid composition, salt concentration and hydration level was assessed and the hydration level was found to be the primary parameter correlated with sample heating. The contribution to RF heating from the dielectric loss appears to be dominant under our experimental conditions. The heat generated by a single scan was approximately calculated from the Q values of the probe, to be a 1.7 degrees C elevation per single pulse sequence iteration under typical sample conditions. The steady-state sample temperature during PISEMA experiments can be estimated based on the method presented here, which correlates the loss factor with the temperature rise induced by the RF heating of the sample. PMID:16483809

Li, Conggang; Mo, Yiming; Hu, Jun; Chekmenev, Eduard; Tian, Changlin; Gao, Fei Philip; Fu, Riqiang; Gor'kov, Peter; Brey, William; Cross, Timothy A

2006-05-01

84

Using 17O solid-state NMR and first principles calculation to characterise structure and dynamics in inorganic framework materials.  

PubMed

The use of solid-state (17)O NMR to determine local chemical environment and to characterise oxygen dynamics is illustrated in studies of zirconium tungstate, ZrW(2)O(8), and tungsten oxide, WO(3). Simple 1D magic-angle spinning (MAS) NMR allows the chemical environments in ZrW(2)O(8) to be readily characterised, and the use of a combination of one- and two-dimensional experiments to characterise oxygen dynamics in its cubic phase is reviewed. Combining local information about structure and dynamics from NMR with long-range structural information from diffraction allows a comprehensive picture of the material to be developed. Recent work is described that uses first principles calculation of NMR parameters to probe subtle asymmetries in the WO(6) octahedra that form the structural motif in WO(3). NMR is shown to be a highly sensitive probe of local structure, allowing different models derived from high-quality neutron diffraction studies to be distinguished. The density functional theory (DFT) calculations allow clear correlations between (17)O chemical shifts and distortions of the structure to be established. PMID:18157838

Soleilhavoup, Anne; Hampson, Matthew R; Clark, Stewart J; Evans, John S O; Hodgkinson, Paul

2007-12-01

85

Protein Folding and Amyloid Formation: Good Questions for Solid State NMR  

NASA Astrophysics Data System (ADS)

Recent results from two ongoing projects will be described. These projects illustrate the expanding capability of solid state NMR spectroscopy to provide unique information about the molecular structure of complex biochemical systems that are of current interest in the biophysical and biomedical research communities. Methodological advances that facilitate progress on these projects will be discussed briefly. In the area of protein folding, we are using solid state NMR spectroscopy to characterize the distributions of molecular structures in unfolded and partially folded states of relatively simple model proteins. The measurements are carried out on frozen glassy solutions at low temperatures. Initial results for the chemical denaturation of the 35-residue helical protein HP35 show that unfolding does not occur by a simple two-state process and that local conformational distributions in the unfolded state are remarkably non-uniform. In the area of amyloid fibrils, we are using solid state NMR to develop experimentally-based models for the molecular structure of peptide fibrils associated with Alzheimer's disease and other amyloid diseases, and to develop an understanding of the interactions that stabilize amyloid fibril structures in general. The NMR data also reveal molecular-level polymorphism in amyloid fibrils, with implications for biomedical issues such as the etiological role of fibrils in amyloid diseases and the structural basis for strains in prion diseases.

Tycko, Robert

2005-03-01

86

Solid-state NMR spectra of lipid-anchored proteins under magic angle spinning.  

PubMed

Solid-state NMR is a promising tool for elucidating membrane-related biological phenomena. We achieved the measurement of high-resolution solid-state NMR spectra for a lipid-anchored protein embedded in lipid bilayers under magic angle spinning (MAS). To date, solid-state NMR measurements of lipid-anchored proteins have not been accomplished due to the difficulty in supplying sufficient amount of stable isotope labeled samples in the overexpression of lipid-anchored proteins requiring complex posttranslational modification. We designed a pseudo lipid-anchored protein in which the protein component was expressed in E. coli and attached to a chemically synthesized lipid-anchor mimic. Using two types of membranes, liposomes and bicelles, we demonstrated different types of insertion procedures for lipid-anchored protein into membranes. In the liposome sample, we were able to observe the cross-polarization and the (13)C-(13)C chemical shift correlation spectra under MAS, indicating that the liposome sample can be used to analyze molecular interactions using dipolar-based NMR experiments. In contrast, the bicelle sample showed sufficient quality of spectra through scalar-based experiments. The relaxation times and protein-membrane interaction were capable of being analyzed in the bicelle sample. These results demonstrated the applicability of two types of sample system to elucidate the roles of lipid-anchors in regulating diverse biological phenomena. PMID:24517164

Nomura, Kaoru; Harada, Erisa; Sugase, Kenji; Shimamoto, Keiko

2014-03-01

87

Solid-state NMR concepts for the investigation of supported transition metal catalysts and nanoparticles.  

PubMed

In recent years, solid-state NMR spectroscopy has evolved into an important characterization tool for the study of solid catalysts and chemical processes on their surface. This interest is mainly triggered by the need of environmentally benign organic transformations ("green chemistry"), which has resulted in a large number of new catalytically active hybrid materials, which are organized on the meso- and nanoscale. Typical examples of these catalysts are supported homogeneous transition metal catalysts or transition metal nanoparticles (MNPs). Solid-state NMR spectroscopy is able to characterize both the structures of these materials and the chemical processes on the catalytic surface. This article presents recent trends both on the characterization of immobilized homogeneous transition metal catalysts and on the characterization of surface species on transition metal surfaces. PMID:23972428

Gutmann, Torsten; Grünberg, Anna; Rothermel, Niels; Werner, Mayke; Srour, Mohamad; Abdulhussain, Safaa; Tan, Shulin; Xu, Yeping; Breitzke, Hergen; Buntkowsky, Gerd

2013-01-01

88

Solid-state NMR: a powerful tool for characterization of metal-organic frameworks.  

PubMed

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. PMID:23131545

Sutrisno, Andre; Huang, Yining

2013-02-01

89

Hydrolysis of Pyrophosphate in a Highly Calcareous Soil: A Solid-State Phosphorus31 NMR Study  

Microsoft Academic Search

PyrophosphateisthemainformofcondensedPinthefluidfertilizer ammonium polyphosphate (APP). When APP is applied to soil, pyro- phosphate is hydrolyzed to orthophosphate. Hydrolysis of pyrophos- phatewas investigated in a highly calcareous soil over 3 wk. Changes in P speciation were measured using solid-state 31 P nuclear magnetic resonance (NMR) spectroscopy for dried soil samples and ion chro- matography for NaOH extracts. Both techniques showed a decrease

T. M. McBeath; R. J. Smernik; E. Lombi; M. J. McLaughlin

90

Applications of Solid-State NMR to the Study of Organic\\/Inorganic Multicomponent Materials  

Microsoft Academic Search

The characterization of a variety of organic\\/inorganic multicomponent materials (OIMM) through solid-state NMR (SSNMR) spectroscopy will be reviewed. Many examples of applications to OIMM will be described, based on the observation of different nuclei and the use of various SSNMR methods, such as 1D and 2D techniques, measurements on relaxation and spin diffusion processes. OIMM are a very general category

Marco Geppi; Silvia Borsacchi; Giulia Mollica; Carlo Alberto Veracini

2009-01-01

91

Two-dimensional solid state NMR characterization of physisorbed siloxane polymer (OV-225) on silica  

Microsoft Academic Search

Physisorbed cyanopropyl–methyl–phenyl–methyl–siloxane polymer on a silica surface was characterized by one- and two-dimensional solid state NMR techniques including heteronuclear proton–silicon correlation spectroscopy. Spin–lattice relaxations of protons of the siloxane polymer exhibited only small changes upon anchoring to the silica surface indicating somewhat altered molecular dynamics of proton moieties that contribute to the relaxation process. However, the same relaxation rates of

Anima B. Bose; Mahinda Gangoda; Mietek Jaroniec; Roger K. Gilpin; Rathindra N. Bose

2006-01-01

92

Practical considerations over spectral quality in solid state NMR spectroscopy of soluble proteins.  

PubMed

Great theoretical and methodological advances are pushing the limits of resolution and sensitivity in solid state NMR (SSNMR). However, sample preparation remains a critical issue for the success of an experiment. The factors affecting spectral quality in SSNMR samples are discussed, examining cases encountered in the literature and presenting new experimental data. A discussion on resolution and sensitivity in sedimented solutes is framed in this context. PMID:23990200

Fragai, Marco; Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico

2013-10-01

93

LARGE SCALE PRODUCTION, PURIFICATION, AND 65CU SOLID STATE NMR OF AZURIN  

SciTech Connect

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.

Gao, A.; Heck, R.W.

2008-01-01

94

Structures of Amyloid Fibrils and Protein Folding Intermediates: New Insights from Solid State NMR  

NASA Astrophysics Data System (ADS)

I will present recent results from two projects: (1) We are using a combination of solid state NMR techniques and electron microscopy techniques to develop full molecular models for amyloid fibrils formed by the beta-amyloid peptide of Alzheimer's disease and by other peptides and proteins. Amyloid fibrils are often polymorphic, so that the detailed molecular structure depends on growth conditions or other factors. I will describe two structural models for beta-amyloid fibrils with two distinct morphologies. I will also describe efforts to determine which fibril structure develops in the brains of Alzheimer's disease patients, and solid state NMR methods that contribute to our amyloid studies; (2) Structural properties of unfolded or partially folded states of proteins are not well understood. In principle, solid state NMR measurements on freeze-trapped samples can reveal site-specific, quantitative aspects of protein structures in unfolded states. I will describe experiments on thermodynamically unfolded states (i.e., denatured states) and on transient states that are trapped by freezing on the microsecond time scale. Both types of experiments reveal structural properties that are unanticipated and could not be detected by more conventional protein folding measurements.

Tycko, Robert

2009-03-01

95

Monitoring the Electrochemical Processes in the Lithium-Air Battery by Solid State NMR Spectroscopy  

PubMed Central

A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

2013-01-01

96

New methods and applications in solid-state NMR spectroscopy of quadrupolar nuclei.  

PubMed

Solid-state nuclear magnetic resonance (NMR) spectroscopy has long been established as offering unique atomic-scale and element-specific insight into the structure, disorder, and dynamics of materials. NMR spectra of quadrupolar nuclei (I > (1)/2) are often perceived as being challenging to acquire and to interpret because of the presence of anisotropic broadening arising from the interaction of the electric field gradient and the nuclear electric quadrupole moment, which broadens the spectral lines, often over several megahertz. Despite the vast amount of information contained in the spectral line shapes, the problems with sensitivity and resolution have, until very recently, limited the application of NMR spectroscopy of quadrupolar nuclei in the solid state. In this Perspective, we provide a brief overview of the quadrupolar interaction, describe some of the basic experimental approaches used for acquiring high-resolution NMR spectra, and discuss the information that these spectra can provide. We then describe some interesting recent examples to showcase some of the more exciting and challenging new applications of NMR spectra of quadrupolar nuclei in the fields of energy materials, microporous materials, Earth sciences, and biomaterials. Finally, we consider the possible directions that this highly informative technique may take in the future. PMID:25296129

Ashbrook, Sharon E; Sneddon, Scott

2014-11-01

97

Resonator with reduced sample heating and increased homogeneity for solid-state NMR  

NASA Astrophysics Data System (ADS)

In the application of solid-state NMR to many systems, the presence of radiofrequency (rf) electric fields inside classical solenoidal coils causes heating of lossy samples. In particular, this is critical for proteins in ionic buffers. Rf sample heating increases proportional to frequency which may result in the need to reduce the rf pulse power to prevent partial or total sample deterioration. In the present paper, we propose a multifrequency-tunable NMR resonator where the sample is electrically shielded from the NMR coil by a conductive sheet that increases the magneto-electric ratio. Expressions for the B1 efficiency as function of magnetic and electric filling factors are derived that allow a direct comparison of different resonators. Rf efficiency, homogeneity, signal-to-noise, and rf sample heating are compared. NMR spectra at 700 MHz on ethylene glycol, glycine, and a model protein were acquired to compare the resonators under realistic experimental conditions.

Krahn, Alexander; Priller, Uwe; Emsley, Lyndon; Engelke, Frank

2008-03-01

98

Solid State NMR Measurements for Preliminary Lifetime Assessments in (gamma)-Irradiated and Thermally Aged Siloxane Elastomers  

SciTech Connect

Siloxanes have a wide variety of applications throughout the aerospace industry which take advantage of their exceptional insulating and adhesive properties and general resilience. They also offer a wide range of tailorable engineering properties with changes in composition and filler content. They are, however, subject to degradation in radiatively and thermally harsh environments. We are using solid state nuclear magnetic resonance techniques to investigate changes in network and interfacial structure in siloxane elastomers and their correlations to changes in engineering performance in a series of degraded materials. Nuclear magnetic resonance (NMR) parameters such as transverse (T{sub 2}) relaxation times, cross relaxation rates, and residual dipolar coupling constants provide excellent probes of changes crosslink density and motional dynamics of the polymers caused by multi-mechanism degradation. The results of NMR studies on aged siloxanes are being used in conjunction with other mechanical tests to provide insight into component failure and degradation kinetics necessary for preliminary lifetime assessments of these materials as well as into the structure-property relationships of the polymers. NMR and magnetic resonance imaging (MRI) results obtained both from high resolution NMR spectrometers as well as low resolution benchtop NMR screening tools will be presented.

Chinn, S C; Herberg, J L; Sawvel, A M; Maxwell, R S

2005-02-03

99

Solid State NMR Measurements for Preliminary Lifetime Assessments in gamma-Irradiated and Thermally Aged Siloxane Elastomers  

SciTech Connect

Siloxanes have a wide variety of applications throughout the aerospace industry which take advantage of their exceptional insulating and adhesive properties and general resilience. They also offer a wide range of tailorable engineering properties with changes in composition and filler content. They are, however, subject to degradation in radiatively and thermally harsh environments. We are using solid state nuclear magnetic resonance techniques to investigate changes in network and interfacial structure in siloxane elastomers and their correlations to changes in engineering performance in a series of degraded materials. NMR parameters such as transverse ( T{sub 2}) relaxation times, cross relaxation rates, and residual dipolar coupling constants provide excellent probes of changes crosslink density and motional dynamics of the polymers caused by multi-mechanism degradation. The results of NMR studies on aged siloxanes are being used in conjunction with other mechanical tests to provide insight into component failure and degradation kinetics necessary for preliminary lifetime assessments of these materials as well as into the structure-property relationships of the polymers. NMR and MRI results obtained both from high resolution NMR spectrometers as well as low resolution benchtop NMR screening tools will be presented.

Chinn, S C; Herberg, J L; Sawvel, A M; Maxwell, R S

2004-11-29

100

Solution and solid state NMR approaches to draw iron pathways in the ferritin nanocage.  

PubMed

Ferritins are intracellular proteins that can store thousands of iron(III) ions as a solid mineral. These structures autoassemble from four-helix bundle subunits to form a hollow sphere and are a prototypical example of protein nanocages. The protein acts as a reservoir, encapsulating iron as ferric oxide in its central cavity in a nontoxic and bioavailable form. Scientists have long known the structural details of the protein shell, owing to very high resolution X-ray structures of the apoform. However, the atomic level mechanism governing the multistep biomineralization process remained largely elusive. Through analysis of the chemical behavior of ferritin mutants, chemists have found the role of some residues in key reaction steps. Using Mössbauer and XAS, they have identified some di-iron intermediates of the catalytic reaction trapped by rapid freeze quench. However, structural information about the iron interaction sites remains scarce. The entire process is governed by a number of specific, but weak, interactions between the protein shell and the iron species moving across the cage. While this situation may constitute a major problem for crystallography, NMR spectroscopy represents an optimal tool to detect and characterize transient species involving soluble proteins. Regardless, NMR analysis of the 480 kDa ferritin represents a real challenge. Our interest in ferritin chemistry inspired us to use an original combination of solution and solid state approaches. While the highly symmetric structure of the homo-24-mer frog ferritin greatly simplifies the spectra, the large protein size hinders the efficient coherence transfer in solution, thus preventing the sequence specific assignments. In contrast, extensive (13)C-spin diffusion makes the solution (13)C-(13)C NOESY experiment our gold standard to monitor protein side chains both in the apoprotein alone and in its interaction with paramagnetic iron species, inducing line broadening on the resonances of nearby residues. We could retrieve the structural information embedded in the (13)C-(13)C NOESY due to a partial sequence specific assignment of protein backbone and side chains we obtained from solid state MAS NMR of ferritin microcrystals. We used the 59 assigned amino acids (?33% of the total) as probes to locate paramagnetic ferric species in the protein cage. Through this approach, we could identify ferric dimers at the ferroxidase site and on their pathway towards the nanocage. Comparison with existing data on bacterioferritins and bacterial ferritins, as well as with eukaryotic ferritins loaded with various nonfunctional divalent ions, allowed us to reinterpret the available information. The resulting picture of the ferroxidase site is slightly different with various ferritins but is designed to provide multiple and generally weak iron ligands. The latter assist binding of two incoming iron(II) ions in two proximal positions to facilitate coupling with oxygen. Subsequent oxidation is accompanied by a decrease in the metal-metal distance (consistent with XAS/Mössbauer) and in the number of protein residues involved in metal coordination, facilitating the release of products as di-iron clusters under the effect of new incoming iron(II) ions. PMID:24000809

Lalli, Daniela; Turano, Paola

2013-11-19

101

Solid-state Ru-99 NMR spectroscopy: a useful tool for characterizing prototypal diamagnetic ruthenium compounds.  

PubMed

The feasibility of (99)Ru NMR spectroscopy as a tool to characterize solid compounds is demonstrated. Results of the first solid-state (99)Ru NMR investigation of diamagnetic compounds are presented for Ru(NH(3))(6)Cl(2), K(4)Ru(CN)(6). xH(2)O (x = 0, 3), LaKRu(CN)(6), and Ru(3)(CO)(12). The sensitivity of the ruthenium magnetic shielding tensor to subtle changes in the local structure about the ruthenium nucleus is highlighted by comparing the (99)Ru isotropic chemical shift of Ru(NH(3))(6)Cl(2) in aqueous solutions and in the solid state. The narrow isotropic (99)Ru NMR peak observed for solid Ru(NH(3))(6)Cl(2) indicates that this compound is an ideal secondary reference sample for solid-state (99)Ru NMR studies. The isotropic (99)Ru chemical shift, (99)Ru nuclear quadrupolar coupling constant, C(Q), and quadrupolar asymmetry parameter of K(4)Ru(CN)(6). xH(2)O (x = 0, 3) are shown to be sensitive to x. For Ru(3)(CO)(12), the magnetic shielding tensors of each of the three nonequivalent Ru nuclei have spans of 1300-1400 ppm, and the (99)Ru C(Q) values are also similar, 1.36-1.85 MHz, and are surprisingly small given that (99)Ru has a moderate nuclear quadrupole moment. Information about the relative orientation of the Ru magnetic shielding and electric field gradient tensors has been determined for Ru(3)(CO)(12) from experimental (99)Ru NMR spectra as well as quantum chemical calculations. PMID:15339183

Ooms, Kristopher J; Wasylishen, Roderick E

2004-09-01

102

Solid-state ²H NMR shows equivalence of dehydration and osmotic pressures in lipid membrane deformation.  

PubMed

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. PMID:21190661

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

2011-01-01

103

Study of Chalcogenide Glasses via Solid-State NMR Gregory S. Boebinger, National High Magnetic Field Laboratory  

E-print Network

.6 T. (b) Isotropic NMR projection obtained from the 2D spectrum in (c), where spinning sidebands dueStudy of Chalcogenide Glasses via Solid-State NMR Gregory S. Boebinger, National High Magnetic Field Laboratory DMR-Award 0654118 NMR Facility Chalcogenide glasses have wide-ranging applications

Weston, Ken

104

Solid-State 13C NMR of Liquid Crystalline Polyesters: Variations in Morphology, Alignment, and Dynamics within a Homologous Series  

E-print Network

D and 2D NMR experiments also illustrated substantial differences in the degree of motional dynamicsSolid-State 13C NMR of Liquid Crystalline Polyesters: Variations in Morphology, Alignment liquid crystals. 13C NMR experiments showed that the nematic ordering achieved by these synthetic

Frydman, Lucio

105

Orientational and motional narrowing of solid-state NMR lineshapes of uniaxially aligned membrane proteins.  

PubMed

A unified theory for the NMR line shapes of aligned membrane proteins arising from uniaxial disorder (mosaic spread) and global rotational diffusion about the director axis is presented. A superoperator formalism allows one to take into account the effects of continuous radiofrequency irradiation and frequency offsets in the presence of dynamics. A general method based on the Stochastic Liouville Equation makes it possible to bridge the static and dynamic limits in a single model. Simulations of solid-state NMR spectra are performed for a uniform ? helix by considering orientational disorder and diffusion of the helix as a whole relative to the alignment axis. The motional narrowing of the resonance lines is highly inhomogeneous and can be used as an additional angular restraint in structure calculations. Experimental solid-state NMR spectra of Pf1 coat protein support the conclusions of the theory for two limiting cases. The static disorder dominates the (15)N NMR spectra of Pf1 aligned on a phage, while fast uniaxial diffusion provides a line narrowing mechanism for the Pf1 protein reconstituted in magnetically aligned bicelles. PMID:22073926

Nevzorov, Alexander A

2011-12-29

106

High-resolution solid-state 13C CP MAS NMR spectra of some ?-cyclodextrin inclusion complexes with nitriles  

NASA Astrophysics Data System (ADS)

?-cyclodextrin inclusion complexes of 3-aminobenzonitrile, 4-aminobenzonitrile, and adamantane-1-carbonitrile were studied by means of high-resolution solid-state CP MAS 13C NMR spectroscopy. The interactions between the host and guest molecules are discussed.

Okazaki, M.; McDowell, C. A.

1983-11-01

107

Correlation of solid-state NMR relaxation times to functional properties such as chemical stability and particle size  

E-print Network

The purpose of the work presented in this dissertation was to investigate the correlation between the particle size of crystalline active pharmaceutical ingredients (APIs) and their solid-state NMR (SSNMR) proton spin-lattice ...

Dempah, Kassibla Elodie

2013-05-31

108

The effects of cholesterol on magnetically aligned phospholipid bilayers: a solid-state NMR and EPR spectroscopy study  

NASA Astrophysics Data System (ADS)

This paper presents the first time that both solid-state NMR spectroscopy and EPR spectroscopy are used to study the effects of cholesterol on magnetically aligned phospholipid bilayers (bicelles). Solid-state deuterium NMR spectroscopy was carried out using both chain perdeuterated 1,2-dimyristoyl- sn-glycero-3-phosphatidylcholine (DMPC-d 54) and a partially deuterated ?-[2,2,3,4,4,6- 2H 6]cholesterol (cholesterol-d 6). Also, EPR spectroscopy was carried out utilizing a 3?-doxyl-5?-cholestane (cholestane) spin probe incorporated into magnetically aligned bilayers to provide a more complete picture about the ordering and dynamics of the phospholipid and cholesterol molecules in the bicelle membrane system. The results demonstrate that cholesterol was successfully incorporated into the phospholipid bilayers. The molecular order parameters extracted directly from the 2H NMR spectra of both DMPC-d 54 and cholesterol-d 6 were compared to that from the EPR study of cholestane. The order parameters indicate that the sterol was motionally restricted, and that the DMPC had high order and low motion for the hydrocarbon segments close to the head groups of the phospholipids and less order and more rapid motion toward the terminal methyl groups. Both methods clearly indicate an overall increase in the degree of ordering of the molecules in the presence of cholesterol and a decrease in the degree of ordering at higher temperatures. However, EPR spectroscopy and 2H NMR spectroscopy exhibit different degrees of sensitivity in detecting the phospholipid molecular motions in the membrane. Finally, cholesterol increases the minimum alignment temperature necessary to magnetically align the phospholipid bilayers.

Lu, Jun-Xia; Caporini, Marc A.; Lorigan, Gary A.

2004-05-01

109

An Active Photoreceptor Intermediate Revealed by In Situ Photoirradiated Solid-State NMR Spectroscopy  

PubMed Central

A novel, to our knowledge, in situ photoirradiation system for solid-state NMR measurements is improved and demonstrated to successfully identify the M-photointermediate of pharaonis phoborhodopsin (ppR or sensory rhodopsin II), that of the complex with transducer (ppR/pHtrII), and T204A mutant embedded in a model membrane. The 13C NMR signals from [20-13C]retinal-ppR and ppR/pHtrII revealed that multiple M-intermediates with 13-cis, 15-anti retinal configuration coexisted under the continuously photoirradiated condition. NMR signals observed from the photoactivated retinal provide insights into the process of photocycle in the ppR/pHtrII complex. PMID:22098758

Tomonaga, Yuya; Hidaka, Tetsurou; Kawamura, Izuru; Nishio, Takudo; Ohsawa, Kazuhiro; Okitsu, Takashi; Wada, Akimori; Sudo, Yuki; Kamo, Naoki; Ramamoorthy, Ayyalusamy; Naito, Akira

2011-01-01

110

Characterization of the disordered phosphate network in CaO–P 2O 5 glasses by 31P solid-state NMR and Raman spectroscopies  

Microsoft Academic Search

In this study, the disordered network of calcium phosphate glasses is investigated by Raman scattering and 31P magic angle spinning (MAS) solid-state NMR spectroscopies. The use of both spectroscopies in a combined approach allows drawing a detailed understanding of the structure of these glasses. The P?O?P connectivity between successive PO4 tetrahedra is probed using through-bond double quantum–single quantum (DQ–SQ) and

Claire Roiland; Franck Fayon; Patrick Simon; Dominique Massiot

2011-01-01

111

Sensitivity and resolution enhancement in solid-state NMR spectroscopy of bicelles  

NASA Astrophysics Data System (ADS)

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.

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

2007-02-01

112

Solid-State NMR Studies of HIV-1 Capsid Protein Assemblies  

SciTech Connect

In mature HIV-1 virions, the 26.6 kDa CA protein is assembled into a characteristic cone-shaped core (capsid) that encloses the RNA viral genome. The assembled capsid structure is best described by a fullerene cone model that is made up from a hexameric lattice containing a variable number of CA pentamers, thus allowing for closure of tubular or conical structures. In this paper, we present a solid-state NMR analysis of the wild-type HIV-1 CA protein, prepared as conical and spherical assemblies that are stable and are not affected by magic angle spinning of the samples at frequencies between 10 and 25 kHz. Multidimensional homo- and heteronuclear correlation spectra of CA assemblies of uniformly 13C,15Nlabeled CA exhibit narrow lines, indicative of the conformational homogeneity of the protein in these assemblies. For the conical assemblies, partial residue-specific resonance assignments were obtained. Analysis of the NMR spectra recorded for the conical and spherical assemblies indicates that the CA protein structure is not significantly different in the different morphologies. The present results demonstrate that the assemblies of CA protein are amenable to detailed structural analysis by solid-state NMR spectroscopy.

Han, Yun; Ahn, Jinwoo; Concel, Jason; Byeon, In-Ja L.; Gronenborn, Angela M.; Yang, Jun; Polenova, Tatyana E.

2010-02-17

113

Experiments Optimized for Magic Angle Spinning and Oriented Sample Solid-State NMR of Proteins  

PubMed Central

Structure determination by solid-state NMR of proteins is rapidly advancing as result of recent developments of samples, experimental methods, and calculations. There are a number of different solid-state NMR approaches that utilize stationary, aligned samples or magic angle spinning of unoriented ‘powder’ samples, and depending on the sample and the experimental method can emphasize the measurement of distances or angles, ideally both, as sources of structural constraints. Multi-dimensional correlation spectroscopy of low-gamma nuclei such as 15N and 13C is an important step for making resonance assignments and measurements of angular restraints in membrane proteins. However, the efficiency of coherence transfer predominantly depends upon the strength of dipole-dipole interaction, and this can vary from site to site and between sample alignments, for example, during the mixing of 13C and 15N magnetization in stationary aligned and in magic angle spinning samples. Here, we demonstrate that the efficiency of polarization transfer can be improved by using adiabatic demagnetization and remagnetization techniques on stationary aligned samples; and proton assisted insensitive nuclei cross-polarization in magic angle sample spinning samples. Adiabatic cross-polarization technique provides an alternative mechanism for spin-diffusion experiments correlating 15N/15N and 15N/13C chemical shifts over large distances. Improved efficiency in cross-polarization with 40% – 100% sensitivity enhancements are observed in proteins and single crystals, respectively. We describe solid-state NMR experimental techniques that are optimal for membrane proteins in liquid crystalline phospholipid bilayers under physiological conditions. The techniques are illustrated with data from both single crystals of peptides and of membrane proteins in phospholipid bilayers. PMID:24044695

Das, Bibhuti B.; Lin, Eugene C.; Opella, Stanley J.

2013-01-01

114

Solid-state NMR study of geopolymer prepared by sol-gel chemistry  

NASA Astrophysics Data System (ADS)

Geopolymers are a new class of materials formed by the condensation of aluminosilicates and silicates obtained from natural minerals or industrial wastes. In this work, the sol-gel method is used to synthesize precursor materials for the preparation of geopolymers. The geopolymer samples prepared by our synthetic route have been characterized by a series of physical techniques, including Fourier-transform infrared, X-ray diffraction, and multinuclear solid-state NMR. The results are very similar to those obtained for the geopolymers prepared from natural kaolinite. We believe that our synthetic approach can offer a good opportunity for the medical applications of geopolymer.

Tsai, Yi-Ling; Hanna, John V.; Lee, Yuan-Ling; Smith, Mark E.; Chan, Jerry C. C.

2010-12-01

115

Solid state 77Se NMR investigations on arsenic-selenium glasses and crystals  

NASA Astrophysics Data System (ADS)

Some resolved solid state 77Se NMR spectra are presented in the As xSe 1- x glass family at ambient temperature. They exhibit three different kinds of Se environments. A comparison with the parent crystalline phases permits to assign the lines to Se- Se-Se, Se- Se-As and As- Se-As Se atom neighborhoods. The measurements of the relative intensities of the lines prove the validity of the intermediate range order structural model known as the "chains crossing model" which is based on AsSe 3 pyramids homogeneously distributed among the divalent Se atoms network. In particular, any scenario involving a selenium clustering process is refuted.

Bureau, Bruno; Troles, Johann; LeFloch, Marie; Smektala, Frédéric; Silly, Gilles; Lucas, Jacques

2003-01-01

116

Structural modeling of Vpu from HIV-1 based on solid-state NMR observables  

NASA Astrophysics Data System (ADS)

Vpu is one of the accessory proteins of HIV-1, and is involved in viral particle release. Viral particle release is enhanced by two proposed functions of Vpu: (i) tetherin interaction and (ii) membrane polarization. Two Vpu functions in viral particle release are still controversial. Here, we investigated the proposed functions by extensive structural modeling of Vpu based on solid-state NMR (Nuclear Magnetic Resonance) observables. We found that Vpu can co-exist in two structural forms: left-handed and right-handed conformation. The co-existence of the two conformations provides a clue to reconcile the controversial issue of its two functions in virus particle release.

Ahn, SeonJoo; Lim, GyuTae; Nam, Seungyoon; Lee, Jinhyuk

2014-04-01

117

Indirectly detected heteronuclear correlation solid-state NMR spectroscopy of naturally abundant 15N nuclei.  

PubMed

Two-dimensional indirectly detected through-space and through-bond (1)H{(15)N} solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse (1)H decoupling are evaluated. Remarkable efficiency of polarization transfer can be achieved at a MAS rate of 40 kHz by both cross-polarization and INEPT, which makes these methods applicable for routine characterizations of natural abundance solids. The first measurement of 2D (1)H{(15)N} HETCOR spectrum of natural abundance surface species is also reported. PMID:24287060

Althaus, Stacey M; Mao, Kanmi; Stringer, John A; Kobayashi, Takeshi; Pruski, Marek

2014-01-01

118

Homogeneous nanoparticles to enhance the efficiency of a hydrophobic drug, antihyperlipidemic probucol, characterized by solid-state NMR.  

PubMed

A low absorption in the gastrointestinal tract of hydrophobic pharmaceutical compounds in use today considerably limits their bioavailability, and therefore they are taken in large doses in order to reach the therapeutic plasma concentration, which inevitably results in undesired side effects. In this study, we demonstrate a new nanoparticle approach to overcome this problem, and our experimental results show that this approach has a high efficiency of drug loading and is easily adaptable to industrial scale. Characterization of nanoparticles containing a cholesterol-lowering hydrophobic drug, probucol, using a variety of biophysical techniques revealed higher homogeneity of these particles compared to those prepared using other approaches. Intermolecular interactions of these nanoparticles are probed at high resolution by magic angle spinning solid-state NMR experiments. PMID:19938876

Io, Takeshi; Fukami, Toshiro; Yamamoto, Kazutoshi; Suzuki, Toyofumi; Xu, Jiadi; Tomono, Kazuo; Ramamoorthy, Ayyalusamy

2010-02-01

119

Low Temperature Solid-State NMR Experiments of Half-Integer Quadrupolar Nuclides: Caveats and Data Analysis  

SciTech Connect

Solid-state NMR spectroscopy of half-integer quadrupolar metals has received a lot of interest recently with the advent of new methodologies and higher magnetic fields. We present here the extension of our previous low temperature method to an 18.8 T system. This new probe entailed a total redesign including a cross coil and variable capacitors that are operational at cryogenic temperatures. The limitations to sensitivity are also discussed; including a new diode network, the utilization of a cryogenic band pass filter, and the consequences of the RF profiles of the coil. Further, details of the spectroscopy of a spin 5/2 metal in a protein are discussed, such as the observation of the outer transitions and how to distinguish them from the desired {+-}1/2 transition

Lipton, Andrew S.; Heck, Robert W.; Sears, Jesse A.; Ellis, Paul D.

2004-03-01

120

Transformer-coupled NMR probe  

NASA Astrophysics Data System (ADS)

In this study, we propose an NMR probe circuit that uses a transformer with a ferromagnetic core for impedance matching. The ferromagnetic core provides a strong but confined coupling that result in efficient energy transfer between the sample coil and NMR spectrometer, while not disturbing the B1 field generated by the sample coil. We built a transformer-coupled NMR probe and found that it offers comparable performance (loss <1 dB) to a conventional capacitor-coupled circuit. Our probe operates over a wide frequency range (500 kHz-5 MHz in this example) without the need for matching adjustments. Such probes could be useful for low-field mobile NMR applications of multi-frequency operation, such as imaging, relaxation, and diffusion measurements, as well as NQR.

Utsuzawa, Shin; Mandal, Soumyajit; Song, Yi-Qiao

2012-03-01

121

Probing Access Resistance of Solid-state Nanopores with a Scanning Probe Microscope Tip  

PubMed Central

An apparatus that integrates solid-state nanopore ionic current measurement with a Scanning Probe Microscope has been developed. When a micrometer-scale scanning probe tip is near a voltage biased nanometer-scale pore (10–100 nm), the tip partially blocks the flow of ions to the pore and increases the pore access resistance. The apparatus records the current blockage caused by the probe tip and the location of the tip simultaneously. By measuring the current blockage map near a nanopore as a function of the tip position in 3D space in salt solution, we estimate the relative pore resistance increase due to the tip, ?R/R0, as a function of the tip location, nanopore geometry, and salt concentration. The amplitude of ?R/R0 also depends on the ratio of the pore length to its radius as Ohm’s law predicts. When the tip is very close to the pore surface, ~10 nm, our experiments show that ?R/R0 depends on salt concentration as predicted by the Poisson and Nernst-Planck equations. Furthermore, our measurements show that ?R/R0 goes to zero when the tip is about five times the pore diameter away from the center of the pore entrance. The results in this work not only demonstrate a way to probe the access resistance of nanopores experimentally, they also provide a way to locate the nanopore in salt solution, and open the door to future nanopore experiments for detecting single biomolecules attached to a probe tip. PMID:22393313

Hyun, Changbae; Rollings, Ryan

2012-01-01

122

STRUCTURAL STUDIES OF BIOMATERIALS USING DOUBLE-QUANTUM SOLID-STATE NMR SPECTROSCOPY  

SciTech Connect

Proteins directly control the nucleation and growth of biominerals, but the details of molecular recognition at the protein-biomineral interface remain poorly understood. The elucidation of recognition mechanisms at this interface may provide design principles for advanced materials development in medical and ceramic composites technologies. Here, we describe both the theory and practice of double-quantum solid-stateNMR(ssNMR) structure-determination techniques, as they are used to determine the secondary structures of surface-adsorbed peptides and proteins. In particular, we have used ssNMR dipolar techniques to provide the first high-resolution structural and dynamic characterization of a hydrated biomineralization protein, salivary statherin, adsorbed to its biologically relevant hydroxyapatite (HAP) surface. Here, we also review NMR data on peptides designed to adsorb from aqueous solutions onto highly porous hydrophobic surfaces with specific helical secondary structures. The adsorption or covalent attachment of biological macromolecules onto polymer materials to improve their biocompatibility has been pursued using a variety of approaches, but key to understanding their efficacy is the verification of the structure and dynamics of the immobilized biomolecules using double-quantum ssNMR spectroscopy.

Drobny, Gary P.; Long, J. R.; Karlsson, T.; Shaw, Wendy J.; Popham, Jennifer M.; Oyler, N.; Bower, Paula M.; Stringer, J.; Gregory, D.; Mehta, M.; Stayton, Patrick S.

2004-10-31

123

[sup 29]Si solid state NMR study of tricalcium silicate and cement hydration at high temperature  

SciTech Connect

Oilwell cementing involves the placement of a cement slurry in the annulus between the metal casing and the geological formation. Its principal functions are to isolate the different zones within the wellbore and to support the casing at each stage of drilling. [sup 29]Si high resolution solid state NMR has been used to follow the hydration kinetics of class G Portland cement and of its major component: tricalcium silicate Ca[sub 3]SiO[sub 5] (C[sub 3]S). Samples were hydrothermally synthesized at temperatures between 60 and 120C; hydration was stopped at selected reaction times, from 30 minutes to 14 days, by the acetone-ether method of water-removing. [sup 29]Si NMR spectra of hydrates clearly show that, in silicate chains, the ratio between the silicon atoms of end groups and those of middle groups depends not only on the time of hydration, but also on the synthesis temperature.

Masse, S.; Zanni, H. (URA CNRS, Paris (France). Lab. de Physique et Mecanique des Milieux Heterogenes Univ. Pierre et Marie Curie, Paris (France)); Lecourtier, J.; Roussel, J.C.; Rivereau, A. (Inst. Francais du Petrole, Rueil Malmaison (France))

1993-09-01

124

Applications of high-resolution 1H solid-state NMR.  

PubMed

This article reviews the large increase in applications of high-resolution (1)H magic-angle spinning (MAS) solid-state NMR, in particular two-dimensional heteronuclear and homonuclear (double-quantum and spin-diffusion NOESY-like exchange) experiments, in the last five years. These applications benefit from faster MAS frequencies (up to 80 kHz), higher magnetic fields (up to 1 GHz) and pulse sequence developments (e.g., homonuclear decoupling sequences applicable under moderate and fast MAS). (1)H solid-state NMR techniques are shown to provide unique structural insight for a diverse range of systems including pharmaceuticals, self-assembled supramolecular structures and silica-based inorganic-organic materials, such as microporous and mesoporous materials and heterogeneous organometallic catalysts, for which single-crystal diffraction structures cannot be obtained. The power of NMR crystallography approaches that combine experiment with first-principles calculations of NMR parameters (notably using the GIPAW approach) are demonstrated, e.g., to yield quantitative insight into hydrogen-bonding and aromatic CH-? interactions, as well as to generate trial three-dimensional packing arrangements. It is shown how temperature-dependent changes in the (1)H chemical shift, linewidth and DQ-filtered signal intensity can be analysed to determine the thermodynamics and kinetics of molecular level processes, such as the making and breaking of hydrogen bonds, with particular application to proton-conducting materials. Other applications to polymers and biopolymers, inorganic compounds and bioinorganic systems, paramagnetic compounds and proteins are presented. The potential of new technological advances such as DNP methods and new microcoil designs is described. PMID:22177472

Brown, Steven P

2012-02-01

125

Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization  

NASA Astrophysics Data System (ADS)

A simple new method is presented that yields quantitative solid-state magic-angle spinning (MAS) 13C NMR spectra of organic materials with good signal-to-noise ratios. It achieves long (>10 ms) cross polarization (CP) from 1H without significant magnetization losses due to relaxation and with a moderate duty cycle of the radio-frequency irradiation, by multiple 1-ms CP periods alternating with 1H spin-lattice relaxation periods that repolarize the protons. The new method incorporates previous techniques that yield less distorted CP/MAS spectra, such as a linear variation (“ramp”) of the radio-frequency field strength, and it overcomes their main limitation, which is T1? relaxation of the spin-locked 1H magnetization. The ramp of the radio-frequency field strength and the asymptotic limit of cross polarization makes the spectral intensity quite insensitive to the exact field strengths used. The new multiCP pulse sequence is a “drop-in” replacement for previous CP methods and produces no additional data-processing burden. Compared to the only reliable quantitative 13C NMR method for unlabeled solids previously available, namely direct-polarization NMR, the measuring time is reduced by more than a factor of 50, enabling higher-throughput quantitative NMR studies. The new multiCP technique is validated with 14-kHz MAS on amino-acid derivatives, plant matter, a highly aromatic humic acid, and carbon materials made by low-temperature pyrolysis.

Johnson, Robert L.; Schmidt-Rohr, Klaus

2014-02-01

126

Analysis of atomic scale chemical environments of boron in coal by 11B solid state NMR.  

PubMed

Atomic scale chemical environments of boron in coal has been studied by solid state NMR spectroscopy including magic angle spinning (MAS), satellite transition magic angle spinning (STMAS), and cross-polarization magic angle spinning (CPMAS). The (11)B NMR spectra can be briefly classified according to the degree of coalification. On the (11)B NMR spectra of lignite, bituminous, and sub-bituminous coals (carbon content of 70-90mass%), three sites assigned to four-coordinate boron ([4])B with small quadrupolar coupling constants (?0.9 MHz) are observed. Two of the ([4])B sites in downfield are considered organoboron complexes with aromatic ligands, while the other in the most upper field is considered inorganic tetragonal boron (BO(4)). By contrast, on the (11)B NMR spectra of blind coal (carbon content >90mass%), the ([4])B which substitutes tetrahedral silicon of Illite is observed as a representative species. It has been considered that the organoboron is decomposed and released from the parent phase with the advance of coal maturation, and then the released boron reacts with the inorganic phase to substitute an element of inorganic minerals. Otherwise boron contained originally in inorganic minerals might remain preserved even under the high temperature condition that is generated during coalification. PMID:21175186

Takahashi, Takafumi; Kashiwakura, Shunsuke; Kanehashi, Koji; Hayashi, Shunichi; Nagasaka, Tetsuya

2011-02-01

127

Molecular-level characterization of probucol nanocrystal in water by in situ solid-state NMR spectroscopy.  

PubMed

The molecular state of colloidal probucol nanoparticles with additives was evaluated by (13)C in situ solid-state NMR spectroscopy. The nanoparticles were obtained by dispersing a ternary co-ground mixture of probucol/polyvinylpyrrolidon (PVP)/sodium dodecyl sulfate (SDS) in water. Their mean particle size was found to be approximately 150 nm by dynamic light scattering and cryogenic-scanning electron microscopy measurements. The results of the (13)C in situ solid-state NMR spectroscopy showed that probucol existed in the crystalline state (form I) in water. (13)C liquid-state NMR results indicated that PVP and SDS interacted with probucol in water. Their broad signals suggested that the surface interaction of the probucol nanocrystal with PVP and SDS stabilized the suspension. In addition, a freeze-dried sample of the suspension was studied by (13)C solid-state NMR and powder X-ray diffraction experiments, which confirmed the presence of the probucol nanocrystals. The combination of the in situ solid-state, solid-state, and liquid-state NMR measurement results provided molecular-level insights about the role of intermolecular interactions in the design of nanoformulations. PMID:22138607

Zhang, Junying; Higashi, Kenjirou; Limwikrant, Waree; Moribe, Kunikazu; Yamamoto, Keiji

2012-02-28

128

Solid-state NMR analysis of membrane proteins and protein aggregates by proton detected spectroscopy  

PubMed Central

Solid-state NMR has emerged as an important tool for structural biology and chemistry, capable of solving atomic-resolution structures for proteins in membrane-bound and aggregated states. Proton detection methods have been recently realized under fast magic-angle spinning conditions, providing large sensitivity enhancements for efficient examination of uniformly labeled proteins. The first and often most challenging step of protein structure determination by NMR is the site-specific resonance assignment. Here we demonstrate resonance assignments based on high-sensitivity proton-detected three-dimensional experiments for samples of different physical states, including a fully-protonated small protein (GB1, 6 kDa), a deuterated microcrystalline protein (DsbA, 21 kDa), a membrane protein (DsbB, 20 kDa) prepared in a lipid environment, and the extended core of a fibrillar protein (?-synuclein, 14 kDa). In our implementation of these experiments, including CONH, CO(CA)NH, CANH, CA(CO)NH, CBCANH, and CBCA(CO)NH, dipolar-based polarization transfer methods have been chosen for optimal efficiency for relatively high protonation levels (full protonation or 100 % amide proton), fast magic-angle spinning conditions (40 kHz) and moderate proton decoupling power levels. Each H–N pair correlates exclusively to either intra- or inter-residue carbons, but not both, to maximize spectral resolution. Experiment time can be reduced by at least a factor of 10 by using proton detection in comparison to carbon detection. These high-sensitivity experiments are especially important for membrane proteins, which often have rather low expression yield. Proton-detection based experiments are expected to play an important role in accelerating protein structure elucidation by solid-state NMR with the improved sensitivity and resolution. PMID:22986689

Nieuwkoop, Andrew J.; Berthold, Deborah A.; Comellas, Gemma; Sperling, Lindsay J.; Tang, Ming; Shah, Gautam J.; Brea, Elliott J.; Lemkau, Luisel R.

2012-01-01

129

Low-E probe for 19F– 1H NMR of dilute biological solids  

Microsoft Academic Search

Sample heating induced by radio frequency (RF) irradiation presents a significant challenge to solid state NMR experiments in proteins and other biological systems, causing the sample to dehydrate which may result in distorted spectra and a damaged sample. In this work we describe a large volume, low-E 19F–1H solid state NMR probe, which we developed for the 2D 19F CPMG

Peter L. Gor’kov; Raiker Witter; Eduard Y. Chekmenev; Farhod Nozirov; Riqiang Fu; William W. Brey

2007-01-01

130

Cross-polarization/magic-angle sample-spinning 13C NMR spectroscopic study of chlorophyll a in the solid state  

PubMed Central

Solid-state cross-polarization/magic-angle sample-spinning 13C NMR spectra have been recorded on chlorophyll a-water aggregates, methyl pyrochlorophyllide a, and methyl pyropheophorbide a (derivatives that lack a phytyl chain). Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid-state spectra. PMID:16593410

Brown, Charles Eric; Spencer, Robert B.; Burger, Vern T.; Katz, Joseph J.

1984-01-01

131

Cross-polarization/magic-angle sample-spinning C NMR spectroscopic study of chlorophyll a in the solid state.  

PubMed

Solid-state cross-polarization/magic-angle sample-spinning (13)C NMR spectra have been recorded on chlorophyll a-water aggregates, methyl pyrochlorophyllide a, and methyl pyropheophorbide a (derivatives that lack a phytyl chain). Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid-state spectra. PMID:16593410

Brown, C E; Spencer, R B; Burger, V T; Katz, J J

1984-01-01

132

Solid state NMR study of SEI formation in lithium ion batteries  

NASA Astrophysics Data System (ADS)

Recently, rechargeable lithium ion batteries, which offer high energy density and long cycle life, are in great demand as power sources for our mobile electronic society. The formation of a solid electrolyte interphase (SEI) on the surface of electrodes in lithium ion batteries plays an essential role in their performance. This thesis presents solid state NMR and MAS NMR results on the SEI, which contribute to our understanding of SEI formation on both cathodes and anodes. This thesis is organized as following: Chapter 1 surveys the history of batteries and the challenges to further development of the lithium ion battery. Fundamental aspects and SEI formation mechanisms are also included in Chapter l. Chapter 2 deals with the principles and experimental techniques of solid state NMR. Chapter 3 presents studies of SEI formation on anode and cathode in lithium ion batteries using electrochemical impedance spectroscopy (EIS) and NMR. The results provide EIS and NMR evidence that cells containing electrolytes with high EC content display less irreversible capacity after high temperature storage. The irreversible capacity is attributed to SEI growth on electrode surfaces. NMR results on cathodes, on the other hand, imply that the presence of Ni in the cathode may reduce cell performance due to the oxidation of Ni 3+ to Ni4+. Our simulations show that a lower EC/DMC ratio is associated with a smaller SEI intensity for the cathode and higher intensity for the anode. Chapter 4 discusses the effect of temperature on SEI formation on anodes and cathodes. NMR measurements show that MCMB graphite based anodes exhibit high stability no chemical shift is evident over a wide temperature range. On cathodes, however, NMR does reveal changes in SEI intensity as a function of temperature. These changes are believed to be the result of decomposition of the SEI. Evidently, then, changes in the performance of the cell as a factor of temperature are, at least in part, due to changes in the SEI with temperature. In Chapter 5 we report on the use of NMR to study the effect of electrolyte/solvent and electrode structure on SEI formation. The intensity of the SEI in a cell containing LiBOB electrolyte with EC and DEC is greater than that in a cell with LiPF6 electrolyte with EC and DMC. This implies that the cell containing LiBOB electrolyte with EC and DEC is more stable. From the analysis of NMR of the cathode, it was found that it is easier to form SEI in layered structure cathode than in a spinel structure, suggesting that spinel structure materials may be better choices as cathode in lithium ion batteries. Evidently, then, the choice of electrolyte/solvent materials and electrode materials are key factors in determining the performance of lithium ion batteries.

Zhao, Dachun

133

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

SciTech Connect

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.

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

2010-12-09

134

Multiple quantum solid-state NMR indicates a parallel, not antiparallel, organization of ?-sheets in Alzheimer's ?-amyloid fibrils  

PubMed Central

Senile plaques associated with Alzheimer's disease contain deposits of fibrils formed by 39- to 43-residue ?-amyloid peptides with possible neurotoxic effects. X-ray diffraction measurements on oriented fibril bundles have indicated an extended ?-sheet structure for Alzheimer's ?-amyloid fibrils and other amyloid fibrils, but the supramolecular organization of the ?-sheets and other structural details are not well established because of the intrinsically noncrystalline, insoluble nature of amyloid fibrils. Here we report solid-state NMR measurements, using a multiple quantum (MQ) 13C NMR technique, that probe the ?-sheet organization in fibrils formed by the full-length, 40-residue ?-amyloid peptide (A?1–40). Although an antiparallel ?-sheet organization often is assumed and is invoked in recent structural models for full-length ?-amyloid fibrils, the MQNMR data indicate an in-register, parallel organization. This work provides site-specific, atomic-level structural constraints on full-length ?-amyloid fibrils and applies MQNMR to a significant problem in structural biology. PMID:11069287

Antzutkin, Oleg N.; Balbach, John J.; Leapman, Richard D.; Rizzo, Nancy W.; Reed, Jennifer; Tycko, Robert

2000-01-01

135

Towards automatic protein backbone assignment using proton-detected 4D solid-state NMR data.  

PubMed

We introduce an efficient approach for sequential protein backbone assignment based on two complementary proton-detected 4D solid-state NMR experiments that correlate [Formula: see text]/Ni with CAi/COi or CAi-1/COi-1. The resulting 4D spectra exhibit excellent sensitivity and resolution and are amenable to (semi-)automatic assignment approaches. This strategy allows to obtain sequential connections with high confidence as problems related to peak overlap and multiple assignment possibilities are avoided. Non-uniform sampling schemes were implemented to allow for the acquisition of 4D spectra within a few days. Rather moderate hardware requirements enable the successful demonstration of the method on deuterated type III secretion needles using a 600 MHz spectrometer at a spinning rate of 25 kHz. PMID:25193427

Xiang, ShengQi; Chevelkov, Veniamin; Becker, Stefan; Lange, Adam

2014-11-01

136

Solid-State NMR Comparison of Various Spiders' Dragline Silk Fiber  

PubMed Central

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

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.

2010-01-01

137

Solid-state NMR comparison of various spiders' dragline silk fiber.  

PubMed

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

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

2010-08-01

138

Orientational order of Australian spider silks as determined by solid-state NMR.  

PubMed

A simple solid-state NMR method was used to study the structure of (13)C- and (15)N-enriched silk from two Australian orb-web spider species, Nephila edulis and Argiope keyserlingi. Carbon-13 and (15)N spectra from alanine- or glycine-labeled oriented dragline silks were acquired with the fiber axis aligned parallel or perpendicular to the magnetic field. The fraction of oriented component was determined from each amino acid, alanine and glycine, using each nucleus independently, and attributed to the ordered crystalline domains in the silk. The relative fraction of ordered alanine was found to be higher than the fraction of ordered glycine, akin to the observation of alanine-rich domains in silk-worm (Bombyx mori) silk. A higher degree of crystallinity was observed in the dragline silk of N. edulis compared with A. keyserlingi, which correlates with the superior mechanical properties of the former. PMID:16463360

Bonev, B; Grieve, S; Herberstein, M E; Kishore, A I; Watts, A; Separovic, F

2006-06-01

139

Solid-state NMR study of geopolymer prepared by sol-gel chemistry  

SciTech Connect

Geopolymers are a new class of materials formed by the condensation of aluminosilicates and silicates obtained from natural minerals or industrial wastes. In this work, the sol-gel method is used to synthesize precursor materials for the preparation of geopolymers. The geopolymer samples prepared by our synthetic route have been characterized by a series of physical techniques, including Fourier-transform infrared, X-ray diffraction, and multinuclear solid-state NMR. The results are very similar to those obtained for the geopolymers prepared from natural kaolinite. We believe that our synthetic approach can offer a good opportunity for the medical applications of geopolymer. -- Graphical abstract: Geopolymer prepared by the sol-gel route has the same spectroscopic properties as the sample prepared from the natural kaolinite. Display Omitted

Tsai, Yi-Ling [Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan ROC (China); Hanna, John V. [Department of Physics, The University of Warwick, Coventry CV4 7AL (United Kingdom); Lee, Yuan-Ling, E-mail: yuanlinglee@ntu.edu.t [Graduate Institute of Clinical Dentistry, National Taiwan University and Hospital, No. 1, Changde Street, Taipei 10048, Taiwan ROC (China); Smith, Mark E., E-mail: M.E.Smith.1@warwick.ac.u [Department of Physics, The University of Warwick, Coventry CV4 7AL (United Kingdom); Chan, Jerry C.C., E-mail: chanjcc@ntu.edu.t [Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan ROC (China)

2010-12-15

140

Structural studies of methyl brevifolincarboxylate in solid state by means of NMR spectroscopy and DFT calculations  

NASA Astrophysics Data System (ADS)

Methyl brevifolincarboxylate isolated from the herb of Potentilla argentea L. (Rosaceae) is a representative of the naturally occurring polyphenols. The compound is of pharmaceutical interest mainly because of its antiviral and antioxidant properties. 13C NMR spectra were recorded for solution and solid phase. 13C CPMAS spectra were assigned by comparison with solution data, dipolar dephasing and short contact time experiments. The correctness of assignments was verified by GIAO DFT calculations of shielding constants. The differences between the solution and solid state chemical shift values were explained in terms of orientation of OH groups and intramolecular hydrogen bonds. The splitting of the C1 dbnd O resonance shows that there exists a polymorphism in the solid phase, which might be due to the formation of intramolecular hydrogen bond involving carbonyl or methoxy oxygen (i.e. C10 sbnd OH⋯O dbnd C or C10 sbnd OH⋯OCH 3).

Wolniak, Micha?; Tomczyk, Micha?; Gudej, Jan; Wawer, Iwona

2006-12-01

141

Tetraphosphine Linker Scaffolds with a Tetraphenyltin Core for Superior Immobilized Catalysts: A Solid-State NMR Study  

E-print Network

already been used in the group to determine the mobility of a deuterated alkyl chain in the coordination sphere of a metal complex.26 Because of this great analytical potential, classical solid-state NMR of the dry materials and HRMAS of slurries... already been used in the group to determine the mobility of a deuterated alkyl chain in the coordination sphere of a metal complex.26 Because of this great analytical potential, classical solid-state NMR of the dry materials and HRMAS of slurries...

Perera, Melanie Ingrid

2012-10-19

142

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

SciTech Connect

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){sup 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 {approx}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. Meanwhile, we have developed new methods to achieve broadband high resolution NMR and improve the accuracy of inter-nuclear distance measurements involving quadrupolar spins. Broadband high resolution NMR of spin-1/2 nuclei has been accomplished by the adaptation of the magic angle turning (MAT) method to fast magic angle spinning, termed fast MAT, by solving technical problems such as off resonance effects. Fast MAT separates chemical shift anisotropy and isotropic chemical shifts over a spectral range of {approx}1.8 {gamma}B{sub 1} without significant distortions. Fast MAT {sup 125}Te NMR has been applied to study technologically important telluride materials with spectra spreading up to 190 kHz. The signal-to-noise ratio of the spectra is significantly improved by using echo-matched Gaussian filtering in offline data processing. The accuracy of the measured distances between spin-1/2 and quadrupolar nuclei with methods such as SPIDER and REAPDOR has been improved by compensating for the fast longitudinal quadrupolar relaxation on the sub-millisecond with a modified S{sub 0} pulse sequence. Also, the T1Q effect on the spin coherence and its spinning speed dependency has been explored and documented with analytical and numerical simulations as well as experimental measurements.

Hu, Yanyan

2011-02-07

143

Structural investigation of aluminium doped ZnO nanoparticles by solid-state NMR spectroscopy.  

PubMed

The electrical conductivity of aluminium doped zinc oxide (AZO, ZnO:Al) materials depends on doping induced defects and grain structure. This study aims at relating macroscopic electrical conductivity of AZO nanoparticles with their atomic structure, which is non-trivial because the derived materials are heavily disordered and heterogeneous in nature. For this purpose we synthesized AZO nanoparticles with different doping levels and narrow size distribution by a microwave assisted polyol method followed by drying and a reductive treatment with forming gas. From these particles electrically conductive, optically transparent films were obtained by spin-coating. Characterization involved energy-dispersive X-ray analysis, wet chemical analysis, X-ray diffraction, electron microscopy and dynamic light scattering, which provided a basis for a detailed structural solid-state NMR study. A multinuclear ((27)Al, (13)C, (1)H) spectroscopic investigation required a number of 1D MAS NMR and 2D MAS NMR techniques (T(1)-measurements, (27)Al-MQMAS, (27)Al-(1)H 2D-PRESTO-III heteronuclear correlation spectroscopy), which were corroborated by quantum chemical calculations with an embedded cluster method (EEIM) at the DFT level. From the combined data we conclude that only a small part of the provided Al is incorporated into the ZnO structure by substitution of Zn. The related (27)Al NMR signal undergoes a Knight shift when the material is subjected to a reductive treatment with forming gas. At higher (formal) doping levels Al forms insulating (Al, H and C containing) side-phases, which cover the surface of the ZnO:Al particles and increase the sheet resistivity of spin-coated material. Moreover, calculated (27)Al quadrupole coupling constants serve as a spectroscopic fingerprint by which previously suggested point-defects can be identified and in their great majority be ruled out. PMID:22801707

Avadhut, Yamini S; Weber, Johannes; Hammarberg, Elin; Feldmann, Claus; Schmedt auf der Günne, Jörn

2012-09-01

144

SIMPSON: A General Simulation Program for Solid-State NMR Spectroscopy  

NASA Astrophysics Data System (ADS)

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 Tcl 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 1D 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 http://nmr.imsb.au.dk. 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.

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

2000-12-01

145

Natural abundance high field (43)Ca solid state NMR in cement science.  

PubMed

This work is a systematic attempt to determine the possibilities and the limitations of the (43)Ca high field solid state NMR in the study of cement-based materials. The low natural abundance (0.135%) and small gyromagnetic ratio of (43)Ca present a serious challenge even in a high magnetic field. The NMR spectra of a number of cement compounds of known structure and composition are examined. The spectra of several phases important in cement science, e.g., anhydrous beta di-calcium silicate (beta-C(2)S) and tri-calcium (C(3)S) silicate were obtained for the first time and the relation of spectroscopic and structural parameters is discussed. The method was also applied to the hydrated C(3)S and synthetic calcium silicate hydrates (C-S-H) of different composition in order to understand the state of calcium and transformations in the structure during hydrolysis. The spectra of hydrated C(3)S reveals a calcium environment similar to that of the C-S-H samples and 11 A Tobermorite. These observations support the validity of using layered crystalline C-S-H systems as structural models for the C-S-H that forms in the hydration of Portland cement. PMID:20463996

Moudrakovski, Igor L; Alizadeh, Rouhollah; Beaudoin, James J

2010-07-14

146

Solid-state NMR study of Li-assisted dehydrogenation of ammonia borane.  

PubMed

The mechanism of thermochemical dehydrogenation of the 1:3 mixture of Li(3)AlH(6) and NH(3)BH(3) (AB) has been studied by the extensive use of solid-state NMR spectroscopy and theoretical calculations. The activation energy for the dehydrogenation is estimated to be 110 kJ mol(-1), which is lower than for pristine AB (184 kJ mol(-1)). The major hydrogen release from the mixture occurs at 60 and 72 °C, which compares favorably with pristine AB and related hydrogen storage materials, such as lithium amidoborane (LiNH(2)BH(3), LiAB). The NMR studies suggest that Li(3)AlH(6) improves the dehydrogenation kinetics of AB by forming an intermediate compound (LiAB)(x)(AB)(1-x). A part of AB in the mixture transforms into LiAB to form this intermediate, which accelerates the subsequent formation of branched polyaminoborane species and further release of hydrogen. The detailed reaction mechanism, in particular the role of lithium, revealed in the present study highlights new opportunities for using ammonia borane and its derivatives as hydrogen storage materials. PMID:22435842

Kobayashi, Takeshi; Hlova, Ihor Z; Singh, Niraj K; Pecharsky, Vitalij K; Pruski, Marek

2012-04-01

147

Solid-state 1H and 27Al NMR studies of amorphous aluminum hydroxides.  

PubMed

Two kinds of amorphous aluminum hydroxides, a sample precipitated from admixing AlCl3 and NaOH aqueous solutions and the commercial product, were measured by 27Al and 1H solid-state NMR spectroscopy. Pentahedral and tetrahedral coordinations, as well as octahedral coordination of oxygen atoms for aluminum, are observed in 27Al magic angle spinning (MAS) spectra of both amorphous samples. In contrast, octahedral coordination is only observed in gibbsite, bayerite, and boehmite. According to 1H MAS-NMR spectra under conditions of high spinning rate (35 kHz) and high field (14.09 T), free waters and OH groups coupled with aluminum for amorphous samples are observed at approximately 5 and approximately 4.5 ppm, respectively, the latter peak being broader. This is consistent with the differential spectra between spin echo and transfer of populations in double resonance. We conclude that the subunits of AlO4, AlO5, and AlO6 in amorphous aluminum hydroxides are bound through hydrogen bonds with a wide distribution of bonding strength. PMID:16256537

Isobe, T; Watanabe, T; d'Espinose de la Caillerie, J B; Legrand, A P; Massiot, D

2003-05-15

148

Frequency-swept pulse sequences for 19F heteronuclear spin decoupling in solid-state NMR  

NASA Astrophysics Data System (ADS)

Heteronuclear spin decoupling pulse sequences in solid-state NMR have mostly been designed and applied for irradiating 1H as the abundant nucleus. Here, a systematic comparison of different methods for decoupling 19F in rigid organic solids is presented, with a special emphasis on the recently introduced frequency-swept sequences. An extensive series of NMR experiments at different MAS frequencies was conducted on fluorinated model compounds, in combination with large sets of numerical simulations. From both experiments and simulations it can be concluded that the frequency-swept sequences SW f-TPPM and SW f-SPINAL deliver better and more robust spin decoupling than the original sequences SPINAL and TPPM. Whereas the existence of a large chemical shift anisotropy and isotropic shift dispersion for 19F does compromise the decoupling efficiency, the relative performance hierarchy of the sequences remains unaffected. Therefore, in the context of rigid organic solids under moderate MAS frequencies, the performance trends observed for 19F decoupling are very similar to those observed for 1H decoupling.

Vinod Chandran, C.; Madhu, P. K.; Wormald, Philip; Bräuniger, Thomas

2010-10-01

149

Wheat bran biodegradation by Pleurotus ostreatus: a solid-state carbon-13 NMR study.  

PubMed

Solid-state (13)C nuclear magnetic resonance (NMR) and elemental analysis techniques were used to monitor the degradation of wheat bran by the white-rot fungus Pleurotus ostreatus during a 62-day cultivation period. The weight loss and in vitro organic matter digestibility of the substrate were also evaluated after fungal treatment. The (13)C NMR spectra of degraded wheat bran samples showed a lower content in carbohydrates and a higher content in aliphatic and carboxylic groups than the untreated control sample. In parallel, changes in the wheat bran elemental composition evidenced a decrease in carbon content and a concomitant increase in nitrogen and oxygen content during mycelium growth. These results clearly indicate the occurrence of progressive changes in the composition of wheat bran during fungal treatment and are interpreted in terms of preferential degradation of amorphous vs. crystalline polysaccharides by the fungal mycelium and accumulation of proteins in the substrate. At the end of the cultivation period, the treated samples experienced an average weight loss of 20% and an increase in organic matter digestibility of 17%. PMID:17920878

Locci, Emanuela; Laconi, Samuela; Pompei, Raffaello; Scano, Paola; Lai, Adolfo; Marincola, Flaminia Cesare

2008-07-01

150

Structure and Transformation of Amorphous Calcium Carbonate: A Solid-State 43Ca NMR and Computational Molecular Dynamics Investigation  

SciTech Connect

Amorphous calcium carbonate (ACC) is a metastable precursor to crystalline CaCO{sub 3} phases that precipitates by aggregation of ion pairs and prenucleation clusters. We use {sup 43}Ca solid-state NMR spectroscopy to probe the local structure and transformation of ACC synthesized from seawater-like solutions with and without Mg{sup 2+} and computational molecular dynamics (MD) simulations to provide more detailed molecular-scale understanding of the ACC structure. The {sup 43}Ca NMR spectra of ACC collected immediately after synthesis consist of broad, featureless resonances with Gaussian line shapes (FWHH = 27.6 {+-} 1 ppm) that do not depend on Mg{sup 2+} or H{sub 2}O content. A correlation between {sup 43}Ca isotropic chemical shifts and mean Ca-O bond distances for crystalline hydrous and anhydrous calcium carbonate phases indicates indistinguishable maximum mean Ca-O bond lengths of {approx}2.45 {angstrom} for all our samples. This value is near the upper end of the published Ca-O bond distance range for biogenic and synthetic ACCs obtained by Ca-X-ray absorption spectroscopy. It is slightly smaller than the values from the structural model of Mgfree ACC by Goodwin et al. obtained from reverse Monte Carlo (RMC) modeling of X-ray scattering data and our own computational molecular dynamics (MD) simulation based on this model. An MD simulation starting with the atomic positions of the Goodwin et al. RMC model using the force field of Raiteri and Gale shows significant structural reorganization during the simulation and that the interconnected carbonate/water-rich channels in the Goodwin et al. model shrink in size over the 2 ns simulation time. The distribution of polyhedrally averaged Ca-O bond distances from the MD simulation is in good agreement with the {sup 43}Ca NMR peak shape, suggesting that local structural disorder dominates the experimental line width of ACC.

Singer, Jared W.; Yazaydin, A. O.; Kirkpatrick, Robert J.; Bowers, Geoffrey M.

2012-05-22

151

Solid-state NMR evidence for elastin-like beta-turn structure in spider dragline silk.  

PubMed

Two-dimensional homo- and heteronuclear solid-state MAS NMR experiments on (13)C/(15)N-proline labeled Argiope aurantia dragline silk provide evidence for an elastin-like beta-turn structure for the repetitive Gly-Pro-Gly-X-X motif prevalent in major ampullate spidroin 2 (MaSp2). PMID:20733981

Jenkins, Janelle E; Creager, Melinda S; Butler, Emily B; Lewis, Randolph V; Yarger, Jeffery L; Holland, Gregory P

2010-09-28

152

High-resolution solid-state NMR of anisotropically mobile molecules under very low-power 1  

E-print Network

]. Low-power decoupling also reduces the radio frequency (rf) load on the spectrometer and allows shorterHigh-resolution solid-state NMR of anisotropically mobile molecules under very low-power 1 H Revised 13 May 2009 Available online 21 May 2009 Keywords: Low-power decoupling Lipid membranes Solid

Hong, Mei

153

Improving the quality of 2D solid-state NMR spectra of microcrystalline proteins by covariance analysisw  

E-print Network

Improving the quality of 2D solid-state NMR spectra of microcrystalline proteins by covariance transformation (2D FT). Since a high spectral resolution is mandatory in both dimensions of 13 C­13 C correlation is obtained from the prescription C = (FT ÁF)1/2 , where F is the matrix of the 2D FT spectrum, FT

154

Characterization of crystal forms of ? -estradiol – thermal analysis, Raman microscopy, X-ray analysis and solid-state NMR  

Microsoft Academic Search

The structure and select crystalline properties of a common drug (estradiol) used in a transdermal drug delivery system are investigated. Four different crystal forms of estradiol (EA, EC, ED and EM) were prepared in the laboratory and characterized by thermal analysis, optical microscopy, Raman microspectroscopy, and solid-state NMR. Variable temperature X-ray studies were carried out on form A (EA) to

N. E. Variankaval; K. I. Jacob; S. M. Dinh

2000-01-01

155

Towards a better description of gallo-phosphate materials in solid state NMR: 1D and 2D correlation studies  

E-print Network

1 Towards a better description of gallo-phosphate materials in solid state NMR: 1D and 2D heteronuclear 31 P-71 Ga correlation using a MAS HMQC experiment in gallo-phosphate materials. The experiment experiment, gallo-phosphates. 1. Introduction Molecular sieves based on metal phosphates have been subject

Boyer, Edmond

156

H Solid-State NMR Investigation of Structure and Dynamics of Anhydrous Proton Conducting Triazole-Functionalized Siloxane Polymers  

E-print Network

1 H Solid-State NMR Investigation of Structure and Dynamics of Anhydrous Proton Conducting Triazole to elucidate the conduction mechanism of an anhydrous proton conducting triazole-functionalized polysiloxane processes of the triazole ring contributing to the proton conduction process are qualitatively

157

Revealing molecular self-assembly and geometry of non-covalent halogen bonding by solid-state NMR spectroscopyw  

E-print Network

Revealing molecular self-assembly and geometry of non-covalent halogen bonding by solid-state NMR813237b We report a new spectroscopic fingerprint of intermolecular contacts in halogen bond-driven self-assembling aggregates and a precise determination of intermolecular NÁ Á ÁI distances in microcrystalline samples. Non-covalent

158

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

E-print Network

ARTICLE Solid-state NMR enhanced by dynamic nuclear polarization as a novel tool for ribosome nanomoles of intact ribosomes and an 800 kDa ribosomal complex we demonstrate that the combination of DNP cellular complexes. The ribosome is a macromolecular machine responsible for cellular protein synthesis

159

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

SciTech Connect

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.

Wang, Tuo; Park, Yong Bum; Caporini, Marc A.; Rosay, Melanie; Zhong, Linghao; Cosgrove, Daniel J.; Hong, Mei

2013-08-29

160

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

SciTech Connect

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.

Wang, Tuo [Ames Laboratory; Park, Yong Bum [Pennsylvania State University; Caporini, Marc A. [Bruker Biospin Corporation; Rosay, Melanie [Bruker Biospin Corporation; Zhong, Linghao [Pennsylvania State University; Cosgrove, Daniel J. [Pennsylvania State University; Hong, Mei [Ames Laboratory

2013-08-29

161

1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems  

NASA Astrophysics Data System (ADS)

Cross polarization (CP) magic angle spinning (MAS) 13C-NMR spectroscopy is a solid state NMR technique widely used to study chemical composition of organic materials with low or no solubility in the common deuterated solvents used to run liquid state NMR experiments. Based on the magnetization transfer from abundant nuclei (with spin of 1 -2) having a high gyromagnetic ratio (?), such as protons, to the less abundant 13C nuclei with low ? values, 13C-CPMAS NMR spectroscopy is often applied in environmental chemistry to obtain quantitative information on the chemical composition of natural organic matter (NOM) (Conte et al., 2004), although its quantitative assessment is still matter of heavy debates. Many authors (Baldock et al., 1997; Conte et al., 1997, 2002; Dria et al., 2002; Kiem et al., 2000; Kögel-Knabner, 2000; Preston, 2001), reported that the application of appropriate instrument setup as well as the use of special pulse sequences and correct spectra elaboration may provide signal intensities that are directly proportional to the amount of nuclei creating a NMR signal. However, many other papers dealt with the quantitative unsuitability of 13C-CPMAS NMR spectroscopy. Among those, Mao et al. (2000), Smernik and Oades (2000 a,b), and Preston (2001) reported that cross-polarized NMR techniques may fail in a complete excitation of the 13C nuclei. In fact, the amount of observable carbons via 13C-CPMAS NMR spectroscopy appeared, in many cases, lower than that measured by a direct observation of the 13C nuclei. As a consequence, cross-polarized NMR techniques may provide spectra where signal distribution may not be representative of the quantitative distribution of the different natural organic matter components. Cross-polarization is obtained after application of an initial 90° x pulse on protons and a further spin lock pulse (along the y axis) having a fixed length (contact time) for both nuclei (1H and 13C) once the Hartmann-Hahn condition is matched. The Hartmann-Hahn condition can be expressed as ?HB1H = ?CB1C, where ?H and ?C are the gyromagnetic ratios of protons and carbons, whereas B1H and B1C are the 1H and 13C radio-frequency (r.f.) fields applied to the nuclei. The Hartmann-Hahn condition is affected by the H-C dipolar interaction strength (Stejskal & Memory, 1994). All the factors affecting dipolar interactions may mismatch the Hartmann-Hahn condition and prevent a quantitative representation of the NOM chemical composition (Conte et al., 2004). It has been reported that under low speed MAS conditions, broad matching profiles are centered around the Hartmann-Hahn condition....... With increasing spinning speed the Hartmann-Hahn matching profiles break down in a series of narrow matching bands separated by the rotor frequency (Stejskal & Memory, 1994). In order to account for the instability of the Hartmann-Hahn condition at higher rotor spin rates (>10 kHz), variable amplitude cross-polarization techniques (RAMP-CP) have been developed (Metz et al., 1996). So far, to our knowledge, the prevailing way used to obtain quantitative 13C-CPMAS NMR results was to optimize the 1H and 13C spin lock r.f. fields on simple standard systems such as glycine and to use those r.f. field values to run experiments on unknown organic samples. The aim of the present study was to experimentally evidence that the stability of the Hartmann-Hahn condition was different for different samples with a known structure. Moreover, Hartmann-Hahn profiles of four different humic acids (HAs) were also provided in order to show that the 1H/13C r.f. spin lock field strength must also be tested on the HAs prior to a quantitative evaluation of their 13C-CPMAS NMR spectra. Baldock, J.A., Oades, J.M., Nelson, P.N., Skene, T.M., Golchin, A. & Clarke, P., 1997. Assessing the extent of decomposition of natural organic materials using solid-state C-13 NMR spectroscopy. Australian Journal of Soil Research, 35, 1061-1083. Conte, P., Piccolo, A., van Lagen, B., Buurman, P. & de Jager, P.A., 1997. Quantitative Aspects of So

Berns, Anne E.; Conte, Pellegrino

2010-05-01

162

Elucidating Metabolic Pathways for Amino Acid Incorporation Into Dragline Spider Silk using 13C Enrichment and Solid State NMR  

PubMed Central

Spider silk has been evolutionarily optimized for contextual mechanical performance over the last 400 million years. Despite precisely balanced mechanical properties, which have yet to be reproduced, the underlying molecular architecture of major ampullate spider silk can be simplified being viewed as a versatile block copolymer. Four primary amino acid motifs: polyalanine, (GA)n, GPGXX, and GGX (X = G,A,S,Q,L,Y) will be considered in this study. Although synthetic mimetics of many of these amino acid motifs have been produced in several biological systems, the source of spider silk’s mechanical integrity remains elusive. Mechanical robustness may be a product not only of the amino acid structure but also of the tertiary structure of the silk. Historically, solid state Nuclear Magnetic Resonance (ssNMR) has been used to reveal the crystalline structure of the polyalanine motif; however, limitations in amino acid labeling techniques have obscured the structures of the GGX and GPGXX motifs thought to be responsible for the structural mobility of spider silk. We describe the use of metabolic pathways to label tyrosine for the first time as well as to improve the labeling efficiency of proline. These improved labeling techniques will allow the previously unknown tertiary structures of major ampullate silk to be probed. PMID:21334448

Creager, Melinda S.; Izdebski, Thomas; Brooks, Amanda E.; Lewis, Randolph V.

2013-01-01

163

Evidence from solid-state NMR for nonhelical conformations in the transmembrane domain of the amyloid precursor protein.  

PubMed

The amyloid precursor protein (APP) is subject to proteolytic processing by ?-secretase within neuronal membranes, leading to Alzheimer's disease-associated ?-amyloid peptide production by cleavage near the midpoint of the single transmembrane (TM) segment of APP. Conformational properties of the TM segment may affect its susceptibility to ?-secretase cleavage, but these properties have not been established definitively, especially in bilayer membranes with physiologically relevant lipid compositions. In this article, we report an investigation of the APP-TM conformation, using (13)C chemical shifts obtained with two-dimensional solid-state NMR spectroscopy as site-specific conformational probes. We find that the APP-TM conformation is not a simple ?-helix, particularly at 37°C in multilamellar vesicles with compositions that mimic the composition of neuronal cell membranes. Instead, we observe a mixture of helical and nonhelical conformations at the N- and C-termini and in the vicinity of the ?-cleavage site. Conformational plasticity of the TM segment of APP may be an important factor in the ?-secretase cleavage mechanism. PMID:21281586

Lu, Jun-Xia; Yau, Wai-Ming; Tycko, Robert

2011-02-01

164

High-Resolution NMR of Quadrupolar Nuclei in the Solid State  

SciTech Connect

This dissertation describes recent developments in solid state nuclear magnetic resonance (NMR), for the most part involving the use of dynamic-angle spinning (DAS) NMR to study quadrupolar nuclei. Chapter 1 introduces some of the basic concepts and theory that will be referred to in later chapters, such as the density operator, product operators, rotations, coherence transfer pathways, phase cycling, and the various nuclear spin interactions, including the quadrupolar interaction. Chapter 2 describes the theory behind motional averaging experiments, including DAS, which is a technique where a sample is spun sequentially about two axis oriented at different angles with respect to the external magnetic field such that the chemical shift and quadrupolar anisotropy are averaged to zero. Work done on various rubidium-87 salts is presented as a demonstration of DAS. Chapter 3 explains how to remove sidebands from DAS and magic-angle spinning (MAS) experiments, which result from the time-dependence of the Hamiltonian under sample spinning conditions, using rotor-synchronized {pi}-pulses. Data from these experiments, known as DAH-180 and MAH-180, respectively, are presented for both rubidium and lead salts. In addition, the applicability of this technique to double rotation (DOR) experiments is discussed. Chapter 4 concerns the addition of cross-polarization to DAS (CPDAS). The theory behind spin locking and cross polarizing quadrupolar nuclei is explained and a method of avoiding the resulting problems by performing cross polarization at 0{sup o} (parallel) with respect to the magnetic field is presented. Experimental results are shown for a sodium-23 compound, sodium pyruvate, and for oxygen-17 labeled L-akmine. In Chapter 5, a method for broadening the Hartmann-Hahn matching condition under MAS, called variable effective field cross-polarization (VEFCI?), is presented, along with experimental work on adamantane and polycarbonate.

Gann, Sheryl Lee

1995-11-30

165

Solid-state NMR analysis of a boron-containing pharmaceutical hydrochloride salt.  

PubMed

A novel crystalline form of the boron-containing antibacterial drug (S)-3-(aminomethyl)-7-(3-hydroxypropoxy)benzo[c] [1,2]oxaborol-1(3H)-ol hydrochloride is studied by solid-state nuclear magnetic resonance (SSNMR) and single-crystal X-ray diffraction techniques. After determination of the crystal structure by X-ray diffraction, SSNMR spectroscopy of this form is performed to obtain structural information using experimental approaches based on dipolar correlation, chemical shift analysis, and quadrupolar interaction analysis. 1H SSNMR experiments at 16.4 T using magic-angle spinning (MAS) and homonuclear dipolar decoupling, 2D SSNMR experiments based on (1)H–(13)C and (1)H–(11)B dipolar heteronuclear correlation, and density functional theory (DFT) calculations are combined in a novel approach to obtain a nearly complete assignment of the (1)H spectrum of this crystalline phase. (11)B and (35)Cl chemical shift and quadrupolar parameters are obtained using the analysis of MAS spectra and are found to be accurately reproduced using DFT calculations. NMR chemical shielding and electric field gradient parameters obtained using these methods are related to hydrogen-bonding trends in the crystal structure. The results illustrate the increasing capability of SSNMR techniques involving (1)H, (11)B, and (35)Cl SSNMR in the analysis of the crystal structure of a pharmaceutical compound containing covalently bonded boron. PMID:23918278

Vogt, Frederick G; Williams, Glenn R; Copley, Royston C B

2013-10-01

166

Distinguishing Polymorphs of the Semiconducting Pigment Copper Phthalocyanine by Solid-state NMR and Raman Spectroscopy  

PubMed Central

Cu(II)(phthalocyanine) (CuPc) is broadly utilized as an archetypal molecular semiconductor and is the most widely used blue printing pigment. CuPc crystallizes in six different forms; the chemical and physical properties are substantially modulated by its molecular packing among these polymorphs. Despite the growing importance of this system, spectroscopic identification of different polymorphs for CuPc has posed difficulties. This study presents the first example of spectroscopic distinction of ?- and ?-forms of CuPc, the most widely used polymorphs, by solid-state NMR (SSNMR) and Raman spectroscopy. 13C high-resolution SSNMR spectra of ?- and ?-CuPc using very-fast magic angle spinning (VFMAS) at 20 kHz show that hyperfine shifts sensitively reflect polymorphs of CuPc. The experimental results were confirmed by ab initio chemical shift calculations. 13C and 1H SSNMR relaxation times of ?- and ?-CuPc under VFMAS also showed marked differences, presumably because of the difference in electronic spin correlation times in the two forms. Raman spectroscopy also provided another reliable method of differentiation between the two polymorphs. PMID:20225842

Shaibat, Medhat A.; Casabianca, Leah B.; Siberio-Perez, Diana Y.; Matzger, Adam J; Ishii, Yoshitaka

2010-01-01

167

Characterization of surface and photooxidative properties of supported metal oxide photocatalysts using solid-state NMR.  

PubMed

In situ solid-state NMR (SSNMR) methodologies have been used to investigate the surface properties and photooxidative reactivities of a number of metal oxide photocatalysts. Adsorption of ethanol on single monolayers of TiO2, SnO2, V205, and WO3 supported on porous Vycor glass results in the formation of hydrogen-bonded ethanol species and metal-bound ethoxide species. The chemical shift of the metal-bound ethoxide species varies with the metal oxide catalyst while the chemical shift of the hydrogen-bonded species is independent of the metal oxide. X-ray powder diffraction, UV-VIS spectroscopy, and SSNMR investigations of ethanol adsorption show that increasing the number of monolayers of TiO2 on the Vycor surface changes the morphology of the catalyst from amorphous at a single monolayer coverage to anatase at a four monolayer coverage. The rate of photocatalytic oxidation of ethanol, acetone, and 2-propanol also increases with increasing TiO2 monolayer coverage. PMID:11993648

Pilkenton, S; Xu, W; Raftery, D

2001-01-01

168

A structural model for Alzheimer's -amyloid fibrils based on experimental constraints from solid state NMR  

NASA Astrophysics Data System (ADS)

We present a structural model for amyloid fibrils formed by the 40-residue -amyloid peptide associated with Alzheimer's disease (A1-40), based on a set of experimental constraints from solid state NMR spectroscopy. The model additionally incorporates the cross- structural motif established by x-ray fiber diffraction and satisfies constraints on A1-40 fibril dimensions and mass-per-length determined from electron microscopy. Approximately the first 10 residues of A1-40 are structurally disordered in the fibrils. Residues 12-24 and 30-40 adopt -strand conformations and form parallel -sheets through intermolecular hydrogen bonding. Residues 25-29 contain a bend of the peptide backbone that brings the two -sheets in contact through sidechain-sidechain interactions. A single cross- unit is then a double-layered -sheet structure with a hydrophobic core and one hydrophobic face. The only charged sidechains in the core are those of D23 and K28, which form salt bridges. Fibrils with minimum mass-per-length and diameter consist of two cross- units with their hydrophobic faces juxtaposed.

Petkova, Aneta T.; Ishii, Yoshitaka; Balbach, John J.; Antzutkin, Oleg N.; Leapman, Richard D.; Delaglio, Frank; Tycko, Robert

2002-12-01

169

Characterization of Stratum Corneum Molecular Dynamics by Natural-Abundance 13C Solid-State NMR  

PubMed Central

Despite the enormous potential for pharmaceutical applications, there is still a lack of understanding of the molecular details that can contribute to increased permeability of the stratum corneum (SC). To investigate the influence of hydration and heating on the SC, we record the natural-abundance 13C signal of SC using polarization transfer solid-state NMR methods. Resonance lines from all major SC components are assigned. Comparison of the signal intensities obtained with the INEPT and CP pulse sequences gives information on the molecular dynamics of SC components. The majority of the lipids are rigid at 32°C, and those lipids co-exist with a small pool of mobile lipids. The ratio between mobile and rigid lipids increases with hydration. An abrupt change of keratin filament dynamics occurs at RH?=?80–85%, from completely rigid to a structure with rigid backbone and mobile protruding terminals. Heating has a strong effect on the lipid mobility, but only a weak influence on the keratin filaments. The results provide novel molecular insight into how the SC constituents are affected by hydration and heating, and improve the understanding of enhanced SC permeability, which is associated with elevated temperatures and SC hydration. PMID:23626744

Bouwstra, Joke A.; Sparr, Emma; Topgaard, Daniel

2013-01-01

170

Structure and backbone dynamics of a microcrystalline metalloprotein by solid-state NMR  

PubMed Central

We introduce a new approach to improve structural and dynamical determination of large metalloproteins using solid-state nuclear magnetic resonance (NMR) with 1H detection under ultrafast magic angle spinning (MAS). The approach is based on the rapid and sensitive acquisition of an extensive set of 15N and 13C nuclear relaxation rates. The system on which we demonstrate these methods is the enzyme Cu, Zn superoxide dismutase (SOD), which coordinates a Cu ion available either in Cu+ (diamagnetic) or Cu2+ (paramagnetic) form. Paramagnetic relaxation enhancements are obtained from the difference in rates measured in the two forms and are employed as structural constraints for the determination of the protein structure. When added to 1H-1H distance restraints, they are shown to yield a twofold improvement of the precision of the structure. Site-specific order parameters and timescales of motion are obtained by a Gaussian axial fluctuation (GAF) analysis of the relaxation rates of the diamagnetic molecule, and interpreted in relation to backbone structure and metal binding. Timescales for motion are found to be in the range of the overall correlation time in solution, where internal motions characterized here would not be observable. PMID:22723345

Knight, Michael J.; Pell, Andrew J.; Bertini, Ivano; Felli, Isabella C.; Gonnelli, Leonardo; Pierattelli, Roberta; Herrmann, Torsten; Emsley, Lyndon; Pintacuda, Guido

2012-01-01

171

Solid-state NMR studies of metal-free SOD1 fibrillar structures.  

PubMed

Copper-zinc superoxide dismutase 1 (SOD1) is present in the protein aggregates deposited in motor neurons of amyotrophic lateral sclerosis (ALS) patients. ALS is a neurodegenerative disease that can be either sporadic (ca. 90%) or familial (fALS). The most widely studied forms of fALS are caused by mutations in the sequence of SOD1. Ex mortuo SOD1 aggregates are usually found to be amorphous. In vitro SOD1, in its immature reduced and apo state, forms fibrillar aggregates. Previous literature data have suggested that a monomeric SOD1 construct, lacking loops IV and VII, (apoSOD?IV-VII), shares the same fibrillization properties of apoSOD1, both proteins having the common structural feature of the central ?-barrel. In this work, we show that structural information can be obtained at a site-specific level from solid-state NMR. The residues that are sequentially assignable are found to be located at the putative nucleation site for fibrillar species formation in apoSOD, as detected by other experimental techniques. PMID:24719206

Banci, Lucia; Blaževitš, Olga; Cantini, Francesca; Danielsson, Jens; Lang, Lisa; Luchinat, Claudio; Mao, Jiafei; Oliveberg, Mikael; Ravera, Enrico

2014-06-01

172

Phosphate defects and apatite inclusions in coral skeletal aragonite revealed by solid-state NMR spectroscopy  

NASA Astrophysics Data System (ADS)

Recent development of paleo-nutrient proxies based on the phosphorus/calcium (P/Ca) ratio in tropical- and deep-water corals (also known as cold-water corals) require an understanding of the processes by which P is incorporated into the coral skeletal aragonite. Here, we apply single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy to determine the speciation of P in coral aragonite. The results show that the majority of P occurs as phosphate defects in the aragonite structure, but in many samples a significant fraction of the P occurs also in crystalline hydroxylapatite inclusions. Quantification of the amount of hydroxylapatite indicates that its presence is not related simply to external environmental factors and that it can occur at varying abundances in different parts of the same corallite. Since there is currently no model available to describe the relationship between dissolved inorganic phosphate and its incorporation as apatite inclusions into carbonates, careful screening of samples which contain only phosphate in the aragonite structure or selective microsampling could improve proxy development.

Mason, Harris E.; Montagna, Paolo; Kubista, Laura; Taviani, Marco; McCulloch, Malcolm; Phillips, Brian L.

2011-12-01

173

Investigations on ferroelectric liquid crystal by high resolution TEM and solid state 13C NMR.  

PubMed

In order to investigate the structural and dynamical properties of ferroelectric liquid crystal (FLC) in different phases a model compound [4-(3)-(S)-methyl-2-(S)-chloropentanoyloxy)]-4'-nonyloxy-biphenyl (3M2CPNOB) is synthesized. High resolution transmission electron microscopy (HR-TEM) is applied to observe the morphology of 3M2CPNOB and temperature-dependent solid state (13)C NMR to record (13)C chemical shifts at different phases. A liquid nitrogen quenching method is used to maintain the conformation of the mesophases for HR-TEM experiments. TEM images show that all the smectic A (SmA), smectic C* (SmC*) and crystalline phases have lamellar morphology. The interplanar distances in the crystalline phase are smaller than those in SmA and SmC* phases because of denser arrangement of the molecules. Both (13)C chemical shifts and line shape vary with different phases. The experimental results suggest that SmC* phase as an intermediate occurs in the anisotropy transition process from SmA to crystalline phase, the helical structure of the SmC* phase unwinds in the magnetic field and the conformations of the SmA and isotropic phase are very similar. PMID:21967597

Zhao, Yongxia; Yang, Yanqin; Xu, Jingwei; Yang, Wei; Zhou, Yunchun; Jiang, Zijiang; Ge, Xin

2011-11-17

174

Improved pulse sequences for pure exchange solid-state NMR spectroscopy.  

PubMed

Spin-exchange experiments are useful for improving the resolution and establishment of sequential assignments in solid-state NMR spectra of uniformly (15)N-labeled proteins oriented macroscopically in phospholipid bilayers. To exploit this advantage fully, it is crucial that the diagonal peaks in the two-dimensional exchange spectra are suppressed. This may be accomplished using the recent pure-exchange (PUREX) experiments, which, however, suffer from up to a threefold reduction of the cross-peak intensity relative to experiments without diagonal-peak suppression. This loss in sensitivity may severely hamper the applicability for the study of membrane proteins. In this paper, we present a two-dimensional exchange experiment (iPUREX) which improves the PUREX sensitivity by 50%. The performance of iPUREX is demonstrated experimentally by proton-mediated (15)N-(15)N spin-exchange experiments for a (15)N-labeled N-acetyl-L-valyl-L-leucine dipeptide. The relevance of exchange experiments with diagonal-peak suppression for large, uniformly (15)N-labeled membrane proteins in oriented phospholipid bilayers is demonstrated numerically for the G-protein coupled receptor rhodopsin. PMID:14745809

Vosegaard, Thomas; Nielsen, Niels C

2004-02-01

175

29Si NMR in solid state with CPMG acquisition under MAS  

SciTech Connect

A remarkable enhancement of sensitivity can be often achieved in {sup 29}Si solid-state NMR by applying the well-known Carr-Purcell-Meiboom-Gill (CPMG) train of rotor-synchronized {pi} pulses during the detection of silicon magnetization. Here, several one- and two-dimensional (1D and 2D) techniques are used to demonstrate the capabilities of this approach. Examples include 1D {sup 29}Si{l_brace}X{r_brace} CPMAS spectra and 2D {sup 29}Si{l_brace}X{r_brace} HETCOR spectra of mesoporous silicas, zeolites and minerals, where X = {sup 1}H or {sup 27}Al. Data processing methods, experimental strategies and sensitivity limits are discussed and illustrated by experiments. The mechanisms of transverse dephasing of {sup 29}Si nuclei in solids are analyzed. Fast magic angle spinning, at rates between 25 and 40 kHz, is instrumental in achieving the highest sensitivity gain in some of these experiments. In the case of {sup 29}Si-{sup 29}Si double-quantum techniques, CPMG detection can be exploited to measure homonuclear J-couplings.

Wiench, J.W.; Lin, V.S.-Y.; Pruski, M.

2008-05-20

176

Characterization of stratum corneum molecular dynamics by natural-abundance ¹³C solid-state NMR.  

PubMed

Despite the enormous potential for pharmaceutical applications, there is still a lack of understanding of the molecular details that can contribute to increased permeability of the stratum corneum (SC). To investigate the influence of hydration and heating on the SC, we record the natural-abundance (13)C signal of SC using polarization transfer solid-state NMR methods. Resonance lines from all major SC components are assigned. Comparison of the signal intensities obtained with the INEPT and CP pulse sequences gives information on the molecular dynamics of SC components. The majority of the lipids are rigid at 32°C, and those lipids co-exist with a small pool of mobile lipids. The ratio between mobile and rigid lipids increases with hydration. An abrupt change of keratin filament dynamics occurs at RH?=?80-85%, from completely rigid to a structure with rigid backbone and mobile protruding terminals. Heating has a strong effect on the lipid mobility, but only a weak influence on the keratin filaments. The results provide novel molecular insight into how the SC constituents are affected by hydration and heating, and improve the understanding of enhanced SC permeability, which is associated with elevated temperatures and SC hydration. PMID:23626744

Björklund, Sebastian; Nowacka, Agnieszka; Bouwstra, Joke A; Sparr, Emma; Topgaard, Daniel

2013-01-01

177

Solid-state NMR investigations of peptide-lipid interactions of the transmembrane domain of a plant-derived protein, Hcf106.  

PubMed

The chloroplast twin arginine translocation system transports highly folded precursor proteins across the thylakoid using the protonmotive force as its only energy source. Hcf106 and another thylakoid protein, cpTatC compose the precursor receptor complex. Hcf106 is predicted to contain a single amino terminal transmembrane domain (TMD) followed by a Pro-Gly hinge, an amphipathic ?-helix, and a loosely structured carboxyl terminus. Hcf106 has been shown biochemically to insert spontaneously into thylakoid membranes; however, how this occurs is not understood. To investigate how Hcf106 inserts itself into the membrane unassisted, solid-state NMR spectroscopy was used to investigate the membrane activity of the TMD. A synthetic peptide of the Hcf106 TMD was incorporated into multilamellar vesicles made of 100% 1-palmitoyl-2-oleoyl-sn-glycero-phosphocholine (POPC) or 85%:15% ratio with monogalactosyl diacylglycerol (POPC/MGDG) to probe peptide-lipid interaction. Solid-state (31)P NMR and (2)H NMR spectroscopic techniques were used to reveal peptide perturbations of the phospholipid membranes. Changes in spectral lineshape, chemical shift anisotropy width, (31)P T1 relaxation time and SCD order parameters demonstrated that the Hcf106 TMD peptide interacted with the phospholipids. Furthermore, the comparison between POPC and POPC/MGDG multilamellar vesicles indicated that lipid bilayer composition affected the peptide-lipid interaction with the peptide interacting preferentially with vesicles that more closely mimic the thylakoid. PMID:24075840

Zhang, Lei; Liu, Lishan; Maltsev, Sergey; Lorigan, Gary A; Dabney-Smith, Carole

2013-01-01

178

Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.  

PubMed

Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined ?iso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and ?33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (?11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements. PMID:24581866

Peri?, Berislav; Gautier, Régis; Pickard, Chris J; Bosio?i?, Marko; Grbi?, Mihael S; Požek, Miroslav

2014-01-01

179

Efficient design of multituned transmission line NMR probes: the electrical engineering approach.  

PubMed

Transmission line-based multi-channel solid state NMR probes have many advantages regarding the cost of construction, number of RF-channels, and achievable RF-power levels. Nevertheless, these probes are only rarely employed in solid state-NMR-labs, mainly owing to the difficult experimental determination of the necessary RF-parameters. Here, the efficient design of multi-channel solid state MAS-NMR probes employing transmission line theory and modern techniques of electrical engineering is presented. As technical realization a five-channel ((1)H, (31)P, (13)C, (2)H and (15)N) probe for operation at 7 Tesla is described. This very cost efficient design goal is a multi port single coil transmission line probe based on the design developed by Schaefer and McKay. The electrical performance of the probe is determined by measuring of Scattering matrix parameters (S-parameters) in particular input/output ports. These parameters are compared to the calculated parameters of the design employing the S-matrix formalism. It is shown that the S-matrix formalism provides an excellent tool for examination of transmission line probes and thus the tool for a rational design of these probes. On the other hand, the resulting design provides excellent electrical performance. From a point of view of Nuclear Magnetic Resonance (NMR), calibration spectra of particular ports (channels) are of great importance. The estimation of the ?/2 pulses length for all five NMR channels is presented. PMID:21316931

Frydel, J A; Krzystyniak, M; Pienkowski, D; Pietrzak, M; de Sousa Amadeu, N; Ratajczyk, T; Idzik, K; Gutmann, T; Tietze, D; Voigt, S; Fenn, A; Limbach, H H; Buntkowsky, G

2011-01-01

180

De?Novo 3D Structure Determination from Sub-milligram Protein Samples by Solid-State 100?kHz MAS NMR Spectroscopy.  

PubMed

Solid-state NMR spectroscopy is an emerging tool for structural studies of crystalline, membrane-associated, sedimented, and fibrillar proteins. A major limitation for many studies is still the large amount of sample needed for the experiments, typically several isotopically labeled samples of 10-20?mg each. Here we show that a new NMR probe, pushing magic-angle sample rotation to frequencies around 100?kHz, makes it possible to narrow the proton resonance lines sufficiently to provide the necessary sensitivity and spectral resolution for efficient and sensitive proton detection. Using restraints from such spectra, a well-defined de novo structure of the model protein ubiquitin was obtained from two samples of roughly 500??g protein each. This proof of principle opens new avenues for structural studies of proteins available in microgram, or tens of nanomoles, quantities that are, for example, typically achieved for eukaryotic membrane proteins by in-cell or cell-free expression. PMID:25225004

Agarwal, Vipin; Penzel, Susanne; Szekely, Kathrin; Cadalbert, Riccardo; Testori, Emilie; Oss, Andres; Past, Jaan; Samoson, Ago; Ernst, Matthias; Böckmann, Anja; Meier, Beat H

2014-11-01

181

Lipid-Protein Correlations in Nanoscale Phospholipid Bilayers by Solid-State NMR  

PubMed Central

Nanodiscs are an example of discoidal nanoscale lipid/protein particles that have been extremely useful for the biochemical and biophysical characterization of membrane proteins. They are discoidal lipid bilayer fragments encircled and stabilized by two amphipathic helical proteins named membrane scaffolding protein (MSP), ~10 nm in size. Nanodiscs are homogeneous, easily prepared with reproducible success, amenable to preparations with a variety of lipids, and stable under a range of temperatures. Here we present solid-state NMR (SSNMR) studies on lyophilized, rehydrated POPC Nanodiscs prepared with uniformly 13C, 15N-labeled MSP1D1 (?1-11 truncated MSP). Under these conditions, by SSNMR we directly determine the gel-to-liquid crystal lipid phase transition to be at 3 ± 2 °C. Above this phase transition, the lipid 1H signals have slow transverse relaxation, enabling filtering experiments as previously demonstrated for lipid vesicles. We incorporate this approach into two- and three-dimensional heteronuclear SSNMR experiments to examine the MSP1D1 residues interfacing with the lipid bilayer. These 1H-13C and 1H-13C-13C correlation spectra are used to identify and quantify the number of lipid-correlated and solvent-exposed residues by amino acid type, which furthermore is compared with molecular dynamics studies of MSP1D1 in Nanodiscs. This study demonstrates the utility of SSNMR experiments with Nanodiscs for examining lipid-protein interfaces and has important applications for future structural studies of membrane proteins in physiologically relevant formulations. PMID:20804175

Kijac, Aleksandra; Shih, Amy Y.; Nieuwkoop, Andrew J.; Schulten, Klaus; Sligar, Stephen G.; Rienstra, Chad M.

2011-01-01

182

Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling  

NASA Astrophysics Data System (ADS)

Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation.

Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

2007-05-01

183

Structural water in carbonated hydroxylapatite and fluorapatite: confirmation by solid state (2)H NMR.  

PubMed

Water is well recognized as an important component in bone, typically regarded as a constituent of collagen, a pore-filling fluid in bone, and an adsorbed species on the surface of bone crystallites. The possible siting and role of water within the structure of the apatite crystallites have not been fully explored. In our experiments, carbonated hydroxyl- and fluorapatites were prepared in D(2)O and characterized by elemental analysis, thermal gravimetric analysis, powder X-ray diffraction, and infrared and Raman spectroscopy. Two hydroxylapatites and two fluorapatites, with widely different amounts of carbonate were analyzed by solid state (2)H NMR spectroscopy using the quadrupole echo pulse sequence, and each spectrum showed one single line as well as a low-intensity powder pattern. The relaxation time of 7.1 ms for 5.9 wt% carbonated hydroxylapatite indicates that the single line is likely due to rapid, high-symmetry jumps in translationally rigid D(2)O molecules, indicative of structural incorporation within the lattice. Discrimination between structurally incorporated and adsorbed water is enhanced by the rapid exchange of surface D(2)O with atmospheric H(2)O. Moreover, a (2)H resonance was observed for samples dried under a variety of conditions, including in vacuo heating to 150°C. In contrast, a sample heated to 500°C produced no deuterium resonance, indicating that structural water had been released by that temperature. We propose that water is located in the c-axis channels. Because structural water is observed even for apatites with very low carbonate content, some of the water molecules must lie between the monovalent ions. PMID:22057814

Yoder, Claude H; Pasteris, Jill D; Worcester, Kimberly N; Schermerhorn, Demetra V

2012-01-01

184

2H-solid state NMR and DSC study of isobutyric acid in mesoporous silica materials.  

PubMed

Solid state deuterium NMR has been used to study the molecular motion of d(6)-isobutyric acid (d(6)-iBA) in the pure (unconfined) state and confined in the cylindrical pores of two periodic mesoporous silica materials (MCM-41, pore size 3.3 nm and SBA-15, pore size 8 nm), and in a controlled pore glass (CPG-10-75, pore size ca. 10 nm). The line shape analysis of the spectra at different temperatures revealed three rotational states of the iBA molecules: liquid (fast anisotropic reorientation of the molecule), solid I (rotation of the methyl group) and solid II (no rotational motion on the time scale of the experiment). Transition temperatures between these states were determined from the temperature dependence of the fraction of molecules in these states. Whereas the solid I-solid II transition temperature is not affected by confinement, a significant lowering of the liquid-solid I transition temperature in the pores relative to the bulk acid was found for the three matrix materials, exhibiting an unusual dependence on pore size and pore morphology. Complementary DSC measurements on the same systems show that the rotational melting (solid I-liquid) of d(6)-iBA in the pores occurs at a temperature 20-45 K below the thermodynamic melting point. This finding indicated that the decoupling of rotational and translational degrees of freedom in phase transitions in confined systems previously found for benzene is not restricted to molecules with non-specific interactions, but represents a more general phenomenon. PMID:17487322

Vyalikh, A; Emmler, Th; Shenderovich, I; Zeng, Y; Findenegg, G H; Buntkowsky, G

2007-06-14

185

The thermal reactions of muscovite studied by high-resolution solid-state 29Si and 27AI NMR  

Microsoft Academic Search

Studies of two muscovites of different iron contents, using solid-state NMR with magic-angle-spinning (MAS) combined with X-ray powder diffraction, thermal analysis and57Fe Mössbauer spectroscopy, suggest that dehydroxylation occurs by a homogeneous rather than an inhomogeneous mechanism, forming a dehydroxylate in which the aluminium is predominantly 5-coordinate. On further decomposition at about 1100° C, the tetrahedral layer and interlayer K+ form

K. J. D. Mackenzie; I. W. M. Brown; C. M. Cardile; R. H. Meinhold

1987-01-01

186

Magic Angle Spinning and Oriented Sample Solid State NMR Structural Restraints Combine for Influenza A M2 Protein Functional Insights  

PubMed Central

As a small tetrameric helical membrane protein, the M2 proton channel structure is highly sensitive to its environment. As a result, structural data from a lipid bilayer environment has proven to be essential for describing the conductance mechanism. While oriented sample solid state NMR has provided a high resolution backbone structure in lipid bilayers, quaternary packing of the helices and many of the sidechain conformations have been poorly restrained. Furthermore, an understanding of the quaternary structural stability has remained a mystery. Here, the isotropic chemical shift data and interhelical cross peaks from magic angle spinning solid state NMR of a liposomal preparation strongly support the quaternary structure of the transmembrane helical bundle as a dimer of dimers structure. The data also explains how the tetrameric stability is enhanced once two charges are absorbed by the His37 tetrad prior to activation of this proton channel. The combination of these two solid state NMR techniques appear to be a powerful approach for characterizing helical membrane protein structure. PMID:22616841

Can, Thach V.; Sharma, Mukesh; Hung, Ivan; Gor'kov, Peter L.; Brey, William W.; Cross, Timothy A.

2012-01-01

187

Dynamics of benzimidazole ethylphosphonate: a solid-state NMR study of anhydrous composite proton-conducting electrolytes.  

PubMed

Imidazole phosphate and phosphonate solid acids model the hydrogen-bonding networks and dynamics of the anhydrous electrolyte candidate for proton exchange membrane fuel cells. Solid-state NMR reveals that phosphate and phosphonate anion dynamics dominate the rate of long-range proton transport, and that the presence of a membrane host facilitates proton mobility, as evidenced by a decreased correlation time of the composites (80 ± 15 ms) relative to the pristine salt (101 ± 5 ms). Benzimidazole ethylphosphonate (Bi-ePA) is chosen as a model salt to investigate the membrane system. The hydrogen-bonding structure of Bi-ePA is established using X-ray diffraction coupled with solid-state (1)H-(1)H DQC NMR. The anion dynamics has been determined using solid-state (31)P CODEX NMR. By comparing the dynamics of ethylphosphonate groups in pristine salt and membrane-salt composites, it is clear that the rotation process involves three-site exchange. Through data interpretation, a stretched exponential function is introduced with the stretching exponent, ?, ranging 0 < ? ? 1. The (31)P CODEX data for pristine salt are fitted with single exponential decay where ? = 1; however, the data for the membrane-salt composites are fitted with stretched exponential functions, where ? has a constant value of 0.5. This ? value suggests a non-Gaussian distribution of the dynamic systems in the composite sample, which is introduced by the membrane host. PMID:24056920

Yan, Z Blossom; De Almeida, Nicole E; Traer, Jason W; Goward, Gillian R

2013-11-01

188

High-field 19.6T 27Al solid-state MAS NMR of in vitro aluminated brain tissue  

Microsoft Academic Search

The combination of 27Al high-field solid-state NMR (19.6T) with rapid spinning speeds (17.8kHz) is used to acquire 27Al NMR spectra of total RNA human brain temporal lobe tissues exposed to 0.10mM Al3+ (as AlCl3) and of human retinal pigment epithelial cells (ARPE-19), grown in 0.10mM AlCl3. The spectra of these model systems show multiple Al3+ binding sites, good signal\\/noise ratios

Pamela L. Bryant; Walter J. Lukiw; Zhehong Gan; Randall W. Hall; Leslie G. Butler

2004-01-01

189

High-field 19.6 T 27Al solid-state MAS NMR of in vitro aluminated brain tissue  

Microsoft Academic Search

The combination of 27Al high-field solid-state NMR (19.6T) with rapid spinning speeds (17.8kHz) is used to acquire 27Al NMR spectra of total RNA human brain temporal lobe tissues exposed to 0.10mM Al3+ (as AlCl3) and of human retinal pigment epithelial cells (ARPE-19), grown in 0.10mM AlCl3. The spectra of these model systems show multiple Al3+ binding sites, good signal\\/noise ratios

Pamela L. Bryant; Walter J. Lukiw; Zhehong Gan; Randall W. Hall; Leslie G. Butler

2004-01-01

190

Lipid bilayer preparations of membrane proteins for oriented and magic-angle spinning solid-state NMR samples  

PubMed Central

Solid-state NMR spectroscopy has been used successfully for characterizing the structure and dynamics of membrane proteins as well as their interactions with other proteins in lipid bilayers. such an environment is often necessary for achieving native-like structures. sample preparation is the key to this success. Here we present a detailed description of a robust protocol that results in high-quality membrane protein samples for both magic-angle spinning and oriented-sample solid-state NMR. the procedure is demonstrated using two proteins: CrgA (two transmembrane helices) and rv1861 (three transmembrane helices), both from Mycobacterium tuberculosis. the success of this procedure relies on two points. First, for samples for both types of NMR experiment, the reconstitution of the protein from a detergent environment to an environment in which it is incorporated into liposomes results in ‘complete’ removal of detergent. second, for the oriented samples, proper dehydration followed by rehydration of the proteoliposomes is essential. By using this protocol, proteoliposome samples for magic-angle spinning NMR and uniformly aligned samples (orientational mosaicity of <1°) for oriented-sample NMR can be obtained within 10 d. PMID:24157546

Das, Nabanita; Murray, Dylan T; Cross, Timothy A

2014-01-01

191

Sodium ion effect on silk fibroin conformation characterized by solid-state NMR and generalized 2D NMR NMR correlation  

NASA Astrophysics Data System (ADS)

In the present work, we investigated Na + ion effect on the silk fibroin (SF) conformation. Samples are Na +-involved regenerated silk fibroin films. 13C CP-MAS NMR demonstrates that as added [Na +] increases, partial silk fibroin conformation transit from helix-form to ?-form at certain Na + ion concentration which is much higher than that in Bombyx mori silkworm gland. The generalized two-dimensional NMR-NMR correlation analysis reveals that silk fibroin undergoes several intermediate states during its conformation transition process as [Na +] increase. The appearance order of the intermediates is followed as: helix and/or random coil ? helix-like ? ?-sheet-like ? ?-sheet, which is the same as that produced by pH decrease from 6.8 to 4.8 in the resultant regenerated silk fibroin films. The binding sites of Na + to silk fibroin might involve the carbonyl oxygen atom of certain amino acids sequence which could promote the formation of ?-sheet conformation. Since the Na +sbnd O bond is weak, the ability of Na + inducing the secondary structure transition is weaker than those of Ca 2+, Cu 2+ and even K +. It is maybe a reason why the sodium content is much lower than potassium in the silkworm gland.

Ruan, Qing-Xia; Zhou, Ping

2008-07-01

192

Solid-State 2H NMR Shows Equivalence of Dehydration and Osmotic Pressures in Lipid Membrane Deformation  

PubMed Central

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 (SCD) 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. PMID:21190661

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

2011-01-01

193

Raman Spectroscopy and Solid State NMR Characterization of Carbonates and Metal-Oxide Clusters  

NASA Astrophysics Data System (ADS)

Presented here is data showing the utility of combining Raman spectroscopy and solid-state Nuclear Magnetic Resonance. These techniques were combined to study local structure of carbonate minerals and metal oxides.

Moore, J. K.; Hammann, B. A.; Surface, J. A.; Ma, Z. L.; Hayes, S. E.

2014-06-01

194

Methods for Increasing Sensitivity and Throughput of Solid-State NMR Spectroscopy of Pharmaceutical Solids  

E-print Network

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy has been demonstrated to be a powerful technique for investigating solid dosage formulations. SSNMR has the ability to determine physical form, molecular structure, ...

Schieber, Loren

2010-01-22

195

Applications of DNP and solid-state NMR for protein structure determination  

E-print Network

Magic Angle Spinning (MAS) solid state nuclear magnetic resonance (SSNMR) is a developing method for determining the structures and studying the dynamics and functions of biological molecules. This method is particularly ...

Mayrhofer, Rebecca Maria

2010-01-01

196

Comprehensive solid-state NMR analysis reveals the effects of N-methylation on the molecular dynamics of glycine.  

PubMed

Molecular dynamics of metabolites are important for their interactions and functions. To understand the structural dependence of molecular dynamics for N-methylated glycines, we comprehensively measured the (13)C and (1)H spin-lattice relaxation times for sarcosine, N,N-dimethylglycine, betaine, and betaine hydrochloride over a temperature range of 178-460 K. We found that the reorientations of methyl groups were observed for all these molecules, whereas reorientations of whole trimethylamine groups were detected in betaines. While similar rotational properties were observed for methyl groups in N,N-dimethylglycine and those in betaine, three methyl groups in betaine hydrochloride had different motional properties (E(a) ? 20.5 kJ/mol, ?(0) ? 1.85 × 10(-13) s; E(a) ? 13.9 kJ/mol, ?(0) ? 2.1 × 10(-12) s; E(a) ? 15.8 kJ/mol, ?(0) ? 1.1 × 10(-12) s). N,N-Dimethylglycine showed a phase transition at 348.5 K with changed relaxation behavior for methyl groups showing distinct E(a) and ?(0) values. The DIPSHIFT experiments showed that CH(3) and CH(2) moieties in these molecules had dipolar-dephasing curves similar to these moieties in alanine and glycine. The activation energies for CH(3) rotations positively correlated with the number of substituted methyl groups. These findings provided useful information for the structural dependence of molecular dynamics for N-methylated glycines and demonstrated solid-state NMR as a useful tool for probing the structure-dynamics relationships. PMID:22142308

Huang, Jing; Jiang, Limiao; Ren, Pingping; Zhang, Limin; Tang, Huiru

2012-01-12

197

P solid-state NMR studies of the dependence of inter-bilayer water dynamics on lipid headgroup structure and membrane peptides  

E-print Network

2D 1 H­31 P solid-state NMR studies of the dependence of inter-bilayer water dynamics on lipid moderate magic-angle spinning, making 1 H 1D and 2D MAS NMR the method of choice for investigating membrane group is not sufficiently strong to be detectable by NMR. Instead, water-31 P correlation peaks in 2D

Hong, Mei

198

250GHz CW gyrotron oscillator for dynamic nuclear polarization in biological solid state NMR.  

PubMed

In this paper, we describe a 250 GHz gyrotron oscillator, a critical component of an integrated system for magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments at 9T, corresponding to 380 MHz (1)H frequency. The 250 GHz gyrotron is the first gyro-device designed with the goal of seamless integration with an NMR spectrometer for routine DNP enhanced NMR spectroscopy and has operated under computer control for periods of up to 21 days with a 100% duty cycle. Following a brief historical review of the field, we present studies of the membrane protein bacteriorhodopsin (bR) using DNP enhanced multidimensional NMR. These results include assignment of active site resonances in [U-(13)C, (15)N]-bR and demonstrate the utility of DNP for studies of membrane proteins. Next, we review the theory of gyro-devices from quantum mechanical and classical viewpoints and discuss the unique considerations that apply to gyrotron oscillators designed for DNP experiments. We then characterize the operation of the 250 GHz gyrotron in detail, including its long-term stability and controllability. We have measured the spectral purity of the gyrotron emission using both homodyne and heterodyne techniques. Radiation intensity patterns from the corrugated waveguide that delivers power to the NMR probe were measured using two new techniques to confirm pure mode content: a thermometric approach based on the temperature-dependent color of liquid crystalline media applied to a substrate and imaging with a pyroelectric camera. We next present a detailed study of the mode excitation characteristics of the gyrotron. Exploration of the operating characteristics of several fundamental modes reveals broadband continuous frequency tuning of up to 1.8 GHz as a function of the magnetic field alone, a feature that may be exploited in future tunable gyrotron designs. Oscillation of the 250 GHz gyrotron at the second harmonic of cyclotron resonance begins at extremely low beam currents (as low 12 mA) at frequencies between 320 and 365 GHz, suggesting an efficient route for the generation of even higher frequency radiation. The low starting currents were attributed to an elevated cavity Q, which is confirmed by cavity thermal load measurements. We conclude with an appendix containing a detailed description of the control system that safely automates all aspects of the gyrotron operation. PMID:17942352

Bajaj, Vikram S; Hornstein, Melissa K; Kreischer, Kenneth E; Sirigiri, Jagadishwar R; Woskov, Paul P; Mak-Jurkauskas, Melody L; Herzfeld, Judith; Temkin, Richard J; Griffin, Robert G

2007-12-01

199

250 GHz CW Gyrotron Oscillator for Dynamic Nuclear Polarization in Biological Solid State NMR  

PubMed Central

In this paper, we describe a 250 GHz gyrotron oscillator, a critical component of an integrated system for magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments at 9T, corresponding to 380 MHz 1H frequency. The 250 GHz gyrotron is the first gyro-device designed with the goal of seamless integration with an NMR spectrometer for routine DNP-enhanced NMR spectroscopy and has operated under computer control for periods of up to 21 days with a 100% duty cycle. Following a brief historical review of the field, we present studies of the membrane protein bacteriorhodopsin (bR) using DNP-enhanced multidimensional NMR. These results include assignment of active site resonances in [U-13C,15N]-bR and demonstrate the utility of DNP for studies of membrane proteins. Next, we review the theory of gyro-devices from quantum mechanical and classical viewpoints and discuss the unique considerations that apply to gyrotron oscillators designed for DNP experiments. We then characterize the operation of the 250 GHz gyrotron in detail, including its long-term stability and controllability. We have measured the spectral purity of the gyrotron emission using both homodyne and heterodyne techniques. Radiation intensity patterns from the corrugated waveguide that delivers power to the NMR probe were measured using two new techniques to confirm pure mode content: a thermometric approach based on the temperature-dependent color of liquid crystalline media applied to a substrate and imaging with a pyroelectric camera. We next present a detailed study of the mode excitation characteristics of the gyrotron. Exploration of the operating characteristics of several fundamental modes reveals broadband continuous frequency tuning of up to 1.8 GHz as a function of the magnetic field alone, a feature that may be exploited in future tunable gyrotron designs. Oscillation of the 250 GHz gyrotron at the second harmonic of cyclotron resonance begins at extremely low beam currents (as low 12 mA) at frequencies between 320–365 GHz, suggesting an efficient route for the generation of even higher frequency radiation. The low starting currents were attributed to an elevated cavity Q, which is confirmed by cavity thermal load measurements. We conclude with an appendix containing a detailed description of the control system that safely automates all aspects of the gyrotron operation. PMID:17942352

Bajaj, Vikram S.; Hornstein, Melissa K.; Kreischer, Kenneth E.; Sirigiri, Jagadishwar R.; Woskov, Paul P.; Mak-Jurkauskas, Melody L.; Herzfeld, Judith; Temkin, Richard J.; Griffin, Robert G.

2009-01-01

200

CHHC and [superscript 1]H–[superscript 1]H magnetization exchange: Analysis by experimental solid-state NMR and 11-spin density-matrix simulations  

E-print Network

A protocol is presented for correcting the effect of non-specific cross-polarization in CHHC solid-state MAS NMR experiments, thus allowing the recovery of the [superscript 1]H–[superscript 1]H magnetization exchange ...

Aluas, Mihaela

201

From molecular complexes to complex metallic nanostructures--2H solid-state NMR studies of ruthenium-containing hydrogenation catalysts.  

PubMed

In the last years, the combination of (2)H solid-state NMR techniques with quantum-chemical calculations has evolved into a powerful spectroscopic tool for the characterization of the state of hydrogen on the surfaces of heterogeneous catalysts. In the present minireview, a brief summary of this development is given, in which investigations of the structure and dynamics of hydrogen in molecular complexes, clusters and nanoparticle systems are presented, aimed to understand the reaction mechanisms on the surface of hydrogenation catalysts. The surface state of deuterium/hydrogen is analyzed employing a combination of variable-temperature (2)H static and magic-angle spinning (MAS) solid-state NMR techniques, in which the dominant quadrupolar interactions of deuterium give information on the binding situation and local symmetry of deuterium/hydrogen on molecular species. Using a correlation database from molecular complexes and clusters, the possibility to distinguish between terminal Ru-D, bridged Ru2-D, three-fold Ru3-D, and interstitial Ru6-D is demonstrated. Combining these results with quantum-chemical density functional theory (DFT) calculations allows the interpretation of (2)H solid-state data of complex "real world" nanostructures, which yielded new insights into reaction pathways at the molecular level. PMID:23658058

Gutmann, Torsten; del Rosal, Iker; Chaudret, Bruno; Poteau, Romuald; Limbach, Hans-Heinrich; Buntkowsky, Gerd

2013-09-16

202

Solid-state 23Na and 7Li NMR investigations of sodium- and lithium-reduced mesoporous titanium oxides.  

PubMed

Mesoporous titanium oxide synthesized using a dodecylamine template was treated with 0.2, 0.6, and 1.0 equiv of Li- or Na-naphthalene. The composite materials were characterized by nitrogen adsorption, powder X-ray diffraction, X-ray photoelectron spectroscopy, elemental analysis, thermogravimetric analysis, and solid-state 23Na and 7Li NMR spectroscopy. In all cases the wormhole mesoporosity was retained as evidenced by BET surface areas from 400 to 700 m(2)/g, Horvath-Kawazoe pore sizes in the 20 Angstroms range, and a lack of hysteresis in the nitrogen adsorption isotherms. Variable-temperature conductivity studies show that the Li-reduced materials are semiconductors, with conductivity values 3 orders of magnitude higher than those of the Na-reduced materials. Electrochemical measurements demonstrate reversible intercalation/deintercalation of Li+ ions into pristine mesoporous Ti oxides with good cycling capacity. Solid-state 23Na NMR reveals two distinct Na environments: one corresponding to sodium ions in the mesoporous channels and the other corresponding to sodium ions intercalated into the metal framework. 23Na NMR spectra also indicate that the relative population of the framework site increases with increased reduction levels. Solid-state 7Li NMR spectra display a single broad resonance, which increases in breadth with increased reduction levels, though individual resonances inferring the presence of channel and framework Li species are not resolved. Comparisons of the lithium chemical shifts with published values suggests an "anatase-like structure" with no long-range order in the least-reduced samples but a "lithium titanate-like structure" with no long-range order in the higher reduced materials. PMID:16472000

Lo, Andy Y H; Schurko, Robert W; Vettraino, Melissa; Skadtchenko, Boris O; Trudeau, Michel; Antonelli, David M

2006-02-20

203

The topology of lysine-containing amphipathic peptides in bilayers by circular dichroism, solid-state NMR, and molecular modeling.  

PubMed Central

In order to better understand the driving forces that determine the alignment of amphipathic helical polypeptides with respect to the surface of phospholipid bilayers, lysine-containing peptide sequences were designed, prepared by solid-phase chemical synthesis, and reconstituted into membranes. CD spectroscopy indicates that all peptides exhibit a high degree of helicity in the presence of SDS micelles or POPC small unilamellar vesicles. Proton-decoupled (31)P-NMR solid-state NMR spectroscopy demonstrates that in the presence of peptides liquid crystalline phosphatidylcholine membranes orient well along glass surfaces. The orientational distribution and dynamics of peptides labeled with (15)N at selected sites were investigated by proton-decoupled (15)N solid-state NMR spectroscopy. Polypeptides with a single lysine residue adopt a transmembrane orientation, thereby locating this polar amino acid within the core region of the bilayer. In contrast, peptides with > or = 3 lysines reside along the surface of the membrane. With 2 lysines in the center of an otherwise hydrophobic amino acid sequence the peptides assume a broad orientational distribution. The energy of lysine discharge, hydrophobic, polar, and all other interactions are estimated to quantitatively describe the polypeptide topologies observed. Furthermore, a molecular modeling algorithm based on the hydrophobicities of atoms in a continuous hydrophilic-hydrophobic-hydrophilic potential describes the experimentally observed peptide topologies well. PMID:11053137

Vogt, B; Ducarme, P; Schinzel, S; Brasseur, R; Bechinger, B

2000-01-01

204

3D DUMAS: Simultaneous Acquisition of Three-Dimensional Magic Angle Spinning Solid-State NMR Experiments of Proteins  

PubMed Central

Using the DUMAS (Dual acquisition Magic Angle Spinning) solid-state NMR approach, we created new pulse schemes that enable the simultaneous acquisition of three dimensional (3D) experiments on uniformly 13C, 15N labeled proteins. These new experiments exploit the simultaneous cross-polarization (SIM-CP) from 1H to 13C and 15N to acquire two 3D experiments simultaneously. This is made possible by bidirectional polarization transfer between 13C and 15N and the long living 15N z-polarization in solid state NMR. To demonstrate the power of this approach, four 3D pulse sequences (NCACX, CANCO, NCOCX, CON(CA)CX,) are combined into two pulse sequences (3D DUMAS-NCACX-CANCO, 3D DUMAS-NCOCX-CON(CA)CX) that allow simultaneous acquisition of these experiments, reducing the experimental time by approximately half. Importantly, the 3D DUMAS-NCACX-CANCO experiment alone makes it possible to obtain the majority of the backbone sequential resonance assignments for microcrystalline U-13C,15N ubiquitin. The DUMAS approach is general and applicable to many 3D experiments, nearly doubling the performance of NMR spectrometers. PMID:22698806

Gopinath, T.; Veglia, Gianluigi

2012-01-01

205

Solid state {sup 31}P NMR study of phosphonate binding sites in guanidine-functionalized, molecular imprinted silica xerogels  

SciTech Connect

Phosphonate binding sites in guanidine and ammonium surface-functionalized silica xerogels were prepared via the molecular imprinting technique and characterized using solid state {sup 31}P MAS NMR. One-point, two-point, and non-specific host-guest interactions between phenylphosphonic acid (PPA) and the functionalized gels were distinguished by characteristic chemical shifts of the observed absorption peaks. Using solid state as well as solution phase NMR analyses, absorptions observed at 15.5 ppm and 6.5 ppm were identified as resulting from the 1:1 (one-point) and 2:1 (two-point) guanidine to phosphonate interactions, respectively. Similar absorptions were observed with the ammonium functionalized gels. By examining the host-guest interactions within the gels, the efficiency of the molecular imprinting procedure with regard to the functional monomer-to-template interaction could be readily assessed. Template removal followed by substrate adsorption studies conducted on the guanidine functionalized gels provided a method to evaluate the binding characteristics of the receptor sites to a phosphonate substrate. During these experiments, {sup 29}Si and {sup 31}P MAS NMR acted as diagnostic monitors to identify structural changes occurring in the gel matrix and at the receptor site from solvent mediated processes.

Sasaki, D.Y.; Alam, T.D.

2000-01-03

206

Solution and Solid-State NMR Structural Studies of Antimicrobial Peptides LPcin-I and LPcin-II  

PubMed Central

Lactophoricin (LPcin-I) is an antimicrobial, amphiphatic, cationic peptide with 23-amino acid residues isolated from bovine milk. Its analogous peptide, LPcin-II, lacks six N-terminal amino acids compared to LPcin-I. Interestingly, LPcin-II does not display any antimicrobial activity, whereas LPcin-I inhibits the growth of both Gram-negative and Gram-positive bacteria without exhibiting any hemolytic activity. Uniformly 15N-labeled LPcin peptides were prepared by the recombinant expression of fusion proteins in Escherichia coli, and their properties were characterized by electrospray ionization mass spectrometry, circular dichroism spectroscopy, and antimicrobial activity tests. To understand the structure-activity relationship of these two peptides, they were studied in model membrane environments by a combination of solution and solid-state NMR spectroscopy. We determined the tertiary structure of LPcin-I and LPcin-II in the presence of dodecylphosphorylcholine micelles by solution NMR spectroscopy. Magnetically aligned unflipped bicelle samples were used to investigate the structure and topology of LPcin-I and LPcin-II by solid-state NMR spectroscopy. PMID:21889457

Park, Tae-Joon; Kim, Ji-Sun; Ahn, Hee-Chul; Kim, Yongae

2011-01-01

207

High-Resolution Solid State NMR Spectroscopy of Steroids and their Derivatives  

Microsoft Academic Search

Steroids are an important class of organic compounds containing a vast array of biologically and physiologically essential molecules. Due to their availability, relatively straightforward derivatizability, and endogeneity, they are widely used in pharmacological applications. The investigation of molecular and physico-chemical properties of active pharmaceutical ingredients (APIs) in the solid state is important, since these properties are directly related to their

Elina Sievänen; Erkki Kolehmainen

2012-01-01

208

Hydrogen bonding pattern in N-benzoyl(- DL-)- L-phenylalanines as revealed by solid-state NMR spectroscopy  

NASA Astrophysics Data System (ADS)

The nature of the hydrogen bonding pattern has been investigated in N-benzoyl- DL-phenylalanine ( 1) and N-benzoyl- L-phenylalanine ( 2) polymorphes by solid-state NMR spectroscopy. It has been shown that the multiple resonances of carboxyl carbon in 2 are directly connected to different types of hydrogen bonding. The differences in intermolecular distances of carboxyl groups involved in different types of hydrogen bonding have been visualized by the 2D exchange and 1D ODESSA experiments. Potential applications of such a new approach include the exploration of intermolecular distances in hydrogen bonded compounds with singly labeled biomolecules.

Potrzebowski, M. J.; Schneider, C.; Tekely, P.

1999-11-01

209

Multiple acquisition/multiple observation separated local field/chemical shift correlation solid-state magic angle spinning NMR spectroscopy  

NASA Astrophysics Data System (ADS)

Multiple acquisition spectroscopy (MACSY) experiments that enable multiple free induction decays to be recorded during individual experiments are demonstrated. In particular, the experiments incorporate separated local field spectroscopy into homonuclear and heteronuclear correlation spectroscopy. The measured heteronuclear dipolar couplings are valuable in structure determination as well as in enhancing resolution by providing an additional frequency axis. In one example four different three-dimensional spectra are obtained in a single experiment, demonstrating that substantial potential saving in experimental time is available when multiple multi-dimensional spectra are required as part of solid-state NMR studies.

Das, Bibhuti B.; Opella, Stanley J.

2014-08-01

210

Multiple acquisition/multiple observation separated local field/chemical shift correlation solid-state magic angle spinning NMR spectroscopy.  

PubMed

Multiple acquisition spectroscopy (MACSY) experiments that enable multiple free induction decays to be recorded during individual experiments are demonstrated. In particular, the experiments incorporate separated local field spectroscopy into homonuclear and heteronuclear correlation spectroscopy. The measured heteronuclear dipolar couplings are valuable in structure determination as well as in enhancing resolution by providing an additional frequency axis. In one example four different three-dimensional spectra are obtained in a single experiment, demonstrating that substantial potential saving in experimental time is available when multiple multi-dimensional spectra are required as part of solid-state NMR studies. PMID:25023566

Das, Bibhuti B; Opella, Stanley J

2014-08-01

211

Proton transfer and hydrogen bonding in the organic solid state: a combined XRD/XPS/ssNMR study of 17 organic acid-base complexes.  

PubMed

The properties of nitrogen centres acting either as hydrogen-bond or Brønsted acceptors in solid molecular acid-base complexes have been probed by N 1s X-ray photoelectron spectroscopy (XPS) as well as (15)N solid-state nuclear magnetic resonance (ssNMR) spectroscopy and are interpreted with reference to local crystallographic structure information provided by X-ray diffraction (XRD). We have previously shown that the strong chemical shift of the N 1s binding energy associated with the protonation of nitrogen centres unequivocally distinguishes protonated (salt) from hydrogen-bonded (co-crystal) nitrogen species. This result is further supported by significant ssNMR shifts to low frequency, which occur with proton transfer from the acid to the base component. Generally, only minor chemical shifts occur upon co-crystal formation, unless a strong hydrogen bond is formed. CASTEP density functional theory (DFT) calculations of (15)N ssNMR isotropic chemical shifts correlate well with the experimental data, confirming that computational predictions of H-bond strengths and associated ssNMR chemical shifts allow the identification of salt and co-crystal structures (NMR crystallography). The excellent agreement between the conclusions drawn by XPS and the combined CASTEP/ssNMR investigations opens up a reliable avenue for local structure characterization in molecular systems even in the absence of crystal structure information, for example for non-crystalline or amorphous matter. The range of 17 different systems investigated in this study demonstrates the generic nature of this approach, which will be applicable to many other molecular materials in organic, physical, and materials chemistry. PMID:24292812

Stevens, Joanna S; Byard, Stephen J; Seaton, Colin C; Sadiq, Ghazala; Davey, Roger J; Schroeder, Sven L M

2014-01-21

212

Investigating the interaction between peptides of the amphipathic helix of Hcf106 and the phospholipid bilayer by solid-state NMR spectroscopy.  

PubMed

The chloroplast twin arginine translocation (cpTat) system transports highly folded precursor proteins into the thylakoid lumen using the protonmotive force as its only energy source. Hcf106, as one of the core components of the cpTat system, is part of the precursor receptor complex and functions in the initial precursor-binding step. Hcf106 is predicted to contain a single amino terminal transmembrane domain followed by a Pro-Gly hinge, a predicted amphipathic ?-helix (APH), and a loosely structured carboxy terminus. Hcf106 has been shown biochemically to insert spontaneously into thylakoid membranes. To better understand the membrane active capabilities of Hcf106, we used solid-state NMR spectroscopy to investigate those properties of the APH. In this study, synthesized peptides of the predicted Hcf106 APH (amino acids 28-65) were incorporated at increasing mol.% into 1-palmitoyl-2-oleoyl-sn-glycero-phosphocholine (POPC) and POPC/MGDG (monogalactosyldiacylglycerol; mole ratio 85:15) multilamellar vesicles (MLVs) to probe the peptide-lipid interaction. Solid-state (31)P NMR and (2)H NMR spectroscopic experiments revealed that the peptide perturbs the headgroup and the acyl chain regions of phospholipids as indicated by changes in spectral lineshape, chemical shift anisotropy (CSA) line width, and (2)H order SCD parameters. In addition, the comparison between POPC MLVs and POPC/MGDG MLVs indicated that the lipid bilayer composition affected peptide perturbation of the lipids, and such perturbation appeared to be more intense in a system more closely mimicking a thylakoid membrane. PMID:24144541

Zhang, Lei; Liu, Lishan; Maltsev, Sergey; Lorigan, Gary A; Dabney-Smith, Carole

2014-01-01

213

Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis  

PubMed Central

Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO43? ?1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO32? range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ?1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. PMID:24273344

McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M. Banaszak; Tecklenburg, Mary M.J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

2013-01-01

214

Crystallinity and compositional changes in carbonated apatites: Evidence from 31P solid-state NMR, Raman, and AFM analysis  

NASA Astrophysics Data System (ADS)

Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and 31P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse 31P NMR linewidth and inverse Raman PO43-?1 bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3-10.3 wt% CO32- range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the 31P NMR chemical shift frequency and the Raman phosphate ?1 band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.

McElderry, John-David P.; Zhu, Peizhi; Mroue, Kamal H.; Xu, Jiadi; Pavan, Barbara; Fang, Ming; Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T.; Holl, Mark M. Banaszak; Tecklenburg, Mary M. J.; Ramamoorthy, Ayyalusamy; Morris, Michael D.

2013-10-01

215

Radiation damping in microcoil NMR probes  

NASA Astrophysics Data System (ADS)

Radiation damping arises from the field induced in the receiver coil by large bulk magnetization and tends to selectively drive this magnetization back to equilibrium much faster than relaxation processes. The demand for increased sensitivity in mass-limited samples has led to the development of microcoil NMR probes that are capable of obtaining high quality NMR spectra with small sample volumes (nL-?L). Microcoil probes are optimized to increase sensitivity by increasing either the sample-to-coil ratio (filling factor) of the probe or quality factor of the detection coil. Though radiation damping effects have been studied in standard NMR probes, these effects have not been measured in the microcoil probes. Here a systematic evaluation of radiation damping effects in a microcoil NMR probe is presented and the results are compared with similar measurements in conventional large volume samples. These results show that radiation-damping effects in microcoil probe is much more pronounced than in 5 mm probes, and that it is critically important to optimize NMR experiments to minimize these effects. As microcoil probes provide better control of the bulk magnetization, with good RF and B0 inhomogeneity, in addition to negligible dipolar field effects due to nearly spherical sample volumes, these probes can be used exclusively to study the complex behavior of radiation damping.

Krishnan, V. V.

2006-04-01

216

Solid-state high-resolution 13C-NMR study of crosslinks in heavily gamma-irradiated polyethylene  

NASA Astrophysics Data System (ADS)

Chemical species produced by heavy ?-irradiation to high-density polyethylene were identified by solid-state high-resolution 13C-NMR, that is, by the CP-MAS method. The majority of chemical species responsible for crosslinks are tertiary carbons, even after such a heavy dosage as 995 Mrad of ?-irradiation. The MAS method, without CP, was used to detect selectively the NMR signal from 13C in amorphous regions. By using a Torchia pulse sequence, spectra from either crystalline or amorphous regions are observed selectively. The results indicate that short branches are produced preferentially in amorphous regions. More crosslinks are produced (by nearly 3.6 times) in amorphous regions than in crystalline regions.

Sohma, J.; Qun, Chen; Yuanshen, Wang; Xue-Wen, Qu; Shiotani, M.

217

Grid-free powder averages: on the applications of the Fokker-Planck equation to solid state NMR.  

PubMed

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. PMID:23942141

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

2013-10-01

218

Effects of strong paramagnetic interactions on solid-state deuterium NMR spectra  

NASA Astrophysics Data System (ADS)

The method for analyzing the 2H NMR spectrum affected by strong paramagnetic interaction is discussed. The 2H NMR spectral simulation including the effects of paramagnetic shift and paramagnetic spin-spin relaxation was performed for several molecular motions. The contribution of distant paramagnetic ions to the paramagnetic shift and the effect of anisotropic spin-spin relaxation on the lineshape of the 2H NMR spectrum were investigated by the spectral simulation. The temperature variation of 2H NMR spectrum of [Mn(H 2O) 6][SiF 6] observed by the Exorcycled quadrupole-echo sequence was well reproduced using the proposed method.

Mizuno, Motohiro; Itakura, Naohisa; Endo, Kazunaka

2005-12-01

219

Water and glucose gradients in the substrate measured with NMR imaging during solid-state fermentation with Aspergillus oryzae.  

PubMed

Gradients inside substrate particles cannot be prevented in solid-state fermentation. These gradients can have a strong effect on the physiology of the microorganisms but have hitherto received little attention in experimental studies. We report gradients in moisture and glucose content during cultivation of Aspergillus oryzae on membrane-covered wheat-dough slices that were calculated from (1)H-NMR images. We found that moisture gradients in the solid substrate remain small when evaporation is minimized. This is corroborated by predictions of a diffusion model. In contrast, strong glucose gradients developed. Glucose concentrations just below the fungal mat remained low due to high glucose uptake rates, but deeper in the matrix glucose accumulated to very high levels. Integration of the glucose profile gave an average concentration close to the measured average content. On the basis of published data, we expect that the glucose levels in the matrix cause a strong decrease in water activity. The results demonstrate that NMR can play an important role in quantitative analysis of water and glucose gradients at the particle level during solid-state fermentation, which is needed to improve our understanding of the response of fungi to this nonconventional fermentation environment. PMID:12209813

Nagel, Frank-Jan; Van As, Henk; Tramper, Johannes; Rinzema, Arjen

2002-09-20

220

Crystallinity and compositional changes in carbonated apatites: Evidence from {sup 31}P solid-state NMR, Raman, and AFM analysis  

SciTech Connect

Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and {sup 31}P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse {sup 31}P NMR linewidth and inverse Raman PO{sub 4}{sup 3?}?{sub 1} bandwidth were both correlated with powder XRD c-axis crystallinity over the 0.3–10.3 wt% CO{sub 3}{sup 2?} range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the {sup 31}P NMR chemical shift frequency and the Raman phosphate ?{sub 1} band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals. - Graphical abstract: Carbonated apatite shows an abrupt change in spectral (NMR, Raman) and morphological (AFM) properties at a composition of about one carbonate substitution per unit cell. Display Omitted - Highlights: • Crystallinity (XRD), particle size (AFM) of carbonated apatites and bone mineral. • Linear relationships among crystallinity, {sup 31}P NMR and Raman inverse bandwidths. • Low and high carbonated apatites use different charge-balancing ion-loss mechanism.

McElderry, John-David P.; Zhu, Peizhi [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Mroue, Kamal H. [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Xu, Jiadi [Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Pavan, Barbara [Department of Chemistry and Science of Advanced Materials Program, Central Michigan University, Mt. Pleasant, MI 48859 (United States); Fang, Ming [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Zhao, Guisheng; McNerny, Erin; Kohn, David H.; Franceschi, Renny T. [School of Dentistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Holl, Mark M.Banaszak [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Tecklenburg, Mary M.J., E-mail: mary.tecklenburg@cmich.edu [Department of Chemistry and Science of Advanced Materials Program, Central Michigan University, Mt. Pleasant, MI 48859 (United States); Ramamoorthy, Ayyalusamy [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055 (United States); Morris, Michael D. [Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 (United States)

2013-10-15

221

A spectrometer designed for 6.7 and 14.1 T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission  

NASA Astrophysics Data System (ADS)

A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer operating at 6.7 T is described and demonstrated. The 187 GHz TE13 fundamental mode of the FU CW VII gyrotron is used as the microwave source for this magnetic field strength and 284 MHz 1H DNP-NMR. The spectrometer is designed for use with microwave frequencies up to 395 GHz (the TE16 second-harmonic mode of the gyrotron) for DNP at 14.1 T (600 MHz 1H NMR). The pulsed microwave output from the gyrotron is converted to a quasi-optical Gaussian beam using a Vlasov antenna and transmitted to the NMR probe via an optical bench, with beam splitters for monitoring and adjusting the microwave power, a ferrite rotator to isolate the gyrotron from the reflected power and a Martin-Puplett interferometer for adjusting the polarisation. The Gaussian beam is reflected by curved mirrors inside the DNP-MAS-NMR probe to be incident at the sample along the MAS rotation axis. The beam is focussed to a ˜1 mm waist at the top of the rotor and then gradually diverges to give much more efficient coupling throughout the sample than designs using direct waveguide irradiation. The probe can be used in triple channel HXY mode for 600 MHz 1H and double channel HX mode for 284 MHz 1H, with MAS sample temperatures ?85 K. Initial data at 6.7 T and ˜1 W pulsed microwave power are presented with 13C enhancements of 60 for a frozen urea solution (1H-13C CP), 16 for bacteriorhodopsin in purple membrane (1H-13C CP) and 22 for 15N in a frozen glycine solution (1H-15N CP) being obtained. In comparison with designs which irradiate perpendicular to the rotation axis the approach used here provides a highly efficient use of the incident microwave beam and an NMR-optimised coil design.

Pike, Kevin J.; Kemp, Thomas F.; Takahashi, Hiroki; Day, Robert; Howes, Andrew P.; Kryukov, Eugeny V.; MacDonald, James F.; Collis, Alana E. C.; Bolton, David R.; Wylde, Richard J.; Orwick, Marcella; Kosuga, Kosuke; Clark, Andrew J.; Idehara, Toshitaka; Watts, Anthony; Smith, Graham M.; Newton, Mark E.; Dupree, Ray; Smith, Mark E.

2012-02-01

222

Planar microcoil-based microfluidic NMR probes  

Microsoft Academic Search

Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300MHz with three different probes having observed sample volumes of respectively 30, 120, and 470nL. The achieved sensitivity enables acquisition of an 1H spectrum of 160?g sucrose in D2O, corresponding to a

C. Massin; F. Vincent; A. Homsy; K. Ehrmann; G. Boero; P.-A Besse; A. Daridon; E. Verpoorte; N. F de Rooij; R. S Popovic

2003-01-01

223

Conformation heterogeneity and mobility of surfactant molecules in intercalated clay minerals studied by solid-state NMR  

SciTech Connect

The conformation heterogeneity and mobility of surfactant molecules in intercalated montmorillonite clay minerals have been investigated using variable-temperature solid-state {sup 13}C NMR and two-dimensional proton wide-line separation (2D WISE) {sup 1}H--{sup 13}C NMR spectroscopy. Previous FTIR studies by Vaia et al. for the first time revealed the existence of a gauche conformation of surfactant molecules in clay minerals and further illustrated the transition from an ordered conformation, to a liquid crystalline state, to completely liquid-like behavior. The NMR study reported in this paper clearly demonstrates the coexistence of order and disordered chain conformations. Two main resonance peaks are resolved and associated with the backbone alkyl chains: the resonance at 33 ppm corresponds to the ordered conformation (all-trans), and the resonance at 30 ppm corresponds to the disordered conformation (mixture of trans and gauche). The NMR technique allows detailed characterization and quantification of the conformational heterogeneity, which is difficult to determine by other techniques. Furthermore, variable-temperature NMR also directly provides quantitative information on the rigidity of the different conformations. Results from cross-polarization time constant T{sub CH} measurements along with 2D WISE NMR suggest that molecules in the ordered all-trans conformation are as rigid as those in solid crystalline materials and that molecules in the disordered conformation are similar to those in liquid crystalline materials. Upon heating, the molecules in the disordered conformation remain more or less unchanged, while the molecules in the ordered conformation become disordered. However, the intercalated molecules in the clay minerals never attained the complete liquid-like behavior even after all the bound surfactant assumed a disordered conformation.

Wang, L.Q.; Liu, J.; Exarhos, G.J.; Flanigan, K.Y.; Bordia, R.

2000-04-06

224

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR  

NASA Astrophysics Data System (ADS)

Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and 13C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.

Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe; Raymundo-Piñero, Encarnación; Ammar, Mohammed Ramzi; Simon, Patrick; Massiot, Dominique; Béguin, François

2013-04-01

225

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR.  

PubMed

Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with (13)C and (11)B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and (13)C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages. PMID:23416727

Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe; Raymundo-Piñero, Encarnación; Ammar, Mohammed Ramzi; Simon, Patrick; Massiot, Dominique; Béguin, François

2013-04-01

226

High-resolution high-frequency dynamic nuclear polarization for biomolecular solid state NMR  

E-print Network

Dynamic Nuclear Polarization (DNP) has exploded in popularity over the last few years, finally realizing its potential to overcome the detrimental lack of sensitivity that has plagued performing NMR experiments. Applied ...

Barnes, Alexander B. (Alexander Benjamin)

2011-01-01

227

Determination of Anion Ordering in Mixed Apatites via Multinuclear Solid-State NMR & X-ray Crystallography  

NASA Astrophysics Data System (ADS)

Subtle changes in crystallographic anion position in apatite sensu latu Ca5(PO4)3(F,OH,Cl) are known to affect greatly its macroscopic physical properties, such as acid resistivity and hardness. While the anion positions in endmember compositions are well described, there exist substantial gaps in our understanding of anion ordering in mixed binary and ternary compositions because of potential steric anion interactions and symmetry changes. X-ray diffraction analysis of these binary/ternary mixtures is well-suited to address the atomic positions and average occupancies of these anion sites for well-ordered systems. Multinuclear solid-state NMR methods complement XRD structure studies if there exist column ordering reversals or disorder in the atomic positions of the anions, as NMR is sensitive to the atomic arrangement within short distances of the nucleus (<4Å). Using these analytical techniques the anion ordering along the F-Cl solid-solution join is reported, and features an off-mirror fluorine site at (0,0,0.167). The migration of fluorine away from its end-member site within the {00l} mirror plane and subsequent migration of chlorine in the opposing direction results in acceptable F-Cl distances in the anion column. Exceptionally low H content in the anion channel was afforded via high-temperature (1200°C) solid-state reaction under vacuum. The speciation of H was determined by 1H{31P} REDOR experiments, from which the REDOR difference spectrum features a single resonance at ?H = 1.6 ppm which can be assigned to OH groups. The abundance of OH was confirmed by comparison of single-pulse (SP) 31P and cross-polarization 31P{1H} NMR (CP) spectral intensities to those of a crystalline synthetic hydroxylapatite, and showed that only 0.4 mol% of the 31P in the composition occurs in hydroxylapatite-like configurations.

Vaughn, J. S.; Phillips, B. L.; Hughes, J. M.; Nekvasil, H.; Ustunisik, G. K.; Lindsley, D. H.; Coraor, A. E.; McCubbin, F. M.; Woerner, W. R.

2013-12-01

228

Observation of a Low-Temperature, Dynamically Driven, Structural Transition in a Polypeptide by Solid State NMR Spectroscopy  

PubMed Central

At reduced temperatures, proteins and other biomolecules are generally found to exhibit dynamic as well as structural transitions. This includes a so-called protein glass transition that is universally observed in systems cooled between 200–230K, and which is generally attributed to interactions between hydrating solvent molecules and protein side chains. However, there is also experimental and theoretical evidence for a low-temperature transition in the intrinsic dynamics of the protein itself, absent any solvent. Here, we use low-temperature solid state NMR to examine site specific fluctuations in atomic structure and dynamics in the absence of solvents. In particular, we employ magic angle spinning NMR to examine a structural phase transition associated with dynamic processes in a solvent-free polypeptide, N-f-MLF-OH, lattice at temperatures as low as 90K. This transition is characterized by the appearance of an extra set of lines in 1D 15N spectra as well as additional cross peaks in 2D 13C-13C and 13C-15N spectra. Interestingly, the gradual, temperature-dependent appearance of the new spectral component is not accompanied by the line broadening typical of dynamic transitions. A direct comparison between the spectra of N-f-MLF-OH and the analog N-f-MLF-OMe, which does not display this transition, indicates a correlation of the structural transition to the temperature dependent motion of the aromatic phenylalanine side chain. Several quantitative solid state NMR experiments were employed to provide site-specific measurements of structural and motional features of the observed transition. PMID:19067520

Bajaj, Vikram S.; van der Wel, Patrick C.A.; Griffin, Robert G.

2009-01-01

229

Reorientational dynamics and solid-phase transformation of ammonium dicyanamide into dicyandiamide: a (2)H solid-state NMR study.  

PubMed

The reorientational dynamics of ammonium dicyanamide ND4[N(C[triple bond]N)2] and the kinetics as well as the mechanism of the solid-state isomerization reaction from ammonium dicyanamide into dicyandiamide (N[triple bond]C-N==C(NH2)2) was studied by means of 2H and 14N solid-state NMR spectroscopy in a temperature range between 38 and 390 K. Whereas in previous investigations the mechanism of the solid-state transformation was investigated by means of vibrational and magic angle spinning solid-state NMR spectroscopy as well as neutron diffraction, we here present a comprehensive 2H study of the ammonium ion dynamics prior to and during the course of the reaction, thereby highlighting possible cross correlations between dynamics and reactivity involving the ammonium ion. The ND4+ group was found to undergo thermally activated random jumps in a tetrahedral potential, which is increasingly distorted with increasing temperature, giving rise to an asymmetrically compressed or elongated tetrahedron with deviations from the tetrahedral angle of up to 6 degrees . The correlation time follows an Arrhenius law with an activation energy of Ea = 25.8(2) kJ mol(-1) and an attempt frequency of tau0(-1) = 440(80) THz. The spin-lattice relaxation times were fitted according to a simple Bloembergen-Purcell-Pound type model with a T1 minimum of 4 ms at 230 K. Temperature-dependent librational amplitudes were extracted by line-shape simulations between 38 and 390 K and contrasted with those obtained by neutron diffraction, their values ranging between 5 and 28 degrees . The onset and progress of the solid-phase transformation were followed in situ at temperatures above 372 K and could be classified as a strongly temperature-dependent, heterogeneous two-step reaction proceeding with rapid evolution of ammonia and comparatively slow subsequent reintegration into the solid. On the microscopic level, this correlates with a rapid proton transfer -- possibly triggered by a coupling between the ammonium ion dynamics and phonon modes on the terahertz time scale -- and an essentially decoupled nucleophilic attack of ammonia at the nitrile carbon, giving rise to significantly differing time constants for the two processes. PMID:17880124

Lotsch, Bettina V; Schnick, Wolfgang; Naumann, Ernst; Senker, Jürgen

2007-10-11

230

Understanding API-Polymer Proximities in Amorphous Stabilized Composite Drug Products Using Fluorine-Carbon 2D HETCOR Solid-State NMR.  

PubMed

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. PMID:25152063

Abraham, Anuji; Crull, George

2014-10-01

231

The structure of aluminophosphate glasses revisited: Application of modern solid state NMR strategies to determine structural motifs on intermediate length scales  

Microsoft Academic Search

In this paper we report a reinvestigation of the network organization in aluminophosphate glasses. Samples were prepared along the 50K2O–xAl2O3–(50?x)P2O5 composition line with 0solid state NMR strategies including 31P{27Al}-CP-HETCOR NMR, 31P{27Al}-REAPDOR NMR, 27Al{31P}-REDOR NMR and 2D 31P-J-RESolved NMR spectroscopy.

Sebastian Wegner; Leo van Wüllen; Grégory Tricot

2008-01-01

232

Investigation of the structure of cold-drawn high-density polyethylene using solid-state NMR  

NASA Astrophysics Data System (ADS)

In this dissertation, the cold-drawing response of a commercial high-density polyethylene (HDPE) resin has been studied using solid-state nuclear magnetic resonance (NMR) spectroscopy and variety of other complementary techniques. Melt-crystallized, isotropic samples of the HDPE have been drawn to various extensions at ambient temperature (21°C) and at a relatively slow strain rate (0.0013 s-1). Using solid-state NMR, the first unambiguous evidence for a major morphological component intermediate to the crystalline and amorphous domains in the cold-drawn HDPE microstructure has been found. Employing an 'inverse 13 C T1 filter' and other filtering techniques, signals from the various components have been selected and compared. The intermediate component comprises chains of all-trans conformation but with significant disorder in packing. The chains show fast, intermediate-amplitude motions about their axes and are generally aligned with the draw direction, but with a greater distribution of orientation angles relative to crystalline phase. A quantitative 13C NMR procedure has been utilized in the analysis of morphological component composition during cold drawing. In the undeformed material, the NMR-derived composition shows excellent agreement with other common techniques. The mass fraction of the intermediate component has been measured by NMR to be as high as 35% in the cold-drawn HDPE, greater than the contributions from the amorphous domains and monoclinic crystals. The intermediate component content dramatically increases by 240% just after necking, along with a doubling in the monoclinic crystals. At the same time, decreases of about 25% in the total crystalline and amorphous phases occur. A general re-ordering in the microstructure takes place during neck propagation and strain hardening. The total crystallinity rises by about 8%, with a corresponding decrease in the monoclinic crystals (50%) and amorphous material (30%). Based on 1H spin diffusion data, a microstructural model of cold-drawn HDPE is offered. The spin diffusion data identify the intermediate component with tie-molecule bundles that connect small 'mosaic block' crystallites (ca. 10--15 nm side dimension) along the draw direction. The bundles consist of about 30 chains and are estimated to be about 2.5 nm in diameter and 3 nm in length.

Mowery, Daniel Michael

233

Molecular dynamics of fullerene-nanowhiskers studied by solid state NMR  

NASA Astrophysics Data System (ADS)

The properties of molecular motion of as-grown C60 nanowhiskers and C70 nanowhiskers were investigated by 13C-CP/MAS NMR, wideline 13C-NMR and '1-NMR techniques. It was confirmed that m-xylene molecules are contained in both C60 and C70 nanowhisekers. It was found that C60 nanowhiskers exhibit an orientational order phase transition at 250 K. The activation energy of C60 molecules below 250 K was evaluated to be 14.7 kJ/mol, which is smaller than that of pristine C60 solid. For C70 nanowhiskers, no clear phase transition was found from 270 K to 170 K. The activation energy of C70 molecules was evaluated to be 13.7 kJ/mol between 270 K and 170 K, which is smaller than that of pristine C70 solid.

Ogata, H.; Motohashi, S.; Tsuchida, S.

2009-04-01

234

High-field 19.6 T 27Al solid-state MAS NMR of in vitro aluminated brain tissue  

NASA Astrophysics Data System (ADS)

The combination of 27Al high-field solid-state NMR (19.6 T) with rapid spinning speeds (17.8 kHz) is used to acquire 27Al NMR spectra of total RNA human brain temporal lobe tissues exposed to 0.10 mM Al 3+ (as AlCl 3) and of human retinal pigment epithelial cells (ARPE-19), grown in 0.10 mM AlCl 3. The spectra of these model systems show multiple Al 3+ binding sites, good signal/noise ratios and apparent chemical shift dispersions. A single broad peak (-3 to 11 ppm) is seen for the aluminated ARPE-19 cells, consistent with reported solution-state NMR chemical shifts of Al-transferrin. The aluminated brain tissue has a considerably different 27Al MAS NMR spectrum. In addition to the transferrin-type resonance, additional peaks are seen. Tentative assignments include: -9 to -3 ppm, octahedral AlO 6 (phosphate and water); 9 ppm, condensed AlO 6 units (Al-O-Al bridges); 24 ppm, tetrahedral AlO 3N and/or octahedral Al-carbonate; and 35 ppm, more N-substituted aluminum and /or tetrahedral AlO 4. Thus, brain tissue is susceptible to a broad range of coordination by aluminum. Furthermore, the moderate 27Al C Q values (all less than 10 MHz) suggest future NMR studies may be performed at 9.4 T and a spin rate of 20 kHz.

Bryant, Pamela L.; Lukiw, Walter J.; Gan, Zhehong; Hall, Randall W.; Butler, Leslie G.

2004-10-01

235

Solid-state 27Al and 29Si NMR investigations on Si-substituted hydrogarnets  

Microsoft Academic Search

Partially deuterated Ca3Al2(SiO4)3?x(OH)4x hydrates prepared by a reaction in the presence of D2O of synthetic tricalcium aluminate with different amounts of amorphous silica were characterized by 29Si and 27Al magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy. The 29Si NMR spectroscopy was used for quantifying the non-reacted silica and the resulting hydrated products. The incorporation of Si into Ca3Al2(SiO4)3?x(OH)4x was followed

J. M. Rivas Mercury; P. Pena; A. H. De Aza; X. Turrillas; I. Sobrados; J. Sanz

2007-01-01

236

Solid-state variable-temperature NMR study of the phase separation of polybutadiene polyurethane zwitterionomers  

NASA Astrophysics Data System (ADS)

Polybutadiene polyurethane (PBDPU) zwitterionomers based on 4,4'-diphenylmethane diisocyanate (MDI), methyl-diethanolamine (MDEA), and hydroxy terminated polybutadiene are studied with variable-temperature (VT) wide-line 1H NMR. Spin—spin relaxation times ( T2) and spin—lattice relaxation times ( T1) are measured. It is found that phase separation of PBDPU does not change significantly upon ionization. The initial incorporation of ionization groups destroys the crystallinity of the hard segment while further ionization enhances physical crosslinks in the hard phase. The results are compared with a previous VT NMR study on polyether polyurethane zwitterionomers based on MDI, MDEA and 1000 Da molecular weight polytetramethylene oxide.

Yang, G.; Chen, Q.; Wang, Y.; Yang, C.; Wu, X.

1994-07-01

237

Structure of Oxide Glasses under Compression and Confinement: Insights from High-resolution Solid-state NMR and Non-resonant Inelastic X-ray Scattering  

NASA Astrophysics Data System (ADS)

The atomic and nano-scale structure of non-crystalline oxides with varying degree of confinement and compression (pressure) are essential to understand the atomic origins of thermo-mechanical properties and kinetic stability of these materials in the earth's surfaces and interiors. Despite this importance, the effect of confinement and pressure on the nature of bonding in the non-crystalline oxides have remained one of the challenging problems in mineral physics and condensed matter physics due to lack of suitable experimental probes. Advances in element-specific experimental probes, such as non-resonant inelastic x-ray scattering (NRIXS) and high resolution solid-state NMR combined with the first principle calculations have revealed structural details of bonding transitions of amorphous oxides under compression and confinement (e.g. Lee, Rev. Min. Geochem. 2013 accepted; Phys. Rev. Letts, 2013 accepted; Proc. Nat. Aca. Sci. 2011, 108, 6847; Kim and Lee, Geochim. Cosmochim Acta. In press; Yi and Lee, Am Min 2012, 97, 897). Here, we present the key recent progress by NRIXS and NMR into the pressure and confinement-induced bonding transitions in non-crystalline oxides. Theoretical calculation of K-edge NRIXS spectrum took into consideration crystallographically-distinct sites and revealed that the edge features systematically shift to higher energy with increasing degree of densification in atomic arrangement in the polymorphs (from enstatite, perovskite, to post-perovskite). On the basis of these results, multi-nuclear (B, O, Li, Ca), multi-edge (K-, L-, and M-) XRS studies of diverse low z-oxide glasses indicated the pressure-induced increases in the fraction of triply coordinated oxygen above 20 GPa and showed evidence for the topologically driven densification in multi-component basaltic glasses. Finally, we report the first high-resolution solid-state NMR results for the amorphous oxides under confinement where the degree of structural disorder tends to decrease with increasing degree of confinement. These results allow us to microscopically confine the geochemical processes involving interactions between melts and fluids.

Lee, S.

2013-12-01

238

Recoupling of chemical shift anisotropies in solid-state NMR under high-speed magic-angle spinning and in uniformly 13C-labeled systems  

NASA Astrophysics Data System (ADS)

We demonstrate the possibility of recoupling chemical shift anisotropy (CSA) interactions in solid-state nuclear magnetic resonance (NMR) under high-speed magic-angle spinning (MAS) while retaining a static CSA powder pattern line shape and simultaneously attenuating homonuclear dipole-dipole interactions. CSA recoupling is accomplished by a rotation-synchronized radio-frequency pulse sequence with symmetry properties that permit static CSA line shapes to be obtained. We suggest a specific recoupling sequence, which we call ROCSA, for which the scaling factors for CSA and homonuclear dipole-dipole interactions are 0.272 and approximately 0.05, respectively. This sequence is suitable for high-speed 13C MAS NMR experiments on uniformly 13C-labeled organic compounds, including biopolymers. We demonstrate the ROCSA sequence experimentally by measuring the 13C CSA patterns of the uniformly labeled, polycrystalline compounds L-alanine and N-acetyl-D,L-valine at MAS frequencies of 11 and 20 kHz. We also present experimental data for amyloid fibrils formed by a 15-residue fragment of the ?-amyloid peptide associated with Alzheimer's disease, in which four amino acid residues are uniformly labeled, demonstrating the applicability to biochemical systems of high molecular weight and significant complexity. Analysis of the CSA patterns in the amyloid fibril sample demonstrates the utility of ROCSA measurements as probes of peptide and protein conformation in noncrystalline solids.

Chan, Jerry C. C.; Tycko, Robert

2003-05-01

239

Solid-State NMR Structural Measurements on the Membrane-Associated Influenza Fusion Protein Ectodomain  

E-print Network

liquid-state NMR structures of IFP in detergent micelles as well as electron spin resonance measurements (IFV) are enclosed by a membrane which is obtained from an infected host cell. Infection of a new cell begins with joining or "fusion" of the viral and host cell membranes with an end result of a single

Weliky, David

240

Immobilization and chelation of metal complexes with bifunctional phosphine ligands: a solid-state NMR study  

E-print Network

, suspension NMR spectroscopy3can be applied routinely. Since most transition metals form stable phosphine com to bonding via one, two, or three siloxane bridges and there is also the possibility of cross- linking.' Therefore, we used the monoethoxy phosphine PPh2(C6H4)SiMe20Et1 that forms just one siloxane bridge when

Bluemel, Janet

241

Mobility and relaxation determinations of lithium in lithium aluminate ceramics using solid-state NMR spectroscopy  

Microsoft Academic Search

Lithium aluminate is one of the materials being considered for fusion reactor blankets. When preparing the ceramic, it is important to be able to monitor the microstructures since it is a controlling factor in the rate of tritium release from the blanket. Nuclear magnetic resonance spectroscopy (NMR) has been shown to be a useful tool for the nondestructive analysis of

F. F. Stewart; E. S. Peterson; J. F. Stebbins; Ian Farnan; S. O. Dunham; E. Adams; P. W. Jennings

1995-01-01

242

Mobility and relaxation determinations of lithium in lithium aluminate ceramics using solid-state NMR spectroscopy  

SciTech Connect

Lithium aluminate is one of the materials being considered for fusion reactor blankets. When preparing the ceramic, it is important to be able to monitor the microstructures since it is a controlling factor in the rate of tritium release from the blanket. Nuclear magnetic resonance spectroscopy (NMR) has been shown to be a useful tool for the nondestructive analysis of ceramics. Studies detailed in this paper include spectral acquisition, assignment, spin-lattice relaxation time measurements, temperature effects, their correlation to structure, and material purity. The ceramic of interest was lithium aluminate, LiAl{sub 5}O{sub 8}. This material was studied by observation of the NMR active nuclei {sup 6}Li, {sup 7}Li, and {sup 27}Al. For these nuclei, spin-lattice relaxation times (T{sub 1}) were measured and were found to vary considerably, correlating to the presence of paramagnetic impurities within the crystalline lattice. Previous research has shown that the coordination about the aluminum nucleus can be determined using {sup 27}Al NMR spectroscopy. Aluminum-27 NMR spectroscopy was successfully applied, and it provided valuable insight into composition of the ceramic. 20 refs., 4 figs., 3 tabs.

Stewart, F.F.; Peterson, E.S. [Idaho National Engineering Lab., Idaho Falls, ID (United States); Stebbins, J.F. [Stanford Univ., CA (United States)] [and others

1995-02-01

243

Structural studies of methyl brevifolincarboxylate in solid state by means of NMR spectroscopy and DFT calculations  

Microsoft Academic Search

Methyl brevifolincarboxylate isolated from the herb of Potentilla argentea L. (Rosaceae) is a representative of the naturally occurring polyphenols. The compound is of pharmaceutical interest mainly because of its antiviral and antioxidant properties. 13C NMR spectra were recorded for solution and solid phase. 13C CPMAS spectra were assigned by comparison with solution data, dipolar dephasing and short contact time experiments.

Michal Wolniak; Michal Tomczyk; Jan Gudej; Iwona Wawer

2006-01-01

244

Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS  

NASA Astrophysics Data System (ADS)

Two-dimensional through-bond 1H{ 13C} solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse 1H decoupling are presented. Remarkable efficiency of polarization transfer can be achieved at MAS rates exceeding 40 kHz, which is instrumental in these measurements. Schemes utilizing direct and indirect detection of heteronuclei are compared in terms of resolution and sensitivity. A simple procedure for optimization of 1H homonuclear decoupling sequences under these conditions is proposed. The capabilities of these techniques were confirmed on two naturally abundant solids, tripeptide N- formyl- L-methionyl- L-leucyl- L-phenylalanine (f-MLF-OH) and brown coal.

Mao, Kanmi; Pruski, Marek

2009-12-01

245

Cationic membrane peptides: atomic-level insight of structure-activity relationships from solid-state NMR.  

PubMed

Many membrane-active peptides, such as cationic cell-penetrating peptides (CPPs) and antimicrobial peptides (AMPs), conduct their biological functions by interacting with the cell membrane. The interactions of charged residues with lipids and water facilitate membrane insertion, translocation or disruption of these highly hydrophobic species. In this review, we will summarize high-resolution structural and dynamic findings towards the understanding of the structure-activity relationship of lipid membrane-bound CPPs and AMPs, as examples of the current development of solid-state NMR (SSNMR) techniques for studying membrane peptides. We will present the most recent atomic-resolution structure of the guanidinium-phosphate complex, as constrained from experimentally measured site-specific distances. These SSNMR results will be valuable specifically for understanding the intracellular translocation pathway of CPPs and antimicrobial mechanism of AMPs, and more generally broaden our insight into how cationic macromolecules interact with and cross the lipid membrane. PMID:23108593

Su, Yongchao; Li, Shenhui; Hong, Mei

2013-03-01

246

Interaction of electrolyte molecules with carbon materials of well-defined porosity: characterization by solid-state NMR spectroscopy.  

PubMed

Electrochemical double-layer capacitors (EDLCs or supercapacitors) are of special potential interest with respect to energy storage. Nearly all EDLCs make use of porous carbons as electrode materials. Further tuning of their performance in EDLC applications requires a better understanding of their properties. In particular, the understanding of the interactions between carbon-based materials and electrolyte solutions is of fundamental interest with respect to future applications. Since the capacitance of carbon-based electrode materials is known to depend on the pore size, we have studied different porous carbon materials of well-defined, variable pore size loaded with 1 M TEABF4 in acetonitrile or with pure acetonitrile using solid-state magic angle spinning (MAS) (1)H, (11)B, and (13)C NMR spectroscopy. PMID:23925570

Borchardt, Lars; Oschatz, Martin; Paasch, Silvia; Kaskel, Stefan; Brunner, Eike

2013-09-28

247

A multinuclear 1H, 13C and 11B solid-state MAS NMR study of 16- and 18-electron organometallic ruthenium and osmium carborane complexes.  

PubMed

The first (1)H, (13)C, (31)P and (11)B solid state MAS NMR studies of electron-deficient carborane-containing ruthenium and osmium complexes [Ru/Os(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)] are reported. The MAS NMR data from these 16-electron complexes are compared to those of free carborane-ligand and an 18-electron triphenylphosphine ruthenium adduct, and reveal clear spectral differences between 16- and 18-electron organometallic carborane systems in the solid state. PMID:24554004

Barry, Nicolas P E; Kemp, Thomas F; Sadler, Peter J; Hanna, John V

2014-04-01

248

An experimental and theoretical NMR study of NH-benzimidazoles in solution and in the solid state: proton transfer and tautomerism  

PubMed Central

Summary This paper reports the 1H, 13C and 15N NMR experimental study of five benzimidazoles in solution and in the solid state (13C and 15N CPMAS NMR) as well as the theoretically calculated (GIAO/DFT) chemical shifts. We have assigned unambiguously the "tautomeric positions" (C3a/C7a, C4/C7 and C5/C6) of NH-benzimidazoles that, in some solvents and in the solid state, appear different (blocked tautomerism). In the case of 1H-benzimidazole itself we have measured the prototropic rate in HMPA-d 18. PMID:25161719

Nieto, Carla I; Cabildo, Pilar; Garcia, M Angeles; Elguero, Jose

2014-01-01

249

Effect of Ca:Mg ratio on precipitated P species identified using 31P solid state NMR  

NASA Astrophysics Data System (ADS)

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

Manimel Wadu, M.

2009-04-01

250

Solid-State NMR Spectroscopy of Membrane-Associated Myelin Basic Protein—Conformation and Dynamics of an Immunodominant Epitope  

PubMed Central

Myelin basic protein (MBP) maintains the tight multilamellar compaction of the myelin sheath in the central nervous system through peripheral binding of adjacent lipid bilayers of oligodendrocytes. Myelin instability in multiple sclerosis (MS) is associated with the loss of positive charge in MBP as a result of posttranslational enzymatic deimination. A highly-conserved central membrane-binding fragment (murine N81-PVVHFFKNIVTPRTPPP-S99, identical to human N83-S101) represents a primary immunodominant epitope in MS. Previous low-resolution electron paramagnetic resonance measurements on the V83-T92 fragment, with Cys-mutations and spin-labeling that scanned the epitope, were consistent with it being a membrane-associated amphipathic ?-helix. Pseudodeimination at several sites throughout the protein, all distal to the central segment, disrupted the ?-helix at its amino-terminus and exposed it to proteases, representing a potential mechanism in the autoimmune pathogenesis of MS. Here, we have used magic-angle spinning solid-state NMR spectroscopy to characterize more precisely the molecular conformation and dynamics of this central immunodominant epitope of MBP in a lipid milieu, without Cys-substitution. Our solid-state NMR measurements have revealed that the ?-helix present within the immunodominant epitope is shorter than originally modeled, and is independent of the pseudodeimination, highlighting the importance of the local hydrophobic effects in helix formation and stability. The main effect of pseudodeimination is to cause the cytoplasmic exposure of the fragment, potentially making it more accessible to proteolysis. These results are the first, to our knowledge, to provide atomic-level detail of a membrane-anchoring segment of MBP, and direct evidence of decreased MBP-membrane interaction after posttranslational modification. PMID:20713009

Ahmed, Mumdooh A.M.; Bamm, Vladimir V.; Harauz, George; Ladizhansky, Vladimir

2010-01-01

251

Hyperpolarized NMR Probes for Biological Assays  

PubMed Central

During the last decade, the development of nuclear spin polarization enhanced (hyperpolarized) molecular probes has opened up new opportunities for studying the inner workings of living cells in real time. The hyperpolarized probes are produced ex situ, introduced into biological systems and detected with high sensitivity and contrast against background signals using high resolution NMR spectroscopy. A variety of natural, derivatized and designed hyperpolarized probes has emerged for diverse biological studies including assays of intracellular reaction progression, pathway kinetics, probe uptake and export, pH, redox state, reactive oxygen species, ion concentrations, drug efficacy or oncogenic signaling. These probes are readily used directly under natural conditions in biofluids and are often directly developed and optimized for cellular assays, thus leaving little doubt about their specificity and utility under biologically relevant conditions. Hyperpolarized molecular probes for biological NMR spectroscopy enable the unbiased detection of complex processes by virtue of the high spectral resolution, structural specificity and quantifiability of NMR signals. Here, we provide a survey of strategies used for the selection, design and use of hyperpolarized NMR probes in biological assays, and describe current limitations and developments. PMID:24441771

Meier, Sebastian; Jensen, Pernille R.; Karlsson, Magnus; Lerche, Mathilde H.

2014-01-01

252

Aluminium27 solid state NMR spectroscopic studies of chloride binding in Portland cement and blends  

Microsoft Academic Search

Alumina-rich pozzolanic and latent hydraulic binders such as pulverised fuel ash, metakaolin, and ground granulated blast furnace slag, together with silica fume, are frequently added to Portland cement concrete to improve performance and to retard chloride ingress and thereby inhibit chloride-induced corrosion of the carbon steel reinforcement. 27Al{1H} MAS and CP\\/MAS NMR spectroscopies have been used to follow both the

J. A. Chudek; G. Hunter; M. R. Jones; S. N. Scrimgeour; P. C. Hewlett; A. B. Kudryavtsev

2000-01-01

253

Investigation of Polymorphism in Aspartame and Neotame Using Solid-State NMR Spectroscopy  

Microsoft Academic Search

We have been studying the artificial sweeteners aspartame (l-aspartyl-l-phenylalanine methyl ester) and neotame (N-(3,3-dimethylbutyl)-l-aspartyl-l-phenylalanine methyl ester) as compounds which exhibit polymorphism. 13C CP\\/MAS NMR shows that aspartame exists in three distinct forms at room temperature, depending on preparation conditions. For two of the forms, there exists three resonances for each carbon, indicating three crystallographically inequivalent sites and therefore three distinct

Mark T Zell; Brian E Padden; David J. W Grant; Stephen A Schroeder; Kurt L Wachholder; Indra Prakash; Eric J Munson

2000-01-01

254

Advanced solid-state NMR characterization of marine dissolved organic matter isolated using the coupled reverse osmosis/electrodialysis method.  

PubMed

Advanced (13)C solid-state techniques were employed to investigate the major structural characteristics of two surface-seawater dissolved organic matter (DOM) samples isolated using the novel coupled reverse osmosis/electrodialysis method. The NMR techniques included quantitative (13)C direct polarization/magic angle spinning (DP/MAS) and DP/MAS with recoupled dipolar dephasing, (13)C cross-polarization/total sideband suppression (CP/TOSS), (13)C chemical shift anisotropy filter, CH, CH(2), and CH(n) selection, two-dimensional (1)H-(13)C heteronuclear correlation NMR (2D HETCOR), 2D HETCOR combined with dipolar dephasing, and (15)N cross-polarization/magic angle spinning (CP/MAS). The two samples (Coastal and Marine DOM) were collected at the mouth of the Ogeechee River and in the Gulf Stream, respectively. The NMR results indicated that they were structurally distinct. Coastal DOM contained significantly more aromatic and carbonyl carbons whereas Marine DOM was markedly enriched in alkoxy carbon (e.g., carbohydrate-like moieties). Both samples contained significant amide N, but Coastal DOM had nitrogen bonded to aromatic carbons. Our dipolar-dephased spectra indicated that a large fraction of alkoxy carbons were not protonated. For Coastal DOM, our NMR results were consistent with the presence of the major structural units of (1) carbohydrate-like moieties, (2) lignin residues, (3) peptides or amino sugars, and (4) COO-bonded alkyls. For Marine DOM, they were (1) carbohydrate-like moieties, (2) peptides or amino sugars, and (3) COO-bonded alkyls. In addition, both samples contained significant amounts of nonpolar alkyl groups. The potential sources of the major structural units of DOM were discussed in detail. Nonprotonated O-alkyl carbon content was proposed as a possible index of humification. PMID:22553962

Mao, Jingdong; Kong, Xueqian; Schmidt-Rohr, Klaus; Pignatello, Joseph J; Perdue, E Michael

2012-06-01

255

Protein fold determined by paramagnetic magic-angle spinning solid-state NMR spectroscopy  

PubMed Central

Biomacromolecules that are challenging for the usual structural techniques can be studied with atomic resolution by solid-state nuclear magnetic resonance. However, the paucity of >5 Å distance restraints, traditionally derived from measurements of magnetic dipole-dipole couplings between protein nuclei, is a major bottleneck that hampers such structure elucidation efforts. Here we describe a general approach that enables the rapid determination of global protein fold in the solid phase via measurements of nuclear paramagnetic relaxation enhancements (PREs) in several analogs of the protein of interest containing covalently-attached paramagnetic tags, without the use of conventional internuclear distance restraints. The method is demonstrated using six cysteine-EDTA-Cu2+ mutants of the 56-residue B1 immunoglobulin-binding domain of protein G, for which ~230 longitudinal backbone 15N PREs corresponding to ~10-20 Å distances were obtained. The mean protein fold determined in this manner agrees with the X-ray structure with a backbone atom root-mean-square deviation of 1.8 Å. PMID:22522262

Sengupta, Ishita; Nadaud, Philippe S.; Helmus, Jonathan J.; Schwieters, Charles D.; Jaroniec, Christopher P.

2012-01-01

256

Comparing quantum-chemical calculation methods for structural investigation of zeolite crystal structures by solid-state NMR spectroscopy.  

PubMed

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. PMID:20623826

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

2010-12-01

257

27Al and 29Si solid-state NMR characterization of calcium-aluminosilicate-hydrate.  

PubMed

Calcium silicate hydrate (C-S-H) is the main constituent of hydrated cement paste and determines its cohesive properties. Because of the environmental impact of cement industry, it is more and more common to replace a part of the clinker in cement by secondary cementitious materials (SCMs). These SCMs are generally alumina-rich and as a consequence some aluminum is incorporated into the C-S-H. This may have consequences on the cohesion and durability of the material, and it is thus of importance to know the amount and the location of Al in C-S-H and what the parameters are that control these features. The present paper reports the (29)Si and (27)Al MAS NMR analyses of well-characterized C-A-S-H samples (C-S-H containing Al). These samples were synthesized using an original procedure that successfully leads to pure C-A-S-H of controlled compositions in equilibrium with well-characterized solutions. The (27)Al MAS NMR spectra were quantitatively interpreted assuming a tobermorite-like structure for C-A-S-H to determine the aluminum location in this structure. For this purpose, an in-house written software was used which allows decomposing several spectra simultaneously using the same constrained spectral parameters for each resonance but with variable intensities. The hypothesis on the aluminum location in the C-A-S-H structure determines the proportion of each silicon site. Therefore, from the (27)Al NMR quantitative results and the chemical composition of each sample, the intensity of each resonance line in the (29)Si spectra was set. The agreement between the experimental and calculated (29)Si MAS NMR spectra corroborates the assumed C-A-S-H structure and the proposed Al incorporation mechanism. The consistency between the results obtained for all compositions provides another means to assess the assumptions on the C-A-S-H structure. It is found that Al substitutes Si mainly in bridging positions and moderately in pairing positions in some conditions. Al in pairing site is observed only for Ca/(Si+Al) ratios greater than 0.95 (equivalent to 4 mmol.L(-1) of calcium hydroxide). Finally, the results suggest that penta and hexa-coordinated aluminum are adsorbed on the sides of the C-A-S-H particles. PMID:22277014

Pardal, Xiaolin; Brunet, Francine; Charpentier, Thibault; Pochard, Isabelle; Nonat, André

2012-02-01

258

Solid-State NMR Reveals the Hydrophobic-Core Location of Poly(amidoamine) Dendrimers in Biomembranes  

PubMed Central

Poly(amidoamine) (PAMAM) dendrimer nanobiotechnology shows great promise in targeted drug delivery and gene therapy. Because of the involvement of cell membrane lipids with the pharmacological activity of dendrimer nanomedicines, the interactions between dendrimers and lipids are of particular relevance to the pharmaceutical applications of dendrimers. In this study, solid-state NMR was used to obtain a molecular image of the complex of generation 5 PAMAM dendrimer with the lipid bilayer. Using 1H radio frequency driven dipolar recoupling (RFDR) and 1H magic angle spinning (MAS) nuclear Overhauser effect spectroscopy (NOESY) techniques, we show that dendrimers are thermodynamically stable when inserted into zwitterionic lipid bilayers. 14N and 31P NMR experiments on static samples and measurements of the mobility of C–H bonds using a 2D proton detected local field protocol under MAS corroborate these results. The localization of dendrimers in the hydrophobic core of lipid bilayers restricts the motion of bilayer lipid tails, with the smaller G5 dendrimer having more of an effect than the larger G7 dendrimer. Fragmentation of the membrane does not occur at low dendrimer concentrations in zwitterionic membranes. Because these results show that the amphipathic dendrimer molecule can be stably incorporated in the interior of the bilayer (as opposed to electrostatic binding at the surface), they are expected to be useful in the design of dendrimer-based nanobiotechnologies. PMID:20481633

Smith, Pieter E. S.; Brender, Jeffrey R.; Durr, Ulrich H. N.; Xu, Jiadi; Mullen, Douglas G.; Banaszak Holl, Mark M.; Ramamoorthy, Ayyalusamy

2010-01-01

259

Expression and initial structural insights from solid-state NMR of the M2 proton channel from influenza A virus.  

PubMed

The M2 protein from influenza A virus has been expressed, purified, and reconstituted into DMPC/DMPG liposomes. SDS-PAGE analysis of reconstituted M2 protein in DMPC/DMPG liposomes demonstrates a stable tetrameric preparation. Circular dichroism spectra of the intact M2 protein in detergent indicate 67% alpha-helix. The uniformly (15)N-labeled M2 protein and both (15)N-Val- and (15)N-Leu-labeled M2 protein have been expressed from defined M9 media. The (1)H-(15)N HSQC (heteronuclear single quantum correlation) solution NMR experiments have been performed on the amino acid specific labeled protein in 300 mM SDS-d(25) micelles, and the data indicate a homogeneous preparation. The reconstituted M2/DMPC/DMPG proteoliposomes were used for preparing uniformly aligned solid-state NMR samples for (15)N-(1)H dipolar/(15)N chemical shift correlation experiments. The spectra support a transmembrane helix in M2 protein having a tilt angle of approximate 25 degrees, quantitatively similar to results obtained on the isolated M2 transmembrane peptide reconstituted in DMPC bilayers (38 degrees ). In addition, the spectra suggest that the tetrameric protein forms a symmetric or at least pseudosymmetric bundle consistent with data obtained by other research groups based on electrophysiological measurements and substituted cysteine scanning mutagenesis experiments that characterize a tetrameric structure. PMID:12220196

Tian, Changlin; Tobler, Kurt; Lamb, Robert A; Pinto, Lawrence H; Cross, T A

2002-09-17

260

Preservation of proteinaceous material during the degradation of the green alga Botryococcus braunii: A solid-state 2D 15N 13C NMR spectroscopy study  

Microsoft Academic Search

Using solid-state cross-polarization-magic-angle-spinning (CPMAS) 13C and 15N nuclear magnetic resonance (NMR) and 2-D double cross polarization (DCP) MAS 15N 13C NMR techniques, microbially degraded Botryococcus braunii was analyzed to study the chemical nature of organic nitrogen in the algal residue. The amide linkage, as found in protein, was observed as the major nitrogen component in 201-day-old degraded algae. No significant

Xu Zang; Reno T. Nguyen; H. Rodger Harvey; Heike Knicker; Patrick G. Hatcher

2001-01-01

261

Complexations of Hg(CN) 2 with imidazolidine-2-thione and its derivatives: Solid state, solution NMR and antimicrobial activity studies  

NASA Astrophysics Data System (ADS)

The preparation and characterization of new mercuric complexes of formula L 2Hg(CN) 2 with L being imidazolidine-2-thione (Imt) and its substituted derivatives, 1,3-diazinane-2-thione (Diaz), 1,3-diazipane-2-thione (Diap), are described. The solution and solid-state 13C NMR show a significant shift of the lbond2 C dbnd S carbon resonance of the ligands, while the other resonances are relatively unaffected, indicating that most likely the solid-state structure is maintained in solution as well. The principal components of the 199Hg shielding tensors were determined from solid-state NMR data. Antimicrobial activity studies of the free ligands and their complexes show that ligands exhibit substantial antibacterial activities compare to their Hg(II) complexes.

Wazeer, Mohamed I. M.; Isab, Anvarhusein A.

2007-12-01

262

Adsorption-desorption induced structural changes of Cu-MOF evidenced by solid state NMR and EPR spectroscopy.  

PubMed

Adsorption-desorption induced structural changes of Cu(bpy)(H(2)O)(2)(BF(4)),(bpy) (bpy = 4,4'-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF's structure as indicated by a high-field shift of the (11)B MAS NMR. After desorption, both EPR and (11)B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption-desorption steps are involved such as gas storage, separation, and catalysis. PMID:19159296

Jiang, Yijiao; Huang, Jun; Kasumaj, Besnik; Jeschke, Gunnar; Hunger, Michael; Mallat, Tamas; Baiker, Alfons

2009-02-18

263

Probing porous media with gas diffusion NMR  

NASA Technical Reports Server (NTRS)

We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks.

Mair, R. W.; Wong, G. P.; Hoffmann, D.; Hurlimann, M. D.; Patz, S.; Schwartz, L. M.; Walsworth, R. L.

1999-01-01

264

Investigation of Ti-doped NaAlH4 by solid-state NMR  

SciTech Connect

In recent years, the development of Ti-doped NaAlH{sub 4} as a hydrogen storage material has gained attention because of its large weight percentage of hydrogen ({approx}5%) compared to traditional interstitial hydrides. The addition of transition-metal dopants, in the form of Ti-halides, such as TiCl{sub 3}, dramatically improves the kinetics of the absorption and desorption of hydrogen from NaAlH{sub 4}. However, the role that Ti plays in enhancing the absorption and desorption of H{sub 2} is still unknown. In the present study, {sup 27}Al, {sup 23}Na, and {sup 1}H MAS (Magic Angle Spinning) NMR (Nuclear Magnetic Resonance) has been performed to understand the titanium speciation in Ti-doped NaAlH{sub 4}. All experiments were performed on a sample of crushed single crystals exposed to Ti during growth, a sample of solvent-mixed 4TiCl{sub 3} + 112NaAlH{sub 4}, a reacted sample of solvent-mixed TiCl{sub 3} + {sup 3}NaAlH{sub 4} with THF, and a reacted sample of ball-milled TiCl3 + 3NaAlH{sub 4}. The {sup 27}Al MAS NMR has shown differences in compound formation between solvent-mixed TiCl{sub 3} + 3NaAlH{sub 4} with THF and the mechanically ball-milled TiCl{sub 3} + 3NaAlH{sub 4}. {sup 27}Al MAS NMR of the mechanically ball-milled mixture of fully-reacted TiCl{sub 3} + 3NaAlH{sub 4} showed spectral signatures of TiAl{sub 3} while, the solvent-mixed 4TiCl{sub 3} + 112NaAlH{sub 4}, which is totally reacted, does not show the presences of TiAl{sub 3}, but shows the existence of Al{sub 2}O{sub 3}.

Maxwell, R; Majzoub, E; Herberg, J

2003-11-24

265

Alkylation of benzene with carbon monoxide over Zn/H-ZSM-5 zeolite studied using in situ solid-state NMR spectroscopy.  

PubMed

Using in situ solid-state NMR spectroscopy we show that CO can act as an alkylating reagent and react with benzene to produce toluene over a Zn/H-ZSM-5 zeolite. In the alkylation reaction, CO provides the methyl group of toluene via a methoxy intermediate. PMID:25126651

Wang, Xiumei; Xu, Jun; Qi, Guodong; Wang, Chao; Wang, Qiang; Deng, Feng

2014-10-01

266

High-Temperature Steam-Treatment of PBI, PEKK, and a PEKK-PBI Blend: A Solid-State NMR and IR Spectroscopic Study  

E-print Network

High-Temperature Steam-Treatment of PBI, PEKK, and a PEKK-PBI Blend: A Solid-State NMR and IR on the behavior and mechanism of polyetherketoneketone (PEKK)/PBI systems in contact with steam or condensed phase steam. In this contribution, the pure polymer components and the PEKK-PBI (60 : 40 wt %) blend are steam

Bluemel, Janet

267

Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy.  

PubMed

The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ~0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR. PMID:23963722

Mote, Kaustubh R; Gopinath, T; Veglia, Gianluigi

2013-10-01

268

Supramolecular assembly of dendritic polymers elucidated by 1H and 13C solid-state MAS NMR spectroscopy.  

PubMed

Advanced solid-state NMR methods under fast magic-angle spinning (MAS) are used to study the structure and dynamics of large supramolecular systems, which consist of a polymer backbone with dendritic side groups and self-assemble into a columnar structure. The NMR experiments are performed on as-synthesized samples, i.e., no isotopic enrichment is required. The analysis of (1)H NMR chemical-shift effects as well as dipolar (1)H-(1)H or (1)H-(13)C couplings provide site-specific insight into the local structure and the segmental dynamics, in particular, of phenyl rings and -CH(2)O- linking units within the dendrons. Relative changes of (1)H chemical shifts (of up to -3 ppm) serve as distance constraints and allow protons to be positioned relative to aromatic rings. Together with dipolar spinning sideband patterns, pi-pi packing phenomena and local order parameters (showing variations between 30% and 100%) are selectively and precisely determined, enabling the identification of the dendron cores as the structure-directing moieties within the supramolecular architecture. The study is carried out over a representative selection of systems which reflect characteristic differences, such as different polymer backbones, sizes of dendritic side groups, or length and flexibility of linking units. While the polymer backbone is found to have virtually no effect on the overall structure and properties, the systems are sensitively affected by changing the generation or the linkage of the dendrons. The results help to understand the self-assembly process of dendritic moieties and aid the chemical design of self-organizing molecular structures. PMID:14570506

Rapp, Almut; Schnell, Ingo; Sebastiani, Daniel; Brown, Steven P; Percec, Virgil; Spiess, Hans Wolfgang

2003-10-29

269

Neutron scattering, solid state NMR and quantum chemistry studies of 11-keto-progesterone  

NASA Astrophysics Data System (ADS)

The molecule geometry, frequency and intensity of the IINS and IR vibrational bands of 11-ketoprogesterone have been obtained by the HF, PM3 and density functional theory (DFT) with the B3LYP functionals and 6-31G(d,p) basis set. The optimised bond lengths and bond angles of the steroid skeleton are in good agreement with the X-ray data. The IR and IINS spectra of ketoprogesterone, computed at the DFT level, well reproduce the vibrational wavenumbers and intensities to an accuracy allowing reliable vibrational assignments. The molecular dynamic study by 1H NMR has confirmed the sequence of onset of reorientations of subsequent methyl groups indicated by the results of quantum chemistry calculations and INS spectra.

Szyczewski, A.; Ho?derna-Natkaniec, K.; Natkaniec, I.

2004-07-01

270

Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR  

NASA Astrophysics Data System (ADS)

The changes caused by heat treatment of gibbsite powder at 300-1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and 27Al magic angle spinning nuclear magnetic resonance spectroscopy (27Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of ?-Al2O3 as an intermediate phase between ?- and ?-Al2O3. The crystallite size of ?-Al2O3 is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in ?-Al2O3 and ?-Al2O3 increases, whereas the expected ratio is observed in ?-Al2O3. The percentage of AlO4 units in the transition aluminas follows the same behaviour as the ratio of Al/O.

Malki, A.; Mekhalif, Z.; Detriche, S.; Fonder, G.; Boumaza, A.; Djelloul, A.

2014-07-01

271

Solid-state NMR studies of interstitial phosphorus atoms in rhodium carbonyl clusters.  

PubMed

Pure samples and as-prepared mixtures of Rh9 and Rh10 carbonyl clusters with interstitial P atoms have been studied quantitatively by 31P MAS and 1H-31P CP/MAS NMR. Information on the 31P chemical shift tensor of the Rh9 and Rh10 clusters has been derived from spinning sideband simulations. The chemical shift anisotropy is slightly larger in the Rh10 clusters (340-400 ppm) than in the Rh9 clusters (230-300 ppm), while the asymmetry parameters are similar (eta = 0.1-0.4). The results contribute to the understanding of the relationship between the shielding anisotropy and the structure of the cluster cavity. PMID:9211624

Rocha, J; Orion, I; Nahring, J; Heaton, B T; Fernandez, C; Amoureux, J P

1997-05-01

272

A solid-state NMR investigation into microphase separation in polyurethane thermoplastic elastomers  

SciTech Connect

A combination of {sup 13}C-CP-MAS and static {sup 2}H-NMR techniques were used to study phase separation in polyurethane thermoplastic elastomers. The segmented polymers were prepared from hard segments comprised of 4,4{prime}-dicyclohexylmethane diisocyanate (DCHDI) chain extended with 1,4-butanediol, and soft segments of either poly(propylene glycol) or poly(butylene adipate). The DCHDI was prepared so as to contain different levels of the various geometric isomers, i.e., the cis,cis, cis,trans and trans,trans isomers, in order to monitor the influence of the trans,trans content on segmental mobility and phase separation. Lineshape analysis of static {sup 2}H-NMR spectra of samples selectively labelled in the chain extender indicate the trans,trans isomer constrains motion much more effectively than the other isomers of DCHDI at temperatures above the dynamic glass transition temperature of the soft phase and below the melting point of the hard domains. This is confirmed both by {sup 1}H-spin diffusion and t{sub 1{rho}} relaxation data. The data also indicate that the samples prepared with less trans-trans DCHDI have a much more significant interphase region than when DCHDI with a higher trans,trans content was employed, or that the higher trans-trans content allows for better hard domain formation. This insinuates that a relatively small amount of the trans,trans isomer of the DCHDI is more effective in allowing for the formation of physical cross-links than a larger amount of a statistical distribution of the diisocyanate, as corroborated by DSC and DMTA.

Meltzer, A.D.; Lantman, C.W.; Steppan, S.; Seneker, S.; Wehrle, B. [Miles Inc., Pittsburgh, PA (United States)

1993-12-31

273

Solid-state NMR studies of the crystalline and amorphous domains within PEO and PEO: LiTf systems.  

PubMed

Solid polymer electrolytes (SPEs) contain amorphous and crystalline regions, each of which have unique contributions to the (13)C NMR spectrum. Understanding and assigning the (13)C NMR signals are vital to interpreting the NMR data collected for each phase. The (13)C CPMAS solid-state NMR spectrum of poly(ethylene oxide), a common polymer electrolyte host material, has superimposed broad and narrow components. Previously, the narrow component has been assigned to the amorphous region and the broad component to the crystalline PEO fraction. These assignments for pure PEO have been applied to various PEO:salt systems. Using lithium triflate salt dissolved in PEO, we revisit the spectral assignments and discover that the narrow component is due to crystalline PEO:LiTf component, which is reversed from the previous pure PEO assignment. This paradigm shift is based on data collected from a 100% crystalline PEO:LiTf with a 3:1 oxygen:lithium ratio sample, which exhibited only the narrow peak. For dilute electrolytes, such as 20:1 PEO:LiTf, the (13)C CPMAS spectra contain the narrow peak superimposed on a broad peak as seen with pure PEO. As dilute electrolytes are heterogeneous with crystalline and amorphous regions of both pure PEO and PEO:LiTf complex, peak assignments for pure PEO and PEO:LiTf are important. Thus, we reexamine the previous assignment for pure PEO using samples of pure powdered PEO, thermally treated pure powdered PEO, and a thin film PEO cast from an acetonitrile solution. With these different samples, we observed the growth of the narrow peak under conditions that favor crystallization. Therefore, for pure PEO, we have reassigned the narrow peak to the crystalline region and the broad peak to the amorphous region. In light of our observations, previous NMR studies of pure PEO and PEO SPEs should be reinvestigated. We also use rotational echo double resonance (REDOR) to study the 20:1 PEO:LiTf created from 2 and 100 kDa PEO. We find that the lithium environment is similar in the respective microcrystalline domains. However, the 100 kDa samples have a larger fraction of pure crystalline PEO. PMID:17587555

Wickham, Jason R; Mason, Rachel N; Rice, Charles V

2007-07-01

274

Exploration of structure and function in biomolecules through solid-state NMR and computational methods  

NASA Astrophysics Data System (ADS)

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 dephasing experiments and 1H-- 13C heteronuclear correlation (HETCOR) experiments. A comparison of spectral data confirms the presence of two molecules in the asymmetric unit for form II (Z'=2) and regions of conformational variation between the two forms are posited. Structural rigidity is found throughout both forms and extends into the alkyl groups at the amine with similarties between form I and form II in this moiety. Likely regions of motion are found around the bond axes formed by C1--C5 in form I. This motion is also observed in one of the two molecules of form II. Tensor differences between the two forms at the tetrahydro-pyrrole center indicate that conformational variation between form I and form II exists in the dihedral angles formed by the atoms C14--C13--C3--C2, O--C12--C2--C1, C10--C5--C1--N1 and C21--C20--N1--C4. Finally, SSNMR is applied in conjunction with quantum mechanical calculations in the analysis of a novel polymorph of the anticancer drug paclitaxel. The three dimensional structure of paclitaxel is established through a combination of SSNMR tensor (13C & 15N) and 1H--13C HETCOR data. With two molecules in the asymmetric unit (Z'=2), this represents the first conformational characterization with Z'>1 established solely by SSNMR. Semi-empirical models are constructed and fitted to experimental data by adjusting the conformation of the paclitaxel models and selecting those conformers which minimize the difference between predicted and measured tensors. This computational grid search exhausively samples the conformation of paclitaxel, utilizing more than 600 independent models. HETCOR data at thirteen key positions provide shift assignment to the asymmetric unit for each comparison. The two distinct molecules of the asymmetric unit possess nearly identical baccatin III moieties with matching conformations of the C10 acetyl moiety. Additionally, both are found to exhibit an extended conformation of the phenylisoserine sidechain at the C13 position. Notable differences between the two forms are centered around the rotation axes of O--C13,

Heider, Elizabeth M.

275

Planar microcoil-based microfluidic NMR probes  

NASA Astrophysics Data System (ADS)

Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120, and 470 nL. The achieved sensitivity enables acquisition of an 1H spectrum of 160 ?g sucrose in D 2O, corresponding to a proof-of-concept for on-chip NMR spectroscopy. Increase of mass-sensitivity with coil diameter reduction is demonstrated experimentally for planar microcoils. Models that enable quantitative prediction of the signal-to-noise ratio and of the influence of microfluidic channel geometry on spectral resolution are presented and successfully compared to the experimental data. The main factor presently limiting sensitivity for high-resolution applications is identified as being probe-induced static magnetic field distortions. Finally, based on the presented model and measured data, future performance of planar microcoil-based microfluidic NMR probes is extrapolated and discussed.

Massin, C.; Vincent, F.; Homsy, A.; Ehrmann, K.; Boero, G.; Besse, P.-A.; Daridon, A.; Verpoorte, E.; de Rooij, N. F.; Popovic, R. S.

2003-10-01

276

Planar microcoil-based microfluidic NMR probes.  

PubMed

Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120, and 470 nL. The achieved sensitivity enables acquisition of an 1H spectrum of 160 microg sucrose in D2O, corresponding to a proof-of-concept for on-chip NMR spectroscopy. Increase of mass-sensitivity with coil diameter reduction is demonstrated experimentally for planar microcoils. Models that enable quantitative prediction of the signal-to-noise ratio and of the influence of microfluidic channel geometry on spectral resolution are presented and successfully compared to the experimental data. The main factor presently limiting sensitivity for high-resolution applications is identified as being probe-induced static magnetic field distortions. Finally, based on the presented model and measured data, future performance of planar microcoil-based microfluidic NMR probes is extrapolated and discussed. PMID:14511593

Massin, C; Vincent, F; Homsy, A; Ehrmann, K; Boero, G; Besse, P-A; Daridon, A; Verpoorte, E; de Rooij, N F; Popovic, R S

2003-10-01

277

FT-IR and solid-state NMR investigation of phosphorus promoted hydrotreating catalyst precursors  

SciTech Connect

The effect of phosphorus on the structure of Ni-Mo/Al{sub 2}O{sub 3} hydrotreating catalyst precursors has been investigated. Calcined and reduced P/Al{sub 2}O{sub 3}, P-Ni/Al{sub 2}O{sub 3}, P-Mo/Al{sub 2}O{sub 3}, and P-Ni-Mo/Al{sub 2}O{sub 3} (where the wt% P = 0.0 to 10.0 wt % Mo = 8.0 to 12.0, and wt% Ni = 4.0) have been studied using FT-IR, XRD, and {sup 27}Al MAS NMR techniques. Phosphoric acid reacts with alumina hydroxyls forming monomeric and polymeric phosphates. At the higher phosphorus loadings, aluminum phosphate is also formed. On calcined P-Ni/Al{sub 2}O{sub 3}, nickel phosphate is formed. This leads to a decrease in density of Ni{sub 0} sites in the reduced state as measured by CO adsorption. The addition of up to 1.5 wt% P to Mo(8)/Al{sub 2}O{sub 3} promotes the formation of octahedral molybdena on the alumina surface. However, the addition of > 2.0 wt% P results in the formation of bulk MoO{sub 3} and Al{sub 2}(MoO{sub 4}){sub 3} in both P-Mo(8)/Al{sub 2}O{sub 3} and P-Mo(12)/Al{sub 2}O{sub 3}. CO adsorption on reduced P-Ni(4)-Mo(8)/Al{sub 2}O{sub 3} samples shows that the presence of 0.5 wt% P causes a significant increase in the number of sites adsorbing CO. Increasing the P loading further causes a decrease in the number of adsorbing sites; this decrease can be attributed to the formation of either nickel phosphate or nickel molybdate.

DeCanio, E.C.; Edwards, J.C.; Scalzo, T.R.; Storm, D.A. (Texaco Inc., Beacon, NY (United States)) Bruno, J.W. (Wesleyan Univ., Middletown, CT (United States))

1991-12-01

278

Perturbations to 27Al electric field gradients in nanocrystalline alpha-Al2O3 studied by high-resolution solid-state NMR.  

PubMed

(27)Al solid-state NMR has been employed to study the perturbations to (27)Al electric field gradients for the aluminum environments in nanocrystalline alpha-alumina. Triple quantum magic angle spinning experiments show that the octahedral aluminum coordination remains unchanged down to 12 nm, although severe perturbations to (27)Al electric field gradients are noticed at 28 nm and below. 3Q-MAS and SATRAS experimental data of nano alpha-alumina have been analyzed through extensive spectral simulations to probe (27)Al electric field gradients of aluminum in the grains and grain boundaries. While the aluminum in the grains has a unique field gradient tensor, the same octahedrally coordinated aluminum environments in the grain boundaries suffer a distribution of electric field gradients. This is evidenced by data analysis of both 3Q-MAS and SATRAS spectra. By invoking the Gaussian isotropic model, in which the (C(Q), eta(Q)) parameter space is discretely sampled by the Czjzek distribution, we have been able to analyze the (27)Al SATRAS spectra of nanocrystalline alpha-alumina samples having grain sizes of 52, 28, 20, and 12 nm. Good agreement between experimental and simulated spectra has led to the quantitative determination of grain and grain boundary components in these materials. PMID:20073527

Sabarinathan, V; Ramasamy, S; Ganapathy, S

2010-02-11

279

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

SciTech Connect

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.

Sumner, S.C.J.

1986-01-01

280

Refocused continuous-wave decoupling: a new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy.  

PubMed

A novel strategy for heteronuclear dipolar decoupling in magic-angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy is presented, which eliminates residual static high-order terms in the effective Hamiltonian originating from interactions between oscillating dipolar and anisotropic shielding tensors. The method, called refocused continuous-wave (rCW) decoupling, is systematically established by interleaving continuous wave decoupling with appropriately inserted rotor-synchronized high-power ? refocusing pulses of alternating phases. The effect of the refocusing pulses in eliminating residual effects from dipolar coupling in heteronuclear spin systems is rationalized by effective Hamiltonian calculations to third order. In some variants the ? pulse refocusing is supplemented by insertion of rotor-synchronized ?/2 purging pulses to further reduce the residual dipolar coupling effects. Five different rCW decoupling sequences are presented and their performance is compared to state-of-the-art decoupling methods. The rCW decoupling sequences benefit from extreme broadbandedness, tolerance towards rf inhomogeneity, and improved potential for decoupling at relatively low average rf field strengths. In numerical simulations, the rCW schemes clearly reveal superior characteristics relative to the best decoupling schemes presented so far, which we to some extent also are capable of demonstrating experimentally. A major advantage of the rCW decoupling methods is that they are easy to set up and optimize experimentally. PMID:23231224

Vinther, Joachim M; Nielsen, Anders B; Bjerring, Morten; van Eck, Ernst R H; Kentgens, Arno P M; Khaneja, Navin; Nielsen, Niels Chr

2012-12-01

281

Solid-state NMR Study Reveals Collagen I Structural Modifications of Amino Acid Side Chains upon Fibrillogenesis*  

PubMed Central

In vivo, collagen I, the major structural protein in human body, is found assembled into fibrils. In the present work, we study a high concentrated collagen sample in its soluble, fibrillar, and denatured states using one and two dimensional {1H}-13C solid-state NMR spectroscopy. We interpret 13C chemical shift variations in terms of dihedral angle conformation changes. Our data show that fibrillogenesis increases the side chain and backbone structural complexity. Nevertheless, only three to five rotameric equilibria are found for each amino acid residue, indicating a relatively low structural heterogeneity of collagen upon fibrillogenesis. Using side chain statistical data, we calculate equilibrium constants for a great number of amino acid residues. Moreover, based on a 13C quantitative spectrum, we estimate the percentage of residues implicated in each equilibrium. Our data indicate that fibril formation greatly affects hydroxyproline and proline prolyl pucker ring conformation. Finally, we discuss the implication of these structural data and propose a model in which the attractive force of fibrillogenesis comes from a structural reorganization of 10 to 15% of the amino acids. These results allow us to further understand the self-assembling process and fibrillar structure of collagen. PMID:23341452

De Sa Peixoto, Paulo; Laurent, Guillaume; Azais, Thierry; Mosser, Gervaise

2013-01-01

282

Crystal Polymorphism of Protein GB1 Examined by Solid-State NMR Spectroscopy and X-ray Diffraction  

SciTech Connect

The study of micro- or nanocrystalline proteins by magic-angle spinning (MAS) solid-state NMR (SSNMR) gives atomic-resolution insight into structure in cases when single crystals cannot be obtained for diffraction studies. Subtle differences in the local chemical environment around the protein, including the characteristics of the cosolvent and the buffer, determine whether a protein will form single crystals. The impact of these small changes in formulation is also evident in the SSNMR spectra; however, the changes lead only to correspondingly subtle changes in the spectra. Here, we demonstrate that several formulations of GB1 microcrystals yield very high quality SSNMR spectra, although only a subset of conditions enable growth of single crystals. We have characterized these polymorphs by X-ray powder diffraction and assigned the SSNMR spectra. Assignments of the 13C and 15N SSNMR chemical shifts confirm that the backbone structure is conserved, indicative of a common protein fold, but side chain chemical shifts are changed on the surface of the protein, in a manner dependent upon crystal packing and electrostatic interactions with salt in the mother liquor. Our results demonstrate the ability of SSNMR to reveal minor structural differences among crystal polymorphs. This ability has potential practical utility for studying the formulation chemistry of industrial and therapeutic proteins, as well as for deriving fundamental insights into the phenomenon of single-crystal growth.

Schmidt,H.; Sperling, L.; Gao, Y.; Wylie, B.; Boettcher, J.; Wilson, S.; Rienstra, C.

2007-01-01

283

Structure and Dynamics Characterization of HMDI- and MDI-based Poly(urethane urea) Elastomers via Solid- State NMR  

NASA Astrophysics Data System (ADS)

High performance elastomers have recently gained considerable interest throughout DoD, particularly for their potential in ballistic impact protection and blast mitigation capabilities. Recent simulation results based on coarse-grained modeling have revealed the role of the intermolecular interaction and the flexibility of interface between hard and soft segments on the morphology and mechanical deformation behavior of poly(urethane urea), PUU, elastomers. In this work, we exploit solid-state nuclear magnetic resonance (NMR) techniques to investigate the influence of hard domain size on molecular dynamics by comparing the diisocyanate chemistry (aliphatic 4,4'-dicyclohexylmethane diisocyanate (HMDI) vs. aromatic 4,4'-diphenylmethane diisocyanate (MDI)) in PUU elastomers. Despite identical stoichiometry and soft segment chemical structure, large difference in the molecular dynamics, indicated by the ^1H dipolar dephasing time (Td), is observed. The Td of HMDI-PUU is shorter and it exhibits higher activation energy, suggesting finer phase mixing. Results from ^1H spin echo measurements are also included for comparison.

Hu, Weiguo; Hsieh, Alex; Rinderspacher, B. Christopher; Chantawansri, Tanya

2013-03-01

284

Crystal Polymorphism of Protein GB1 Examined by Solid-State NMR Spectroscopy and X-ray Diffraction  

PubMed Central

The study of micro- or nanocrystalline proteins by magic-angle spinning (MAS) solid-state NMR (SSNMR) gives atomic-resolution insight into structure in cases when single crystals cannot be obtained for diffraction studies. Subtle differences in the local chemical environment around the protein, including the characteristics of the co-solvent and the buffer, determine whether a protein will form single crystals. The impact of these small changes in formulation is also evident in the SSNMR spectra, but leads only to correspondingly subtle changes in the spectra. Here we demonstrate that several formulations of GB1 microcrystals yield very high-quality SSNMR spectra, although only a subset of conditions enable growth of single crystals. We have characterized these polymorphs by X-ray powder diffraction and assigned the SSNMR spectra. Assignments of the 13C and 15N SSNMR chemical shifts confirm that the backbone structure is conserved, indicative of a common protein fold, but sidechain chemical shifts are changed on the surface of the protein, in a manner dependent upon crystal packing and electrostatic interactions with salt in the mother liquor. Our results demonstrate the ability of SSNMR to reveal minor structural differences among crystal polymorphs. This ability has potential practical utility for studying formulation chemistry of industrial and therapeutic proteins, as well as for deriving fundamental insights into the phenomenon of single crystal growth. PMID:18052145

Frericks Schmidt, Heather L.; Sperling, Lindsay J.; Gao, Yi Gui; Wylie, Benjamin J.; Boettcher, John M.; Wilson, Scott R.; Rienstra, Chad M.

2009-01-01

285

Solid-State Selective 13C Excitation and Spin Diffusion NMR to Resolve Spatial Dimensions in Plant Cell Walls  

SciTech Connect

The average spatial dimensions between major biopolymers within the plant cell wall can be resolved using a solid-state NMR technique referred to as a {sup 13}C cross-polarization (CP) SELDOM (selectively by destruction of magnetization) with a mixing time delay for spin diffusion. Selective excitation of specific aromatic lignin carbons indicates that lignin is in close proximity to hemicellulose followed by amorphous and finally crystalline cellulose. {sup 13}C spin diffusion time constants (T{sub SD}) were extracted using a two-site spin diffusion theory developed for {sup 13}C nuclei under magic angle spinning (MAS) conditions. These time constants were then used to calculate an average lower-limit spin diffusion length between chemical groups within the plant cell wall. The results on untreated {sup 13}C enriched corn stover stem reveal that the lignin carbons are, on average, located at distances {approx}0.7-2.0 nm from the carbons in hemicellulose and cellulose, whereas the pretreated material had larger separations.

Foston, M.; Katahira, R.; Gjersing, E.; Davis, M. F.; Ragauskas, A. J.

2012-02-15

286

Fast acquisition of multi-dimensional spectra in solid-state NMR enabled by ultra-fast MAS  

NASA Astrophysics Data System (ADS)

The advantages offered by ultra-fast (>60 kHz) magic angle spinning (MAS) rotation for the study of biological samples, notably containing paramagnetic centers are explored. It is shown that optimal conditions for performing solid-state 13C NMR under 60 kHz MAS are obtained with low-power CW 1H decoupling, as well as after a low-power 1H, 13C cross-polarization step at a double-quantum matching condition. Acquisition with low-power decoupling highlights the existence of rotational decoupling sidebands. The sideband intensities and the existence of first and second rotary conditions are explained in the framework of the Floquet-van Vleck theory. As a result, optimal 13C spectra of the oxidized, paramagnetic form of human copper zinc superoxide dismutase (SOD) can be obtained employing rf-fields which do not exceed 40 kHz during the whole experiment. This enables the removal of unwanted heating which can lead to deterioration of the sample. Furthermore, combined with the short 1H T 1s, this allows the repetition rate of the experiments to be shortened from 3 s to 500 ms, thus compensating for the sensitivity loss due to the smaller sample volume in a 1.3 mm rotor. The result is that 2D 13C- 13C correlation could be acquired in about 24 h on less than 1 mg of SOD sample.

Laage, Ségolène; Sachleben, Joseph R.; Steuernagel, Stefan; Pierattelli, Roberta; Pintacuda, Guido; Emsley, Lyndon

2009-02-01

287

Fast acquisition of multi-dimensional spectra in solid-state NMR enabled by ultra-fast MAS.  

PubMed

The advantages offered by ultra-fast (>60 kHz) magic angle spinning (MAS) rotation for the study of biological samples, notably containing paramagnetic centers are explored. It is shown that optimal conditions for performing solid-state (13)C NMR under 60 kHz MAS are obtained with low-power CW (1)H decoupling, as well as after a low-power (1)H,(13)C cross-polarization step at a double-quantum matching condition. Acquisition with low-power decoupling highlights the existence of rotational decoupling sidebands. The sideband intensities and the existence of first and second rotary conditions are explained in the framework of the Floquet-van Vleck theory. As a result, optimal (13)C spectra of the oxidized, paramagnetic form of human copper zinc superoxide dismutase (SOD) can be obtained employing rf-fields which do not exceed 40 kHz during the whole experiment. This enables the removal of unwanted heating which can lead to deterioration of the sample. Furthermore, combined with the short (1)H T(1)s, this allows the repetition rate of the experiments to be shortened from 3 s to 500 ms, thus compensating for the sensitivity loss due to the smaller sample volume in a 1.3 mm rotor. The result is that 2D (13)C-(13)C correlation could be acquired in about 24 h on less than 1 mg of SOD sample. PMID:19028122

Laage, Ségolène; Sachleben, Joseph R; Steuernagel, Stefan; Pierattelli, Roberta; Pintacuda, Guido; Emsley, Lyndon

2009-02-01

288

SSB Binding to Single-Stranded DNA Probed Using Solid-State Nanopore Sensors.  

PubMed

Single-stranded DNA (ssDNA) binding protein plays an important role in the DNA replication process in a wide range of organisms. It binds to ssDNA to prevent premature reannealing and to protect it from degradation. Current understanding of SSB/ssDNA interaction points to a complex mechanism, including SSB motion along the DNA strand. We report on the first characterization of this interaction at the single-molecule level using solid-state nanopore sensors, namely without any labeling or surface immobilization. Our results show that the presence of SSB on the ssDNA can control the speed of nanopore translocation, presumably due to strong interactions between SSB and the nanopore surface. This enables nanopore-based detection of ssDNA fragments as short as 37 nt, which is normally very difficult with solid-state nanopore sensors, due to constraints in noise and bandwidth. Notably, this fragment is considerably shorter than the 65 nt binding motif, typically required for SSB binding at high salt concentrations. The nonspecificity of SSB binding to ssDNA further suggests that this approach could be used for fragment sizing of short ssDNA. PMID:25222770

Japrung, Deanpen; Bahrami, Azadeh; Nadzeyka, Achim; Peto, Lloyd; Bauerdick, Sven; Edel, Joshua B; Albrecht, Tim

2014-10-01

289

Sensitivity and resolution enhanced solid-state NMR for paramagnetic systems and biomolecules under very fast magic angle spinning.  

PubMed

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 A? 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 prospects for studying bimolecules using (13)C SSNMR under ultrafast MAS at the spinning speed of ?100 kHz. PMID:23889329

Parthasarathy, Sudhakar; Nishiyama, Yusuke; Ishii, Yoshitaka

2013-09-17

290

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

PubMed Central

CONSPECTUS Recent research in fast magic angle spinning (MAS) methods has drastically improved in the resolution and sensitivity for NMR spectroscopy of biomolecules and materials in solids. In this Account, we summarizes recent and ongoing developments in this area by presenting 13C and 1H 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 20 kHz allows us to overcome major difficulties in 1H and 13C 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) using short 1H T1 values we can perform 1H SSNMR micro-analysis of paramagnetic systems in the ?g scale with greatly improved sensitivity over that for diamagnetic systems. Second, we discuss how VFMAS at a spinning speed greater than ~40 kHz can enhance the sensitivity and resolution of 13C biomolecular SSNMR measurements. Low-power 1H decoupling schemes under VFMAS offer excellent spectral resolution for 13C SSNMR by nominal 1H RF irradiation at ~10 kHz. By combining the VFMAS approach and enhanced 1H T1 relaxation by paramagnetic doping we can achieve extremely fast recycling in modern biomolecular SSNMR experiments. Experiments for 13C-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 13C SSNMR measurements for biomolecules under faster MAS at a higher field. Our preliminary 13C SSNMR data of A? amyloid fibrils and GB1 microcrystals acquired at 1H NMR frequencies of 750-800 MHz suggest that the combined use of the PACC approach and the ultra-high fields could allow for routine multi-dimensional SSNMR analyses of proteins at the 50-200 nmol level. Also, we briefly discuss the prospects for studying bimolecules using 13C SSNMR under ultra fast MAS at the spinning speed of ~100 kHz. PMID:23889329

PARTHASARATHY, SUDHAKAR; NISHIYAMA, YUSUKE; ISHII, YOSHITAKA

2013-01-01

291

Membrane binding of an acyl-lactoferricin B antimicrobial peptide from solid-state NMR experiments and molecular dynamics simulations  

PubMed Central

One approach to the growing health problem of antibiotic resistant bacteria is the development of antimicrobial peptides (AMPs) as alternative treatments. The mechanism by which these AMPs selectively attack the bacterial membrane is not well understood, but is believed to depend on differences in membrane lipid composition. N-acylation of the small amidated hexapeptide, RRWQWR-NH2 (LfB6) derived from the 25 amino acid bovine lactoferricin (LfB25) can be an effective means to improve its antimicrobial properties. Here, we investigate the interactions of C6-LfB6, N-acylated with a 6 carbon fatty acid, with model lipid bilayers with two distinct compositions: 3:1 POPE:POPG (negatively charged) and POPC (zwitterionic). Results from solid-state 2H and 31P NMR experiments are compared with those from an ensemble of all-atom molecular dynamics simulations running in aggregate more than 8.6 microseconds. 2H NMR spectra reveal no change in the lipid acyl chain order when C6-LfB6 is bound to the negatively charged membrane and only a slight decrease in order when it is bound to the zwitterionic membrane. 31P NMR spectra show no significant perturbation of the phosphate headgroups of either lipid system in the presence of C6-LfB6. Molecular dynamics simulations show that for the negatively charged membrane, the peptide’s arginines drive the initial association with the membrane, followed by attachment of the tryptophans at the membrane-water interface, and finally by the insertion of the C6 tails deep into the bilayer. In contrast, the C6 tail leads the association with the zwitterionic membrane, with the tryptophans and arginines associating with the membrane-water interface in roughly the same amount of time. We find similar patterns in the order parameters from our simulations. Moreover, we find in the simulations that the C6 tail can insert 1–2 Å more deeply into the zwitterionic membrane and can exist in a wider range of angles than in the negatively charged membrane. We propose this is due to the larger area per lipid in the zwitterionic membrane, which provides more space for the C6 to insert and assume different orientations. PMID:21477580

Romo, Tod D.; Bradney, Laura A.; Greathouse, Denise V.; Grossfield, Alan

2011-01-01

292

Solid-state NMR adiabatic TOBSY sequences provide enhanced sensitivity for multidimensional high-resolution magic-angle-spinning 1H MR spectroscopy  

NASA Astrophysics Data System (ADS)

We propose a solid-state NMR method that maximizes the advantages of high-resolution magic-angle-spinning (HRMAS) applied to intact biopsies when compared to more conventional liquid-state NMR approaches. Theoretical treatment, numerical simulations and experimental results on intact human brain biopsies are presented. Experimentally, it is proven that an optimized adiabatic TOBSY (TOtal through Bond correlation SpectroscopY) solid-state NMR pulse sequence for two-dimensional 1H- 1H homonuclear scalar-coupling longitudinal isotropic mixing provides a 20%-50% improvement in signal-to-noise ratio relative to its liquid-state analogue TOCSY (TOtal Correlation SpectroscopY). For this purpose we have refined the C9151 symmetry-based 13C TOBSY pulse sequence for 1H MRS use and compared it to MLEV-16 TOCSY sequence. Both sequences were rotor-synchronized and implemented using WURST-8 adiabatic inversion pulses. As discussed theoretically and shown in simulations, the improved magnetization-transfer comes from actively removing residual dipolar couplings from the average Hamiltonian. Importantly, the solid-state NMR techniques are tailored to perform measurements at low temperatures where sample degradation is reduced. This is the first demonstration of such a concept for HRMAS metabolic profiling of disease processes, including cancer, from biopsies requiring reduced sample degradation for further genomic analysis.

Andronesi, Ovidiu C.; Mintzopoulos, Dionyssios; Struppe, Jochem; Black, Peter M.; Tzika, A. Aria

2008-08-01

293

51V Solid-state NMR and Density-Functional Theory Studies of Eight-Coordinate Non-Oxo Vanadium Complexes: Oxidized Amavadin  

PubMed Central

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

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

2014-01-01

294

Solid-State and Solution NMR Studies of the CAP-Gly Domain of Mammalian Dynactin and Its Interaction with Microtubules  

SciTech Connect

Microtubules (MTs) and microtubule binding proteins (MTBPs) play fundamental physiological roles including vesicle and organelle transport, cell motility, and cell division. Despite the importance of the MT/MTBP assemblies, there remains virtually no structural or dynamic information about their interaction at the atomic level due to the inherent insolubility and lack of long-range order of MTs. In this study, we present a combined magic angle spinning solid-state and solution NMR study of the MTBP CAP-Gly domain of mammalian dynactin and its interaction with paclitaxel-stabilized microtubules. We report resonance assignments and secondary structure analysis of the free CAP-Gly in solution and in the solid state by a combination of two- and three-dimensional homo- and heteronuclear correlation spectra. In solution, binding of CAP-Gly to microtubules is accompanied by the broadening of the majority of the peaks in HSQC spectra except for the residues at the termini, precluding further structural analysis of the CAP-Gly/microtubule complexes. In the solid state, DARR spectra of free CAP-Gly and its complex with microtubules display well-resolved lines, permitting residue-specific resonance assignments. Interestingly, a number of chemical shifts in the solid-state DARR spectra of the CAP-Gly/microtubule complex are perturbed compared to those of the free CAP-Gly, suggesting that conformational changes occur in the protein upon binding to the microtubules. These results indicate that CAP-Gly/microtubule assemblies are amenable to detailed structural characterization by magic angle spinning NMR spectroscopy and that solid-state NMR is a viable technique to study MT/protein interactions in general.

Sun, Shangjin; Siglin, Amanda; Williams, John C.; Polenova, Tatyana E.

2009-07-29

295

Molecular-level secondary structure, polymorphism, and dynamics of full-length -synuclein fibrils studied by solid-state NMR  

NASA Astrophysics Data System (ADS)

The 140-residue protein -synuclein (AS) is able to form amyloid fibrils and as such is the main component of protein inclusions involved in Parkinson's disease. We have investigated the structure and dynamics of full-length AS fibrils by high-resolution solid-state NMR spectroscopy. Homonuclear and heteronuclear 2D and 3D spectra of fibrils grown from uniformly 13C/15N-labeled AS and AS reverse-labeled for two of the most abundant amino acids, K and V, were analyzed. 13C and 15N signals exhibited linewidths of <0.7 ppm. Sequential assignments were obtained for 48 residues in the hydrophobic core region. We identified two different types of fibrils displaying chemical-shift differences of up to 13 ppm in the 15N dimension and up to 5 ppm for backbone and side-chain 13C chemical shifts. EM studies suggested that molecular structure is correlated with fibril morphology. Investigation of the secondary structure revealed that most amino acids of the core region belong to -strands with similar torsion angles in both conformations. Selection of regions with different mobility indicated the existence of monomers in the sample and allowed the identification of mobile segments of the protein within the fibril in the presence of monomeric protein. At least 35 C-terminal residues were mobile and lacked a defined secondary structure, whereas the N terminus was rigid starting from residue 22. Our findings agree well with the overall picture obtained with other methods and provide insight into the amyloid fibril structure and dynamics with residue-specific resolution. EM | protein structure | amyloid | Parkinson's disease | protein aggregation


Heise, Henrike; Hoyer, Wolfgang; Becker, Stefan; Andronesi, Ovidiu C.; Riedel, Dietmar; Baldus, Marc

2005-11-01

296

Membrane structure and conformational changes of the antibiotic heterodimeric peptide distinctin by solid-state NMR spectroscopy  

PubMed Central

The heterodimeric antimicrobial peptide distinctin is composed of 2 linear peptide chains of 22- and 25-aa residues that are connected by a single intermolecular S-S bond. This heterodimer has been considered to be a unique example of a previously unrecorded class of bioactive peptides. Here the 2 distinctin chains were prepared by chemical peptide synthesis in quantitative amounts and labeled with 15N, as well as 15N and 2H, at selected residues, respectively, and the heterodimer was formed by oxidation. CD spectroscopy indicates a high content of helical secondary structures when associated with POPC/POPG 3:1 vesicles or in membrane-mimetic environments. The propensity for helix formation follows the order heterodimer >chain 2 >chain 1, suggesting that peptide-peptide and peptide-lipid interactions both help in stabilizing this secondary structure. In a subsequent step the peptides were reconstituted into oriented phospholipid bilayers and investigated by 2H and proton-decoupled 15N solid-state NMR spectroscopy. Whereas chain 2 stably inserts into the membrane at orientations close to perfectly parallel to the membrane surface in the presence or absence of chain 1, the latter adopts a more tilted alignment, which further increases in the heterodimer. The data suggest that membrane interactions result in considerable conformational rearrangements of the heterodimer. Therefore, chain 2 stably anchors the heterodimer in the membrane, whereas chain 1 interacts more loosely with the bilayer. These structural observations are consistent with the antimicrobial activities when the individual chains are compared to the dimer. PMID:19805350

Resende, Jarbas M.; Moraes, Cleria Mendonca; Munhoz, Victor H. O.; Aisenbrey, Christopher; Verly, Rodrigo M.; Bertani, Philippe; Cesar, Amary; Pilo-Veloso, Dorila; Bechinger, Burkhard

2009-01-01

297

Direct Speciation of Phosphorus in Alum-Amended Poultry Litter: Solid-State 31P NMR Investigation  

SciTech Connect

Amending poultry litter (PL) with aluminum sulfate (alum) has proven to be effective in reducing water-soluble phosphorus (P) in the litter and in runoff from fields that have received PL applications; it has therefore been suggested as a best management practice. Although its effectiveness has been demonstrated on a macroscopic scale in the field, little is known about P speciation in either alumamended or unamended litter. This knowledge is important for the evaluation of the long-term stability and bioavailability of P, which is a necessary prerequisite for the assessment of the sustainability of intensive poultry operations. Both solid state MAS and CP-MAS {sup 31}P NMR as well as {sup 31}P({sup 27}Al) TRAPDOR were used to investigate P speciation in alumamended and unamended PL. The results indicate the presence of a complex mixture of organic and inorganic orthophosphate phases. A calcium phosphate phase, probably a surface precipitate on calcium carbonate, could be identified in both unamended and alum-amended PL, as well as physically bound HPO{sub 4}{sup 2-}. Phosphate associated with Al was found in the alum-amended PL, most probably a mixture of a poorly ordered wavellite and phosphate surface complexes on aluminum hydroxide that had been formed by the hydrolysis of alum. However, a complex mixture of organic and inorganic phosphate species could not be resolved. Phosphate associated with Al comprised on average 40{+-}14% of the total P in alum-amended PL, whereas calcium phosphate phases comprised on average 7{+-}4% in the alum-amended PL and 14{+-}5% in the unamended PL.

Hunger, Stefan; Cho, Herman M.; Sims, James T.; Sparks, Donald L.

2004-02-01

298

YPdSn and YPd2Sn: Structure, 89Y solid state NMR and 119Sn Mössbauer spectroscopy  

NASA Astrophysics Data System (ADS)

The stannides YPdSn and YPd2Sn were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both structures were refined on the basis of single crystal X-ray diffractometer data: TiNiSi type, Pnma, a=715.4(1), b=458.8(1), c=789.1(1) pm, wR2=0.0461, 510 F2 values, 20 variables for YPdSn and MnCu2Al type, Fm3barm, a=671.44(8), wR2=0.0740, 55 F2 values, 5 parameters for YPd2Sn. The yttrium atoms in the new stannide YPdSn are coordinated by two tilted Pd3Sn3 hexagons (ordered AlB2 superstructure). In the Heusler phase YPd2Sn each yttrium atom has octahedral tin coordination and additionally eight palladium neighbors. The cubic site symmetry of yttrium is reflected in the 119Sn Mössbauer spectrum which shows no quadrupole splitting. In contrast, YPdSn shows a single signal at ?=1.82(1) mm/s subjected to quadrupole splitting of ?EQ=0.93(1) mm/s. Both compounds have been characterized by high-resolution 89Y solid state NMR spectroscopy, which indicates the presence of strong Knight shifts. The spectrum of YPd2Sn is characterized by an unusually large linewidth, suggesting the presence of a Knight shift distribution reflecting local disordering effects. The range of 89Y Knight shifts of several binary and ternary intermetallic yttrium compounds is briefly discussed.

Höting, Christoph; Eckert, Hellmut; Langer, Thorsten; Schellenberg, Inga; Pöttgen, Rainer

2012-06-01

299

Structural changes of a light-activated G protein-coupled receptor determined by solid-state NMR: Channeling light energy into the visual pigment rhodopsin  

Microsoft Academic Search

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

Evan Daniel Crocker

2005-01-01

300

The structural properties of the transmembrane segment of the integral membrane protein phospholamban utilizing 13C CPMAS, 2H, and REDOR solid-state NMR spectroscopy  

Microsoft Academic Search

Solid-state NMR spectroscopic techniques were used to investigate the secondary structure of the transmembrane peptide phospholamban (TM-PLB), a sarcoplasmic Ca2+ regulator. 13C cross-polarization magic angle spinning spectra of 13C carbonyl-labeled Leu39 of TM-PLB exhibited two peaks in a pure 1-palmitoyl-2-oleoyl-phosphocholine (POPC) bilayer, each due to a different structural conformation of phospholamban as characterized by the corresponding 13C chemical shift. The

Ethan S. Karp; Elvis K. Tiburu; Shadi Abu-Baker; Gary A. Lorigan

2006-01-01

301

A practical synthesis of the 13C/15N-labelled tripeptide N-formyl-Met-Leu-Phe, useful as a reference in solid-state NMR spectroscopy  

PubMed Central

Summary A mild synthetic method for N-formyl-Met-Leu-Phe-OH (1) is described. After Fmoc solid phase peptide synthesis, on-bead formylation and HPLC purification, more than 30 mg of the fully 13C/15N-labelled tripeptide 1 could be isolated in a typical batch. This peptide can be easily crystallised and is therefore well suited as a standard sample for setting up solid-state NMR experiments. PMID:18982075

Lopez, Jakob J; Durner, Gerd; Glaubitz, Clemens

2008-01-01

302

Modification of H-ZSM-5 zeolites with phosphorus. 2. Interaction between phosphorus and aluminum studied by solid-state NMR spectroscopy  

Microsoft Academic Search

A suite of one- and two-dimensional solid-state NMR methods was used to follow the complex structural changes in different types of phosphorus species in P-ZSM-5 zeolites that were generated upon treatment of H-ZSM5 zeolites with 0–15% P2O5, followed by calcination or calcination and steaming. Through space and through bond 27Al–31P correlations were used for the first time to study the

K. Damodaran; J. W. Wiench; S. M. Cabral de Menezes; Y. L. Lam; J. Trebosc; J.-P. Amoureux; M. Pruski

2006-01-01

303

1D and 2D solid state NMR investigations of the framework structure of As-synthesized AlPO 4-14  

Microsoft Academic Search

The framework structure of As-synthesized A1PO4-14 has been investigated with a combination of different one-dimensional 27Al and 31P solid state NMR techniques and 27Al31P double resonance methods. The results are found to be fully consistent with the assumed structural model. 27Al MAS and DOR experiments at three different magnetic field strengths together with simulations show the presence of two tetrahedral

C. A. Fyfe; H. Meyer zu Altenschildesche; K. C. Wong-Moon; H. Grondey; J. M. Chezeau

1997-01-01

304

High-resolution paramagnetically enhanced solid-state NMR spectroscopy of membrane proteins at fast magic angle spinning.  

PubMed

Magic angle spinning nuclear magnetic resonance (MAS NMR) is well suited for the study of membrane proteins in membrane mimetic and native membrane environments. These experiments often suffer from low sensitivity, due in part to the long recycle delays required for magnetization and probe recovery, as well as detection of low gamma nuclei. In ultrafast MAS experiments sensitivity can be enhanced through the use of low power sequences combined with paramagnetically enhanced relaxation times to reduce recycle delays, as well as proton detected experiments. In this work we investigate the sensitivity of (13)C and (1)H detected experiments applied to 27 kDa membrane proteins reconstituted in lipids and packed in small 1.3 mm MAS NMR rotors. We demonstrate that spin diffusion is sufficient to uniformly distribute paramagnetic relaxation enhancement provided by either covalently bound or dissolved CuEDTA over 7TM alpha helical membrane proteins. Using paramagnetic enhancement and low power decoupling in carbon detected experiments we can recycle experiments ~13 times faster than under traditional conditions. However, due to the small sample volume the overall sensitivity per unit time is still lower than that seen in the 3.2 mm probe. Proton detected experiments, however, showed increased efficiency and it was found that the 1.3 mm probe could achieve sensitivity comparable to that of the 3.2 mm in a given amount of time. This is an attractive prospect for samples of limited quantity, as this allows for a reduction in the amount of protein that needs to be produced without the necessity for increased experimental time. PMID:24338448

Ward, Meaghan E; Wang, Shenlin; Krishnamurthy, Sridevi; Hutchins, Howard; Fey, Michael; Brown, Leonid S; Ladizhansky, Vladimir

2014-01-01

305

Acid sites and oxidation center in molybdena supported on tin oxide as studied by solid-state NMR spectroscopy and theoretical calculation.  

PubMed

Solid-state NMR spectroscopy and density functional theory (DFT) calculations were employed to study the structure and properties, especially the solid acidity, of molybdenum oxide supported on tin oxide. As demonstrated by solid-state NMR experiments, Mo species are mainly dispersed on the surface of SnO(2) support rather than significantly dissolved into the SnO(2) structure and Brønsted as well as Lewis acid sites are present on the MoO(3)/SnO(2) catalyst. Acid strength of the supported metal oxide is stronger than those of zeolites, e.g., HY and HZSM-5, though the concentration of acid sites is relatively lower. The DFT calculated (13)C chemical shift for acetone adsorbed on MoO(3)/SnO(2) is in good agreement with the experimental value, which confirms our proposed structure of -Mo-(OH)-Sn- for the Brønsted acid site. Reducibility of the supported metal oxide is also demonstrated by solid-state NMR experiments and an active oxidation center of this catalyst is proposed as well. PMID:16710485

Wang, Jiqing; Su, Yongchao; Xu, Jun; Ye, Chaohui; Deng, Feng

2006-05-28

306

Solid-state NMR studies of the adsorption and photooxidation of ethanol on mixed TiO2--SnO2 photocatalysts.  

PubMed

In situ solid-state NMR methodologies have been used to investigate the photocatalytic oxidation of ethanol (CH3CH2OH) over a series of SnO2-based photocatalysts. The adsorption of ethanol on commercially available SnO2 powder was studied using both cross-polarization 13C NMR and REDOR experiments, and showed the formation of two surface ethanol species, hydrogen-bonded ethanol at surface hydroxyl groups and ethanol chemisorbed to the SnO2 surface (Sn--OCH2CH3). 13C NMR of the adsorbed ethanol was used to characterize the surface of monolayer SnO2--TiO2 coupled photocatalysts supported on porous Vycor glass. In situ solid-state NMR studies showed that the photooxidation of ethanol over the monolayer photocatalysts was slower than that over a supported TiO2 monolayer photocatalyst due to the build-up of reaction intermediates such as acetic acid on the catalyst surface. 119Sn NMR experiments characterized the tin species on the porous Vycor glass support. PMID:14642419

Pilkenton, Sarah; Raftery, Daniel

2003-12-01

307

Thermal phase transformations in LaGaO(3) and LaAlO(3) perovskites: an experimental and computational solid-state NMR study.  

PubMed

Multinuclear (71)Ga, (69)Ga, (27)Al and (17)O NMR parameters of various polymorphs of LaGaO(3) and LaAlO(3) perovskites were obtained from the combination of solid-state MAS NMR with solid-state DFT calculations. Some of the materials studied are potential candidate electrolyte materials with applications in intermediate temperature solid oxide fuel cells (ITSOFCs). Small variations in the local distortions of the subject phases are experimentally observed by (71)Ga (and (69)Ga) and (27)Al NMR in the LaGaO(3) and LaAlO(3) phases, respectively, with heating to 1400 K. The orthorhombic-to-rhombohedral phase transformation occurring in LaGaO(3) at approximately 416 K is clearly observed in the (71)Ga/(69)Ga NMR spectra and is associated with a significant increase in the quadrupolar coupling constant (QCC). Thereafter a gradual decrease in QCC is observed, consistent with increased motion of the GaO(6) octahedral units and a reduction in the degree of octahedral tilting. The experimental and theoretical (71)Ga, (69)Ga, (27)Al and (17)O NMR parameters (including isotropic and anisotropic chemical shift parameters, quadrupolar coupling constants, and associated asymmetries) of the low and high temperature polymorphs are compared. In general, the calculated values display good agreement with experimental data, although some significant deviations are identified and discussed. PMID:22341485

Blanc, Frédéric; Middlemiss, Derek S; Buannic, Lucienne; Palumbo, John L; Farnan, Ian; Grey, Clare P

2012-04-01

308

Probing the spatial organization of bacteriochlorophyll C by solid-state nuclear magnetic resonance.  

PubMed

Green sulfur bacteria, which live in extremely low-light environments, use chlorosomes to harvest light. A chlorosome is the most efficient, and arguably the simplest, light-harvesting antenna complex, which contains hundreds of thousands of densely packed bacteriochlorophylls (BChls). To harvest light efficiently, BChls in a chlorosome form supramolecular aggregates; thus, it is of great interest to determine the organization of the BChls in a chlorosome. In this study, we conducted a (13)C solid-state nuclear magnetic resonance and Mg K-edge X-ray absorption analysis of chlorosomes from wild-type Chlorobaculum tepidum. The X-ray absorption results indicated that the coordination number of the Mg in the chlorosome must be >4, providing evidence that electrostatic interactions formed between the Mg of a BChl and the carbonyl group or the hydroxyl group of the neighboring BChl molecule. According to the intermolecular distance constraints obtained on the basis of (13)C homonuclear dipolar correlation spectroscopy, we determined that the molecular assembly of BChls is dimer-based and that the hydrogen bonds among the BChls are less extensive than commonly presumed because of the twist in the orientation of the BChl dimers. This paper also reports the first (13)C homonuclear correlation spectrum acquired for carotenoids and lipids-which are minor, but crucial, components of chlorosomes-extracted from wild-type Cba. tepidum. PMID:25141176

Luo, Shih-Chi; Khin, Yadana; Huang, Shing-Jong; Yang, Yanshen; Hou, Tsai-Yi; Cheng, Yuan-Chung; Chen, Hao Ming; Chin, Yi-Ying; Chen, Chien-Te; Lin, Hong-Ji; Tang, Joseph Kuo-Hsiang; Chan, Jerry Chun Chung

2014-09-01

309

A solid-state NMR and DFT study of compositional modulations in Al(x)Ga(1-x)As.  

PubMed

We have conducted (75)As and (69)Ga Nuclear Magnetic Resonance (NMR) experiments to investigate order/disorder in Al(x)Ga(1-x)As lift-off films with x? 0.297 and 0.489. We were able to identify all possible As(Al(n)Ga(4-n)) sites with n = 0-4 coordinations in (75)As NMR spectra using spin-echo experiments at 18.8 Tesla. This was achieved by employing high rf field strengths using a small solenoid coil and an NMR probe specifically designed for this purpose. Spectral deconvolution, using an evolutionary algorithm, complies with the absence of long-range order if a CuAu based order parameter is imposed. An unconstrained fit shows a deviation of the statistics imposed by this type of ordering. The occupational disorder in the Ga and Al positions is reflected in a distribution of the Electric Field Gradients (EFGs) experienced at the different arsenic sites. We established that this can be modelled by summing the effects of the first coordination sphere and a Czjzek type distribution resulting from the compositional variation in the Al/Ga sub-lattice in the higher coordination spheres. (69)Ga 3QMAS and nutation data exclude the presence of highly symmetric sites and also show a distribution in EFG. The experimentally obtained quadrupolar interactions are in good agreement with calculations based on Density Functional Theory (DFT). Using additivity of EFG tensors arising from distant charge perturbations, we could use DFT to model the EFG distributions of the n = 0-4 sites, reproducing the Czjzek and extended Czjzek distributions that were found experimentally. On the basis of these calculations we conclude that the (75)As quadrupolar interaction is sensitive to compositional modulations up to the 7th coordination shell in these systems. PMID:20676445

Knijn, Paulus J; van Bentum, P Jan M; van Eck, Ernst R H; Fang, Changming; Grimminck, Dennis L A G; de Groot, Robert A; Havenith, Remco W A; Marsman, Martijn; Meerts, W Leo; de Wijs, Gilles A; Kentgens, Arno P M

2010-10-01

310

INVESTIGATING THE EFFECT OF ENANTIOMERIC RATIO AND PREPARATION METHOD ON CRYSTALLINE FORMS OF PROLINE USING SOLID-STATE NMR SPECTROSCOPY  

E-print Network

Chiral molecules are prevalent among currently marketed pharmaceutical products, many of which are solid formulations. The solid-state form of a drug can have a dramatic effect on its solubility, dissolution rate (hence bioavailability), physical...

Berendt, Robert Thomas

2010-08-26

311

Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H --> 19F CP/MAS NMR spectroscopy.  

PubMed

The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H --> 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1rho(F) values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 degrees C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2-CF2 linkage in the E-TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 degrees C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 degrees C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H --> 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 degrees C. This is due to the averaging of 1H-19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1rho(F) and 1H --> 19F CP measurements in the phase transition temperature range. PMID:15181627

Aimi, Keitaro; Ando, Shinji

2004-07-01

312

Solid State  

NSDL National Science Digital Library

This is a webpage filled with Solid State learning objects with over 40 lessons in: Semiconductor Diodes, Rectifier Flitering and Regulation, D/A and A/D Converters, Opto Electronic Devices, Operational Amplifiers, Transistors, Thyristors, and Timers.

2012-12-28

313

The structure of phosphate and borosilicate glasses and their structural evolution at high temperatures as studied with solid state NMR spectroscopy: Phase separation, crystallisation and dynamic species exchange  

NASA Astrophysics Data System (ADS)

In this contribution we present an in-depth study of the network structure of different phosphate based and borosilicate glasses and its evolution at high temperatures. Employing a range of advanced solid state NMR methodologies, complemented by the results of XPS, the structural motifs on short and intermediate length scales are identified. For the phosphate based glasses, at temperatures above the glass transition temperature Tg, structural relaxation processes and the devitrification of the glasses were monitored in situ employing MAS NMR spectroscopy and X-ray diffraction. Dynamic species exchange involving rapid P-O-P and P-O-Al bond breaking and reforming was observed employing in situ27Al and 31P MAS NMR spectroscopy and could be linked to viscous flow. For the borosilicate glasses, an atomic scale investigation of the phase separation processes was possible in a combined effort of ex situ NMR studies on glass samples with different thermal histories and in situ NMR studies using high temperature MAS NMR spectroscopy including 11B MAS, 29Si MAS and in situ29Si{ 11B} REAPDOR NMR spectroscopy.

Wegner, Sebastian; van Wüllen, Leo; Tricot, Gregory

2010-04-01

314

Solid-state NMR structure characterization of a 13CO-Labeled Ir(I) complex with a P,N-donor ligand including ultrafast MAS methods.  

PubMed

The structural characterization of a (13)CO-labeled Ir(I) complex bearing an P,N-donor ligand (1-[2-(diphenylphosphino)ethyl]pyrazole), [Ir(PyP)((13)CO)Cl] is demonstrated using a series of tailored solid-state NMR techniques based on ultrafast (60 kHz) Magic Angle Spinning (MAS), which facilitates correlations with narrow proton line-widths. Our 1D (1)H MAS and 2D (13)C and (31)P CP-MAS NMR spectra provided structural information similar to that obtained using NMR spectroscopy in solution. We employed high-resolution 2D solid-state correlation spectroscopy ((1)H-(13)C HETCOR, (1)H-(31)P correlation) to characterize the networks of dipolar couplings between protons and carbon/phosphorus. (1)H-(1)H SQ-SQ correlation spectra showed the dipolar contacts between all protons in a similar fashion to its solution counterpart, NOESY. The use of the (1)H single quantum/double quantum experiments made it possible to observe the dipolar-coupling contacts between immediately adjacent protons. Additionally, internuclear (13)CO-(31)P distance measurements were performed using REDOR. The combination of all of these techniques made it possible to obtain comprehensive structural information on the molecule [Ir(PyP)((13)CO)Cl] in the solid state, which is in excellent agreement with the single crystal X-ray structure of the complex, and demonstrates the enormous value of ultrafast MAS NMR techniques for a broad range of future applications. PMID:24992359

Tregubov, Andrey A; Linser, Rasmus; Vuong, Khuong Q; Rawal, Aditiya; Gehman, John D; Messerle, Barbara A

2014-07-21

315

Energy and density measurements of sloshing ions in tandem-mirror-experiment upgrade using solid-state probe techniques  

SciTech Connect

The energy and flux of charge-exchange neutrals from the sloshing ions in the endplug of tandem-mirror-experiment upgrade were measured using solid-state probes. An average energy of the sloshing ions of 6 keV was inferred from the depth profile of deuterium implanted in a silicon sample exposed to the charge-exchange neutrals. A bounce-averaged Fokker--Planck code was used to calculate the sloshing-ion energy distribution. The calculated depth profile of deuterium in the silicon sample resulting from this energy distribution is in good agreement with the measured profile. Carbon resistance probes were used to measure the charge-exchange flux from which the central chord sloshing-ion line density was inferred. The line density of particles with energies>2 keV was deduced to account for 60% of the total plasma line density in the endplug. By folding the sloshing-ion line density into the diamagnetic loop data, it was shown that the 1/e radial extent of the sloshing ions remained relatively constant from shot to shot at 14 cm.

Hsu, W.L.; Bastasz, R.; Wampler, W.R.; Rensink, M.E.; Allen, S.L.; Grubb, D.P.; Simonen, T.C.

1985-07-01

316

Determination of Structural Topology of a Membrane Protein in Lipid -Bilayers using Polarization Optimized Experiments (POE) for Static and MAS Solid State NMR Spectroscopy  

PubMed Central

The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments (POE), for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ? 0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional O-ssNMR and MAS-ssNMR. PMID:23963722

Mote, Kaustubh R.; Gopinath, T.; Veglia, Gianluigi

2013-01-01

317

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

PubMed Central

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 ?-helical conformation in membrane environments starting at residue 7 and extending to the C-terminal carboxyamide. Furthermore, DD K has been labeled with 15N at a single alanine position that is located within the helical core region of the sequence. When reconstituted into oriented phosphatidylcholine membranes the resulting 15N 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 31P 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. PMID:19289046

Verly, Rodrigo M.; Moraes, Cleria Mendonca de; Resende, Jarbas M.; Aisenbrey, Christopher; Bemquerer, Marcelo Porto; Pilo-Veloso, Dorila; Valente, Ana Paula; Almeida, Fabio C.L.; Bechinger, Burkhard

2009-01-01

318

Structure and Topology of the Huntingtin 1-17 Membrane Anchor by a Combined Solution and Solid-State NMR Approach  

PubMed Central

The very amino-terminal domain of the huntingtin protein is directly located upstream of the protein’s polyglutamine tract, plays a decisive role in several important properties of this large protein and in the development of Huntington’s disease. This huntingtin 1–17 domain is on the one hand known to markedly increase polyglutamine aggregation rates and on the other hand has been shown to be involved in cellular membrane interactions. Here, we determined the high-resolution structure of huntingtin 1–17 in dodecyl phosphocholine micelles and the topology of its helical domain in oriented phosphatidylcholine bilayers. Using two-dimensional solution NMR spectroscopy the low-energy conformations of the polypeptide were identified in the presence of dodecyl phosphocholine detergent micelles. In a next step a set of four solid-state NMR angular restraints was obtained from huntingtin 1–17 labeled with 15N and 2H at selected sites. Of the micellar ensemble of helical conformations only a limited set agrees in quantitative detail with the solid-state angular restraints of huntingtin 1–17 obtained in supported planar lipid bilayers. Thereby, the solid-state NMR data were used to further refine the domain structure in phospholipid bilayers. At the same time its membrane topology was determined and different motional regimes of this membrane-associated domain were explored. The pronounced structural transitions of huntingtin 1–17 upon membrane-association result in a ?-helical conformation from K6 to F17, i.e., up to the very start of the polyglutamine tract. This amphipathic helix is aligned nearly parallel to the membrane surface (tilt angle ?77°) and is characterized by a hydrophobic ridge on one side and an alternation of cationic and anionic residues that run along the hydrophilic face of the helix. This arrangement facilitates electrostatic interactions between huntingtin 1–17 domains and possibly with the proximal polyglutamine tract. PMID:23931318

Michalek, Matthias; Salnikov, Evgeniy S.; Bechinger, Burkhard

2013-01-01

319

Phosphorus-31 two-dimensional solid-state exchange NMR. Application to model membrane and biological systems.  

PubMed Central

Two-dimensional solid-state 31P NMR has been used to investigate the orientational exchange of phospholipids in gel and liquid-crystalline aqueous multilamellar dispersions and oriented multibilayers, and in biological membranes. In liquid-crystalline L alpha multilamellar dispersions, orientational exchange originates from the lateral diffusion of phospholipid molecules over the curved surface of the liposomes and is manifest by an increase in off-diagonal intensity, which correlates the 90 and 0 degrees orientations of the membrane normal with respect to the magnetic field when the system is fully exchanged. Spectral simulations of the time evolution of exchange allowed determination of the correlation times tau d for lateral diffusion. For DMPC and DPPC at comparable reduced temperatures, tau d values of 44 and 8 ms were obtained, respectively. The nature and rate of exchange observed for POPE at 30 degrees C is similar to that of DMPC at the same temperature. The measured correlation times are consistent with diffusion rates obtained by FRAP for liposomes with radii in the 1 micron range. In the gel phase of DPPC (30 degrees C), little orientational exchange is observed at mixing times up to 200 ms, demonstrating that the lateral diffusion is very slow. The correlation time for orientational exchange obtained from spectral simulations was approximately 900 ms; thus, exchange in the gel state is at least two orders of magnitude slower than in the liquid-crystalline state. In the P beta (ripple) phase, at temperatures between 34 and 39 degrees C, significant exchange is observed for mixing times between 50 and 200 ms. Exchange is also observed in oriented samples of DPPC in the P beta phase for mixing times of 50 ms, but not for oriented liquid-crystalline samples for mixing times up to 100 ms. The exchange observed in the ripple phase could originate from rapid lateral diffusion of "fast" diffusing phospholipid within defect structures, and/or from "slow" lateral diffusion of ordered phospholipid over the ripples. 2D experiments were also performed on pig erythrocyte ghosts and on intact pig spinal cord. Significant orientational exchange was observed with the erythrocyte ghosts at a mixing time of 200 ms, but almost no exchange was observed with the spinal cord at the same mixing time. Spectral simulations suggest tau d values of approximately 400 ms and 1.3 s for the erythrocyte ghosts and spinal cord at 30 degrees C. The results demonstrate that exchange in the biological membranes is significantly slower than in the model membrane systems, which suggests that the cell surfaces are relatively "smooth," i.e., any local surface perturbations are either present in small number or have little effect on the mean orientation of the phospholipids with respect to the membrane normal. PMID:2015390

Fenske, D. B.; Jarrell, H. C.

1991-01-01

320

Crystal Structures and Vibrational and Solid-State (CPMAS) NMR Spectroscopy of Some Bis(triphenylphosphine)silver(I) Sulfate, Selenate and Phosphate Systems.  

SciTech Connect

The complexes [Ag2(PPh3)4EO4].2H2O(E=S, Se) (1,2), [Ag(PPh3)2HEO4].H2O (E=S, Se)(3,4) and [Ag9PPh3)2H2PO4].2EtOH (5) have been prepared and studied by X-ray crystallography and by infrared and solid-state 13C and 31 P cross-polarization, magic-angle-spinning (CPMAS) NMR spectroscopy.

Bowmaker, Graham A.; Hanna, John V.; Rickard, Clifton E.; Lipton, Andrew S.

2001-01-01

321

Solid-state 19F and 13C NMR of room temperature fluorinated graphite and samples thermally treated under fluorine: Low-field and high-resolution studies  

NASA Astrophysics Data System (ADS)

Room temperature graphite fluorides consisting of raw material and samples post-treated in pure fluorine atmosphere in the temperature range 100-500 °C have been studied by solid-state NMR. Several NMR approaches have been used, both high and low-field 19F, 19F MAS and 13C MAS with 19F to 13C cross polarization. The modifications, in the graphitic lattice, of the catalytic iodine fluorides products have been examined. A transformation of the C-F bond character from semi-ionic to covalent has been found to occur at a post-treatment temperature close to 400 °C. It is shown that covalency increases with temperature.

Giraudet, J.; Dubois, M.; Guérin, K.; Pinheiro, J. P.; Hamwi, A.; Stone, W. E. E.; Pirotte, P.; Masin, F.

2005-04-01

322

Solid-state 13C NMR study of banana liquid crystals - 2: Alkyl tail-group packing environments in the hexagonal columnar phase  

NASA Astrophysics Data System (ADS)

Solid-state 13C nuclear magnetic resonance (NMR) measurements were performed in order to obtain the packing structure of alkyl tail in the hexagonal columnar phase of the banana-shaped N(1,7)-S16 molecule. In this phase, NMR chemical shifts assigned to the internal methylene carbons at an amorphous state appear as two peaks, indicating that the two alkyl tails are placed under two different chemical environments. From combined cross-polarization/magic-angle spinning and pulse saturation transfer/magical-angle spinning measurements, two alkyl tails were found to have the different mobility. Such two different environments are not unusual in conventional mesophases, but in the hexagonal columnar phase formed by cylindrical columns composed of enclosed smectic layers; one of the alkyl tails is located inside and the other is located outside the columnar structure.

Kurosu, Hiromichi; Endo, Yumi; Kimura, Saori; Hashimoto, Tomoko; Harada, Motoi; Lee, Eun-Woo; Sone, Masato; Watanabe, Junji; Kang, Sungmin

2013-05-01

323

Solid-state [sup 13]C NMR studies of ionic surfactants adsorbed on C-18 and C-8 silicas: Implications for micellar liquid chromatography  

SciTech Connect

Solid-state [sup 13]C NMR spectroscopy techniques, including cross polarization (CP), magic angle spinning (MAS), and high-power proton decoupling, have been used to study the interactions of two ionic surfactants with octadecylsilica (C-18) and octylsilica (C-8) HPLC stationary phases. The two surfactants, cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS), are commonly used in micellar reversed-phase liquid chromatography (RPLC). Variable contact time CP/MAS [sup 13] C NMR data suggest that differences in selectivity between SDS and CTAB micellar RPLC are due to the differing nature of the SDS and CTAB-bonded phase association. For CTAB the association leads to a more hydrophobic bulk stationary phase, whereas SDS adsorption results in the formation of an anionic, hydrophilic surface layer. These results suggest that proper matching of surfactant monomer and bonded stationary phase is critical to ensure selective separations in micellar RPLC.

Lavine, B.K.; Hendayana, S.; Han, J.H.; Tetreault, J. (Clarkson Univ., Potsdam, NY (United States). Dept. of Chemistry); Cooper, W.T. III; He, Y. (Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry)

1994-07-01

324

Structural features of a bituminous coal and their changes during low-temperature oxidation and loss of volatiles investigated by advanced solid-state NMR spectroscopy  

USGS Publications Warehouse

Quantitative and advanced 13C solid-state NMR techniques were employed to investigate (i) the chemical structure of a high volatile bituminous coal, as well as (ii) chemical structural changes of this coal after evacuation of adsorbed gases, (iii) during oxidative air exposure at room temperature, and (iv) after oxidative heating in air at 75 ??C. The solid-state NMR techniques employed in this study included quantitative direct polarization/magic angle spinning (DP/MAS) at a high spinning speed of 14 kHz, cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH, CH2, and CHn selection, 13C chemical shift anisotropy (CSA) filtering, two-dimensional (2D) 1H-13C heteronuclear correlation NMR (HETCOR), and 2D HETCOR with 1H spin diffusion. With spectral editing techniques, we identified methyl CCH 3, rigid and mobile methylene CCH2C, methine CCH, quaternary Cq, aromatic CH, aromatic carbons bonded to alkyls, small-sized condensed aromatic moieties, and aromatic C-O groups. With direct polarization combined with spectral-editing techniques, we quantified 11 different types of functional groups. 1H-13C 2D HETCOR NMR experiments indicated spatial proximity of aromatic and alkyl moieties in cross-linked structures. The proton spin diffusion experiments indicated that the magnetization was not equilibrated at a 1H spin diffusion time of 5 ms. Therefore, the heterogeneity in spatial distribution of different functional groups should be above 2 nm. Recoupled C-H long-range dipolar dephasing showed that the fraction of large charcoal-like clusters of polycondensed aromatic rings was relatively small. The exposure of this coal to atmospheric oxygen at room temperature for 6 months did not result in obvious chemical structural changes of the coal, whereas heating at 75 ??C in air for 10 days led to oxidation of coal and generated some COO groups. Evacuation removed most volatiles and caused a significant reduction in aliphatic signals in its DP/MAS spectrum. DP/MAS, but not CP/MAS, allowed us to detect the changes during low-temperature oxidation and loss of volatiles. These results demonstrate the applicability of advanced solid-state NMR techniques in chemical characterization of coal. ?? 2010 American Chemical Society.

Mao, J.-D.; Schimmelmann, A.; Mastalerz, M.; Hatcher, P.G.; Li, Y.

2010-01-01

325

Assessing the phosphate distribution in bioactive phosphosilicate glasses by 31P solid-state NMR and molecular dynamics simulations.  

PubMed

Melt-derived bioactive phosphosilicate glasses are widely utilized as bone-grafting materials for various surgical applications. However, the insight into their structural features over a medium-range scale up to ? 1 nm remains limited. We present a comprehensive assessment of the spatial distribution of phosphate groups across the structures of 11 Na2O-CaO-SiO2-P2O5 glasses that encompass both bioactive and nonbioactive compositions, with the P contents and silicate network connectivities varied independently. Both parameters are known to strongly influence the bioactivity of the glass in vitro. The phosphate distribution was investigated by double-quantum (31)P nuclear magnetic resonance (NMR) experiments under magic-angle spinning (MAS) conditions and by molecular dynamics (MD) simulations. The details of the phosphate-ion dispersion were probed by evaluating the MD-derived glass models against various scenarios of randomly distributed, as well as clustered, phosphate groups. From comparisons of the P-P interatomic-distance spreads and the statistics of small phosphate clusters assessed for variable cutoff radii, we conclude that the spatial arrangement of the P atoms in phosphosilicate glasses is well-approximated by a statistical distribution, particularly across a short-range scale of ? 450 pm. The primary distinction is reflected in slightly closer P-P interatomic contacts in the MD-derived structures over the distance span of 450-600 pm relative to that of randomly distributed phosphate groups. The nature of the phosphate-ion dispersion remains independent of the silicate network polymerization and nearly independent of the P content of the glass throughout our explored parameter space of 1-6 mol % P2O5 and silicate network connectivities up to 2.9. PMID:24967834

Stevensson, Baltzar; Mathew, Renny; Edén, Mattias

2014-07-24

326

51V solid-state NMR and density functional theory studies of vanadium environments in V(V)O2 dipicolinic acid complexes  

NASA Astrophysics Data System (ADS)

51V solid-state NMR and density functional theory (DFT) investigations are reported for a series of pentacoordinate dioxovanadium(V)-dipicolinate [V(V)O2-dipicolinate] and heptacoordinate aquahydroxylamidooxovanadium(V)-dipicolinate [V(V)O-dipicolinate] complexes. These compounds are of interest because of their potency as phosphatase inhibitors as well as their insulin enhancing properties and potential for the treatment of diabetes. Experimental solid-state NMR results show that the electric field gradient tensors in the V(V)O2-dipicolinate derivatives are affected significantly by substitution on the dipicolinate ring and range from 5.8 to 8.3 MHz. The chemical shift anisotropies show less dramatic variations with respect to the ligand changes and range between -550 and -600 ppm. To gain insights on the origins of the NMR parameters, DFT calculations were conducted for an extensive series of the V(V)O2- and V(V)O-dipicolinate complexes. To assess the level of theory required for the accurate calculation of the 51V NMR parameters, different functionals, basis sets, and structural models were explored in the DFT study. It is shown that the original x-ray crystallographic geometries, including all counterions and solvation water molecules within 5 A? of the vanadium, lead to the most accurate results. The choice of the functional and the basis set at a high level of theory has a relatively minor impact on the outcome of the chemical shift anisotropy calculations; however, the use of large basis sets is necessary for accurate calculations of the quadrupole coupling constants for several compounds of the V(V)O2 series. These studies demonstrate that even though the vanadium compounds under investigations exhibit distorted trigonal bipyramidal coordination geometry, they have a ``perfect'' trigonal bipyramidal electronic environment. This observation could potentially explain why vanadate and vanadium(V) adducts are often recognized as potent transition state analogs.

Bolte, Stephanie E.; Ooms, Kristopher J.; Polenova, Tatyana; Baruah, Bharat; Crans, Debbie C.; Smee, Jason J.

2008-02-01

327

Induced Secondary Structure and Polymorphism in an Intrinsically Disordered Structural Linker of the CNS: Solid-State NMR and FTIR Spectroscopy of Myelin Basic Protein Bound to Actin  

PubMed Central

Abstract The 18.5 kDa isoform of myelin basic protein (MBP) is a peripheral membrane protein that maintains the structural integrity of the myelin sheath of the central nervous system by conjoining the cytoplasmic leaflets of oligodendrocytes and by linking the myelin membrane to the underlying cytoskeleton whose assembly it strongly promotes. It is a multifunctional, intrinsically disordered protein that behaves primarily as a structural stabilizer, but with elements of a transient or induced secondary structure that represent binding sites for calmodulin or SH3-domain-containing proteins, inter alia. In this study we used solid-state NMR (SSNMR) and Fourier transform infrared (FTIR) spectroscopy to study the conformation of 18.5 kDa MBP in association with actin microfilaments and bundles. FTIR spectroscopy of fully 13C,15N-labeled MBP complexed with unlabeled F-actin showed induced folding of both protein partners, viz., some increase in ?-sheet content in actin, and increases in both ?-helix and ?-sheet content in MBP, albeit with considerable extended structure remaining. Solid-state NMR spectroscopy revealed that MBP in MBP-actin assemblies is structurally heterogeneous but gains ordered secondary structure elements (both ?-helical and ?-sheet), particularly in the terminal fragments and in a central immunodominant epitope. The overall conformational polymorphism of MBP is consistent with its in vivo roles as both a linker (membranes and cytoskeleton) and a putative signaling hub. PMID:19134474

Ahmed, Mumdooh A.M.; Bamm, Vladimir V.; Shi, Lichi; Steiner-Mosonyi, Marta; Dawson, John F.; Brown, Leonid; Harauz, George; Ladizhansky, Vladimir

2009-01-01

328

Accurate measurements of ¹³C-¹³C distances in uniformly ¹³C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy.  

PubMed

Application of sets of (13)C-(13)C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important (13)C-(13)C distances in uniformly (13)C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl ((13)C') and aliphatic ((13)C(aliphatic)) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly (13)C,(15)N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of (13)C'-(13)C(aliphatic) distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform (13)C,(15)N-labeling on the FGAIL fragment. PMID:25240350

Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Khaneja, Navin; Nielsen, Niels Chr

2014-09-21

329

Accurate measurements of 13C-13C distances in uniformly 13C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy  

NASA Astrophysics Data System (ADS)

Application of sets of 13C-13C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important 13C-13C distances in uniformly 13C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl (13C') and aliphatic (13Caliphatic) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly 13C,15N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of 13C'-13Caliphatic distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform 13C,15N-labeling on the FGAIL fragment.

Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Khaneja, Navin; Nielsen, Niels Chr.

2014-09-01

330

Utilizing Afterglow Magnetization from Cross-Polarization Magic-Angle-Spinning Solid-State NMR Spectroscopy to Obtain Simultaneous Heteronuclear Multidimensional Spectra  

PubMed Central

The time required for data acquisition and subsequent spectral assignment are limiting factors for determining biomolecular structure and dynamics using solid state NMR spectroscopy. While strong magnetic dipolar couplings give rise to relatively broad spectra lines, the couplings also mediate the coherent magnetization transfer via the Hartmann Hahn cross polarization (HH-CP) experiment. This mechanism is used in nearly all backbone assignment experiments for carrying out polarization transfer between 1H, 15N, and 13C. In this Article, we describe a general spectroscopic approach to use the residual or afterglow magnetization from the 15N to 13C selective HH-CP experiment to collect a second multidimensional heteronuclear dataset. This approach allowed for the collection of two multidimensional (2D NCA and NCO or 3D NCACX and NCOCX) datasets at the same time. These experiments were performed using instrumentation available on all standard solid state NMR spectrometers configured for magic angle spinning and were demonstrated on uniformly [13C,15N] and [1,3-13C] glycerol labeled ubiquitin. This method is compatible with several other sensitivity enhancement experiments and can be used as an isotopic filtering tool to reduce the spectral complexity and decrease the time needed for assigning spectra. PMID:22582831

Banigan, James R.; Traaseth, Nathaniel J.

2012-01-01

331

Solid-State NMR Enhanced by Dynamic Nuclear Polarization as a novel Tool for Ribosome Structural Biology  

E-print Network

half of the NMR rotor for easy removal after centrifugation. The rotor holder is screwed into the 'core for concentration of ribosome complexes into NMR rotors, designed to fit Beckman swing- out and fixed angle Rotors in 1a and 1b. Both adaptors are composed of three parts: the rotor holder (I), which hosts the lower

332

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

NASA Astrophysics Data System (ADS)

Approximately 6 years ago, while at the Geophysical Laboratory, James Scott became interested in the application of Solid State Nuclear Magnetic Resonance Spectroscopy to study bacterial metabolism. As often happens, other experiments intervened and the NMR experiments were not pursued. We have revisited Jame's question and find that using a multi-nuclear approach (1H, 2H, and 13C Solid State NMR) on laboratory cell culture has some distinct advantages. Our experiments involved batch cultures of E. coli (MG1655) harvested at stationary phase. In all experiments the growth medium consisted of MOPS medium for enterobacteria, where the substrate is glucose. In one set of experiments, 10 % of the water was D2O; in another 10 % of the glucose was per-deuterated. The control experiment used both water and glucose at natural isotopic abundance. A kill control of dead E. coli immersed in pure D2O for an extended period exhibited no deuterium incorporation. In both deuterium enriched experiments, considerable incorporation of deuterium into E. coli's biomolecular constituents was detected via 2H Solid State NMR. In the case of the D2O enriched experiment, 58 % of the incorporated deuterium is observed in a sharp peak at a frequency of 0.31 ppm, consistent with D incorporation in the cell membrane lipids, the remainder is observed in a broad peak at a higher frequency (centered at 5.4 ppm, but spanning out to beyond 10 ppm) that is consistent with D incorporation into predominantly DNA and RNA. In the case of the D-glucose experiments, 61 % of the deuterium is observed in a sharp resonance peak at 0.34 ppm, also consistent with D incorporation into membrane lipids, the remainder of the D is observed at a broad resonance peak centered at 4.3 ppm, consistent with D enrichment in glycogen. Deuterium abundance in the E. coli cells grown in 10 % D2O is nearly 2X greater than that grown with 10 % D-glucose. Very subtle differences are observed in both the 1H and 13C solid-state 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.

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

2011-12-01

333

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

NASA Astrophysics Data System (ADS)

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 Mg3sbnd OH, Mg2Gasbnd OH and intergallery water molecules were assigned and quantified using {1H,71Ga} HETCOR and 1H MAS NMR. A single 71Ga site originating from the unique Ga site in the MgGa LDH's was observed in 71Ga MAS and 3QMAS NMR spectra. Both 1H MAS NMR spectra recorded at 21.1 T (900 MHz) and elemental 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 Gasbnd Osbnd Ga connectivities or defects were detected for the MgGa LDH's.

Petersen, Line Boisen; Lipton, Andrew S.; Zorin, Vadim; Nielsen, Ulla Gro

2014-11-01

334

N Solid-State NMR Provides a Sensitive Probe of Oxidized Flavin Reactive Sites  

E-print Network

for "pyridine-type" N's, consistent with their electrophilic and nucleophilic chemical reactivities chemistry to execute reactions ranging from oxygenation, oxidation and reduction, disulfide formation

Koder, Ronald

335

Untangling the Condensation Network of Organosiloxanes on Nanoparticles using 2D (29)Si-(29)Si Solid-State NMR Enhanced by Dynamic Nuclear Polarization.  

PubMed

Silica (SiO2) nanoparticles (NPs) were functionalized by silanization to produce a surface covered with organosiloxanes. Information about the surface coverage and the nature, if any, of organosiloxane polymerization, whether parallel or perpendicular to the surface, is highly desired. To this extent, two-dimensional homonuclear (29)Si solid-state NMR could be employed. However, owing to the sensitivity limitations associated with the low natural abundance (4.7%) of (29)Si and the difficulty and expense of isotopic labeling here, this technique would usually be deemed impracticable. Nevertheless, we show that recent developments in the field of dynamic nuclear polarization under magic angle spinning (MAS-DNP) could be used to dramatically increase the sensitivity of the NMR experiments, resulting in a timesaving factor of ?625 compared to conventional solid-state NMR. This allowed the acquisition of previously infeasible data. Using both through-space and through-bond 2D (29)Si-(29)Si correlation experiments, it is shown that the required reaction conditions favor lateral polymerization and domain growth. Moreover, the natural abundance correlation experiments permitted the estimation of (2)J(Si-O-Si)-couplings (13.8 ± 1.4 Hz for surface silica) and interatomic distances (3.04 ± 0.08 Å for surface silica) since complications associated with many-spin systems and also sensitivity were avoided. The work detailed herein not only demonstrates the possibility of using MAS-DNP to greatly facilitate the acquisition of 2D (29)Si-(29)Si correlation spectra but also shows that this technique can be used in a routine fashion to characterize surface grafting networks and gain structural constraints, which can be related to a system's chemical and physical properties. PMID:25153717

Lee, Daniel; Monin, Guillaume; Duong, Nghia Tuan; Lopez, Isabel Zamanillo; Bardet, Michel; Mareau, Vincent; Gonon, Laurent; De Paëpe, Gaël

2014-10-01

336

Hydrido-ruthenium cluster complexes as models for reactive surface hydrogen species of ruthenium nanoparticles. Solid-state 2H NMR and quantum chemical calculations.  

PubMed

The (2)H quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state (2)H MAS NMR techniques are used in the investigations of two ruthenium clusters, D(4)Ru(4)(CO)(12) (1) and D(2)Ru(6)(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the (2)H MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu(6)(CO)(18)](-) (2(-)) and cationic [D(3)Ru(6)(CO)(18)](+) (2(+)). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the (2)H nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles. PMID:20684514

Gutmann, Torsten; Walaszek, Bernadeta; Yeping, Xu; Wächtler, Maria; del Rosal, Iker; Grünberg, Anna; Poteau, Romuald; Axet, Rosa; Lavigne, Guy; Chaudret, Bruno; Limbach, Hans-Heinrich; Buntkowsky, Gerd

2010-08-25

337

Evolution of crystalline aluminates from hybrid gel-derived precursors studied by XRD and multinuclear solid state MAS NMR  

Microsoft Academic Search

X-ray amorphous calcium aluminate gels of dialuminate and hexaluminate composition were prepared, the former by two methods, and their thermal crystallisation was monitored by thermal analysis, X-ray powder diffraction and 27Al MAS NMR. Both gel compositions lose a large amount of solvent and organic by-products below 600°C, forming amorphous precursors with 27Al NMR spectra containing resonances corresponding to tetrahedral and

K. J. D MacKenzie; M Schmücker; M. E Smith; I. J. F Poplett; T Kemmitt

2000-01-01

338

Evolution of crystalline aluminates from hybrid gel-derived precursors studied by XRD and multinuclear solid state MAS NMR  

Microsoft Academic Search

A hybrid gel synthesis is described which produces crystalline lanthanum hexaluminate at 1200°C without the intermediate appearance of LaAlO3. XRD in conjunction with 27Al and 139La MAS NMR indicates that until the exothermic appearance of ?-alumina at about 900°C, the gel remains amorphous and contains Al in three types of site, one of which is characterised by an NMR resonance

K. J. D MacKenzie; M Schmucker; L Mayer

1999-01-01

339

Conformational studies by dynamic NMR. 33. Possible applications of the magic angle spinning technique for identifying meso and racemic conformers in the solid state  

SciTech Connect

The /sup 13/C magic angle spinning NMR spectrum of a meso compound in the solid often displays a different number of lines with respect to its racemic isomer. Usually the meso isomers that have a symmetric conformation in the crystal are expected to yield the same spectral multiplicity as in solution (e.g., meso-2,3-dimethylsuccinic acid). Exceptions might in principle occur in the few cases when the center of molecular symmetry is not coincident with a center of crystallographic symmetry: examples of this type, however, were not encountered in the present work. On the other hand the isomeric racemic derivatives are normally expected to have solid-state spectra with a larger number of lines than in solution (e.g., d,l-2,3-dimethylsuccinic acid). In a very limited number of cases solid-state spectra with unsplit lines can be encountered: an example (trans-1,2-cyclohexanedicarboxylic acid) is reported here and discussed. In the case of N,N'-diisopropyl-N,N'-dimethyl-1,5-naphthyldiamine (1) the /sup 13/C solution spectrum at -90/degrees/C does show the existence of two conformers with unequal proportions: one of them being meso, the other racemic. The solid-state spectrum of 1 shows that some of the lines of the major conformer are split into two with respect to the solution spectrum whereas those of the minor conformer are unsplit, as in solution. On this basis the racemic structure has been tentatively assigned to the major conformer and the meso structure to the minor conformer. In favorable circumstances, as those here reported, these features might possibly be helpful in discriminating meso from racemic conformers when they cannot be physically separated nor investigated by X-ray diffraction.

Casarini, D.; Lunazzi, L.; Macciantelli, D.

1988-01-08

340

Proton chemical shift anisotropy measurements of hydrogen-bonded functional groups by fast magic-angle spinning solid-state NMR  

E-print Network

b changes in orientation of 31 P chemical shielding tensors due to hydrogen bonding have beenProton chemical shift anisotropy measurements of hydrogen-bonded functional groups by fast magic-state NMR spectroscopy for probing 1 H chemical shift anisotropy of hydrogen-bonded species has been

341

Molecular level investigations of phosphate sorption on corundum (?-Al2O3) by 31P solid state NMR, ATR-FTIR and quantum chemical calculation  

NASA Astrophysics Data System (ADS)

Phosphate sorption at the corundum (?-Al2O3)/water interface was investigated as a function of phosphate concentration (0.1-1 mM) and pH (3-11) by 31P solid state NMR spectroscopy, ATR-FTIR, and quantum chemical calculation. The 31P NMR spectra indicate that under these experimental conditions phosphate adsorbs onto corundum mainly as inner-sphere complexes that yield a peak at ?P = -2.8 ppm with full width at half maximum (FWHM) of 9.2 ppm, with a small amount aluminum phosphate surface precipitates as suggested by an NMR signal observed from ?P = -12 to -20 ppm. We employed 31P{27Al} rotational echo adiabatic passage double resonance (REAPDOR) to further analyze the phosphate adsorption samples prepared at pH 5 and 9 in order to determine the phosphate/Al coordination. To aid interpretation of the NMR data, a series of bidentate and monodentate structural models of phosphate adsorbed on corundum (0 0 1) and (0 1 2) surfaces were calculated using density function theory (DFT). By comparing the experimental REAPDOR curves and those simulated from these models, we can assign the dominant peaks to bidentate binuclear surface complexes. Formation of bidentate binuclear surface complexes is supported by the ATR/FTIR spectra combined with DFT calculation, which further suggests a mixture of non-protonated bidentate and mono-protonated bidentate surface complexes on the corundum surface at pH 5. At pH 9, both NMR and ATR/FTIR indicate the formation of bidentate surface complexes on corundum surface.

Li, Wei; Pierre-Louis, Andro-Marc; Kwon, Kideok D.; Kubicki, James D.; Strongin, Daniel R.; Phillips, Brian L.

2013-04-01

342

Humic acids from particulate organic matter in the Saguenay Fjord and the St. Lawrence Estuary investigated by advanced solid-state NMR  

NASA Astrophysics Data System (ADS)

Detailed structural information on two humic acids extracted from two sinking particulate matter samples at a water depth of 20 m in the Saguenay Fjord (F-20-HA) and the St. Lawrence Estuary (E-20-HA) (Canada), was obtained by advanced solid-state NMR. Spectral-editing analyses provided numerous structural details rarely reported in geochemical studies. The NMR data account almost quantitatively for the elemental compositions. The two humic acids were found to be quite similar, consisting of four main structural components: peptides (ca. 39 ± 3% vs. 34 ± 3% of all C for E-20-HA and F-20-HA, respectively); aliphatic chains, 14-20 carbons long (ca. 25 ± 5% vs. 17 ± 5% of all C); aromatic structures (ca. 17 ± 2% vs. 26 ± 2% of all C); and sugar rings (14 ± 2% vs. 15 ± 2% of all C). Peptides were identified by 13C{ 14N} SPIDER NMR, which selects signals of carbons bonded to nitrogen, and by dipolar DEPT, which selects CH-group signals, in particular the NCH band of peptides. The SPIDER spectra also indicate that heterocycles constitute a significant fraction of the aromatic structures. The aliphatic (CH 2) n chains, which are highly mobile, contain at least one double bond per two chains and end in methyl groups. 1H spin diffusion NMR experiments showed that these mobile aliphatic chains are in close (<10 nm) proximity to the other structural components. A major bacterial contribution to these two samples could explain why the samples, which have different dominant organic matter sources (terrestrial vs. marine), are similar to each other as well as to degraded algae and particles from other waters. The NMR data suggest structures containing mobile lipids in close proximity to peptides and carbohydrates (e.g., peptidoglycan) as found in bacterial cell walls. Measured yields of muramic acid and D-amino acids confirmed the presence of bacterial cell wall components in the studied samples.

Mao, J.-D.; Tremblay, L.; Gagné, J.-P.; Kohl, S.; Rice, J.; Schmidt-Rohr, K.

2007-11-01

343

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

SciTech Connect

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.

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

1998-12-31

344

{sup 29}Si solid state NMR investigation of pozzolanic reaction occurring in lime-treated Ca-bentonite  

SciTech Connect

Lime is widely used as additive to improve the mechanical properties of natural soil used in earthworks. However, the physico-chemical mechanisms involved are yet not well understood. In order to develop and optimize this treatment method, a better understanding of the interaction between lime and the minerals of the soils, in particular clay minerals, is required. In this study, Ca-bentonite was treated with 2, 5 and 10 wt.% of lime during 1 to 98 days. Modifications in the Si local environment were then monitored by solid state nuclear magnetic resonance to investigate the pozzolanic reaction. All the soil mineral phases contribute to the release of Si and to the pozzolanic reaction, with a rapid and total consumption of Si-polymorph and an exacerbated dissolution of montmorillonite. Mechanism of C-S-H formation, function of the Ca content in the system, was found to match the sorosilicate-tobermorite model described in cement systems.

Pomakhina, Elena [Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France); Deneele, Dimitri, E-mail: dimitri.deneele@ifsttar.fr [Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France); UNAM, IFSTTAR, Institut Francais des Sciences et des Technologies des Transports, de l'Amenagement et des Reseaux, BP 4129, route de Bouaye, 44332 Bouguenais (France); Gaillot, Anne-Claire; Paris, Michael; Ouvrard, Guy [Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France)

2012-04-15

345

High-resolution structure of the Shigella type-III secretion needle by solid-state NMR and cryo-electron microscopy  

NASA Astrophysics Data System (ADS)

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.

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

2014-09-01

346

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

PubMed

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. PMID:25264107

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

2014-01-01

347

Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves  

NASA Astrophysics Data System (ADS)

We report solid state 13C and 1H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, 1H and cross-polarized 13C NMR signals from 15N,13C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations.

Thurber, Kent R.; Tycko, Robert

2014-05-01

348

Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves.  

PubMed

We report solid state (13)C and (1)H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, (1)H and cross-polarized (13)C NMR signals from (15)N,(13)C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations. PMID:24832263

Thurber, Kent R; Tycko, Robert

2014-05-14

349

?-Sheet nanocrystalline domains formed from phosphorylated serine-rich motifs in caddisfly larval silk: a solid state NMR and XRD study.  

PubMed

Adhesive silks spun by aquatic caddisfly (order Trichoptera) larvae are used to build both intricate protective shelters and food harvesting nets underwater. In this study, we use (13)C and (31)P solid-state NMR and wide angle X-ray diffraction (WAXD) as tools to elucidate molecular protein structure of caddisfly larval silk from the species Hesperophylax consimilis . Caddisfly larval silk is a fibroin protein based biopolymer containing mostly repetitive amino acid motifs. NMR and X-ray results provide strong supporting evidence for a structural model in which phosphorylated serine repeats (pSX)4 complex with divalent cations Ca(2+) and Mg(2+) to form rigid nanocrystalline ?-sheet structures in caddisfly silk. (13)C NMR data suggests that both phosphorylated serine and neighboring valine residues exist in a ?-sheet conformation while glycine and leucine residues common in GGX repeats likely reside in random coil conformations. Additionally, (31)P chemical shift anisotropy (CSA) analysis indicates that the phosphates on phosphoserine residues are doubly ionized, and are charge-stabilized by divalent cations. Positively charged arginine side chains also likely play a role in charge stabilization. Finally, WAXD results finds that the silk is at least 7-8% crystalline, with ?-sheet interplane spacings of 3.7 and 4.5 Å. PMID:23452243

Addison, J Bennett; Ashton, Nicholas N; Weber, Warner S; Stewart, Russell J; Holland, Gregory P; Yarger, Jeffery L

2013-04-01

350

?-Sheet Nanocrystalline Domains Formed from Phosphorylated Serine-Rich Motifs in Caddisfly Larval Silk: A Solid State NMR and XRD Study  

PubMed Central

Adhesive silks spun by aquatic caddisfly (order Trichoptera) larvae are used to build both intricate protective shelters and food harvesting nets underwater. In this study, we use 13C and 31P solid-state Nuclear Magnetic Resonance (NMR) and Wide Angle X-ray Diffraction (WAXD) as tools to elucidate molecular protein structure of caddisfly larval silk from the species Hesperophylax consimilis. Caddisfly larval silk is a fibroin protein based biopolymer containing mostly repetitive amino acid motifs. NMR and X-ray results provide strong supporting evidence for a structural model in which phosphorylated serine repeats (pSX)4 complex with divalent cations Ca2+ and Mg2+ to form rigid nanocrystalline ?-sheet structures in caddisfly silk. 13C NMR data suggests that both phosphorylated serine and neighboring valine residues exist in a ?-sheet secondary structure conformation while glycine and leucine residues common in GGX repeats likely reside in random coil conformations. Additionally, 31P chemical shift anisotropy (CSA) analysis indicates that the phosphates on phosphoserine residues are doubly ionized, and are charge-stabilized by divalent cations. Positively charged arginine side chains also likely play a role in charge stabilization. Finally, WAXD results finds that the silk is at least 7–8% crystalline, with ?-sheet inter-plane spacings of 3.7 and 4.5 Å. PMID:23452243

Addison, J. Bennett; Ashton, Nicholas N.; Weber, Warner S.; Stewart, Russell J.; Holland, Gregory P.; Yarger, Jeffery L.

2013-01-01

351

Sensitivity enhancement in natural-abundance solid-state 33S MAS NMR spectroscopy employing adiabatic inversion pulses to the satellite transitions.  

PubMed

The WURST (wideband uniform rate smooth truncation) and hyperbolic secant (HS) pulse elements have each been employed as pairs of inversion pulses to induce population transfer (PT) between the four energy levels in natural abundance solid-state (33)S (spin I=3/2) MAS NMR, thereby leading to a significant gain in intensity for the central transition (CT). The pair of inversion pulses are applied to the satellite transitions for a series of inorganic sulfates, the sulfate ions in the two cementitious materials ettringite and thaumasite, and the two tetrathiometallates (NH(4))(2)WS(4) and (NH(4))(2)MoS(4). These materials all exhibit (33)S quadrupole coupling constants (C(Q)) in the range 0.1-1.0 MHz, with precise C(Q) values being determined from analysis of the PT enhanced (33)S MAS NMR spectra. The enhancement factors for the WURST and HS elements are quite similar and are all in the range 1.74-2.25 for the studied samples, in excellent agreement with earlier reports on HS enhancement factors (1.6-2.4) observed for other spin I=3/2 nuclei with similar C(Q) values (0.3-1.2 MHz). Thus, a time saving in instrument time by a factor up to five has been achieved in natural abundance (33)S MAS NMR, a time saving which is extremely welcome for this important low-gamma nucleus. PMID:18082436

Hansen, Michael Ryan; Brorson, Michael; Bildsøe, Henrik; Skibsted, Jørgen; Jakobsen, Hans J

2008-02-01

352

Methane dehydro-aromatization over Mo/HZSM-5 in the absence of oxygen: A multinuclear solid-state NMR study of the interaction between supported Mo species and HZSM-5 zeolite with different crystal sizes  

SciTech Connect

The interaction between Mo species and a conventionally microsized and particularly nanosized HZSM-5 support was studied by high-resolution multinuclear solid-state NMR techniques. As proved by {sup 27}Al and {sup 29}Si MAS as well as CP/MAS NMR investigations, this interaction was so strong that the framework aluminum of both microsized and nanosized HZSM-5 zeolites could be extracted. With increasing Mo loading, more nonframework aluminum, resonance at ca. 30 ppm, appeared in the {sup 27}Al MAS NMR spectrum of the Mo-loaded nanosized HZSM-5 catalyst. Meanwhile, this strong interaction led to the formation of more new Al{sub 2}(MoO{sub 4}){sub 3} crystallines on the nanosized HZSM-5 support than on the microsized HZSM-5 support. The appearance of Al{sub 2}(MoO{sub 4}){sub 3} crystallines resulted in fewer active catalysts for the methane dehydro-aromatization. The results of {sup 1}H MAS NMR using perfluorotributyl amine as a probe molecule demonstrated that Mo species preferentially reacted with the silanols and nonframework AlOH on the external surface of microsized and nanosized HZSM-5 zeolites. In addition, impregnated Mo species remained predominantly on the external surface of the nanosized HZSM-5 zeolite, although there was a possibility that they might migrate into the lattice channels of the microsized HZSM-5 zeolite. The migration of some Mo species into the zeolite channels might be beneficial for the conversion of methane to aromatics in the absence of oxygen.

Zhang, W.; Ma, D.; Han, X.; Liu, X.; Bao, X.; Guo, X.; Wang, X.

1999-12-10

353

Peptidelipid interactions of the -hairpin antimicrobial peptide tachyplesin and its linear derivatives from solid-state NMR  

E-print Network

are investigated to gain insight into the mechanism of antimicrobial activity. 31 P and 2 H NMR spectra the structure­activity relationship of membrane destructive antimicrobial peptides is to investigatePeptide­lipid interactions of the -hairpin antimicrobial peptide tachyplesin and its linear

Hong, Mei

354

Solid State Separated-Local-Field NMR Spectroscopy on Half-Integer Quadrupolar Nuclei: Principles and Applications  

E-print Network

and dynamics of a variety of boron-containing samples. These experimental SLF schemes were also extended to 3D NMR experiments that incorporate multiple-quantum MAS, thus enabling the resolution needed to studyHz) and use rotor-synchronized constant-time pulse sequences to achieve nearly arbitrary amplifications

Frydman, Lucio

355

Solid-state {sup 17}O magic-angle and dynamic-angle spinning NMR study of the SiO{sub 2} polymorph coesite  

SciTech Connect

Five distinctly resolved {sup 17}O solid-state NMR resonances in room temperature coesite, an SiO{sub 2} polymorph, have been observed and assigned using dynamic angle spinning (DAS) at 11.7 T along with magic angle spinning (MAS) spectra at 9.4 and 11.7 T. The {sup 17}O quadrupolar parameters for each of the five oxygen environments in coesite are correlated with the Si-O-Si bridging bond angles determined by diffraction experiments. The sign of e{sup 2}-qQ/h along with the orientation of the electric field gradient for oxygen in the Si-O-Si linkage were determined from a Townes-Dailey analysis of the data. 41 refs., 7 figs., 5 tabs.

Grandinetti, P.J. [Ohio State Univ., Columbus, OH (United States); Baltisberger, J.H. [Berea College, KY (United States); Farnan, I.; Stebbins, J.F. [Stanford Univ., CA (United States); Werner, U.; Pines, A. [Lawrence Berkeley Lab., CA (United States)]|[Univ. of California, Berkeley, CA (United States)

1995-08-10

356

"NaB15": a new structural description based on X-ray and neutron diffraction, electron microscopy, and solid-state NMR spectroscopy  

PubMed

A boron-rich sodium boride, formerly known as NaB15, has been subjected to a comprehensive structural reinvestigation using X-ray single-crystal and powder diffraction, low-temperature neutron and electron diffraction, high-resolution transmission electron microscopy, and 23Na solid-state NMR spectroscopy. The results indicate that the previously published orthorhombic space group is incorrect. Consistent with all of the experimental results a modified structural description is developed in the monoclinic space group Ilml (a = 585.92(3), b= 1039.92(6), c = 833.17(5) pin, beta = 90.373(5) from powder data). Because one of the interstitial boron atom positions remains unoccupied, the accurate compositional formula is NaB145 or Na2B29. PMID:10961397

Albert; Hofmann; Fild; Eckert; Schleifer; Gruehn

2000-07-14

357

Resolution and measurement of heteronuclear dipolar couplings of a noncrystalline protein immobilized in a biological supramolecular assembly by proton-detected MAS solid-state NMR spectroscopy  

NASA Astrophysics Data System (ADS)

Two-dimensional 15N chemical shift/1H chemical shift and three-dimensional 1H-15N dipolar coupling/15N chemical shift/1H chemical shift MAS solid-state NMR correlation spectra of the filamentous bacteriophage Pf1 major coat protein show single-site resolution in noncrystalline, intact-phage preparations. The high sensitivity and resolution result from 1H detection at 600 MHz under 50 kHz magic angle spinning using ˜0.5 mg of perdeuterated and uniformly 15N-labeled protein in which the exchangeable amide sites are partially or completely back-exchanged (reprotonated). Notably, the heteronuclear 1H-15N dipolar coupling frequency dimension is shown to select among 15N resonances, which will be useful in structural studies of larger proteins where the resonances exhibit a high degree of overlap in multidimensional chemical shift correlation spectra.

Park, Sang Ho; Yang, Chen; Opella, Stanley J.; Mueller, Leonard J.

2013-12-01

358

Probe for high resolution NMR with sample reorientation  

DOEpatents

An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions are zero.

Pines, Alexander (Berkeley, CA); Samoson, Ago (Tallinn, SU)

1990-01-01

359

Low-E probe for (19)F-(1)H NMR of dilute biological solids.  

PubMed

Sample heating induced by radio frequency (RF) irradiation presents a significant challenge to solid state NMR experiments in proteins and other biological systems, causing the sample to dehydrate which may result in distorted spectra and a damaged sample. In this work we describe a large volume, low-E (19)F-(1)H solid state NMR probe, which we developed for the 2D (19)F CPMG studies of dilute membrane proteins in a static and electrically lossy environment at 600MHz field. In (19)FCPMG and related multi-pulse (19)F-(1)H experiments the sample is heated by the conservative electric fields E produced in the sample coil at both (19)F and (1)H frequencies. Instead of using a traditional sample solenoid, our low-E (19)F-(1)H probe utilizes two orthogonal loop-gap resonators in order to minimize the conservative electric fields responsible for sample heating. Absence of the wavelength effects in loop-gap resonators results in homogeneous RF fields and enables the study of large sample volumes, an important feature for the dilute protein preparations. The orthogonal resonators also provide intrinsic isolation between the (19)F and (1)H channels, which is another major challenge for the (19)F-(1)H circuits where Larmor frequencies are only 6% apart. We detail steps to reduce (19)F background signals from the probe, which included careful choice of capacitor lubricants and manufacture of custom non-fluorinated coaxial cables. Application of the probe for two-dimensional (19)F CPMG spectroscopy in oriented lipid membranes is demonstrated with Flufenamic acid (FFA), a non-steroidal anti-inflammatory drug. PMID:17920316

Gor'kov, Peter L; Witter, Raiker; Chekmenev, Eduard Y; Nozirov, Farhod; Fu, Riqiang; Brey, William W

2007-12-01

360

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

PubMed

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, ? = 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, ? = 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, ? = 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 ?(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. PMID:23374070

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

2013-02-18

361

NMR Crystallography of Enzyme Active Sites: Probing Chemically-Detailed, Three-Dimensional Structure in Tryptophan Synthase  

PubMed Central

Conspectus NMR crystallography – the synergistic combination of X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry – offers unprecedented insight into three-dimensional, chemically-detailed structure. From its initial role in refining diffraction data of organic and inorganic solids, NMR crystallography is now being developed for application to active sites in biomolecules, where it reveals chemically-rich detail concerning the interactions between enzyme site residues and the reacting substrate that is not achievable when X-ray, NMR, or computational methodologies are applied in isolation. For example, typical X-ray crystal structures (1.5 to 2.5 Å resolution) of enzyme-bound intermediates identify possible hydrogen-bonding interactions between site residues and substrate, but do not directly identify the protonation state of either. Solid-state NMR can provide chemical shifts for selected atoms of enzyme-substrate complexes, but without a larger structural framework in which to interpret them, only empirical correlations with local chemical structure are possible. Ab initio calculations and molecular mechanics can build models for enzymatic processes, but rely on chemical details that must be specified. Together, however, X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry can provide consistent and testable models for structure and function of enzyme active sites: X-ray crystallography provides a coarse framework upon which models of the active site can be developed using computational chemistry; these models can be distinguished by comparison of their calculated NMR chemical shifts with the results of solid-state NMR spectroscopy experiments. Conceptually, each technique is a puzzle piece offering a generous view of the big picture. Only when correctly pieced together, however, can they reveal the big picture at highest resolution. In this Account, we detail our first steps in the development of NMR crystallography for application to enzyme catalysis. We begin with a brief introduction to NMR crystallography and then define the process that we have employed to probe the active site in the ?-subunit of tryptophan synthase with unprecedented atomic-level resolution. This approach has resulted in a novel structural hypothesis for the protonation state of the quinonoid intermediate in tryptophan synthase and its surprising role in directing the next step in the catalysis of L-Trp formation. PMID:23537227

Dunn, Michael F.

2013-01-01

362

Investigation of the surface chemistry of phosphine-stabilized ruthenium nanoparticles--an advanced solid-state NMR study.  

PubMed

(31)P-(13)C REDOR NMR measurements allowed a reasonable approximation of distances between stabilizing ligands and carbon monoxide (CO) molecules on the surface of phosphine-stabilized ruthenium nanoparticles (RuNPs). The studied systems are RuNPs in the size range of 1-2 nm stabilized with 1,3,5-triaza-7-phosphaadamantane (PTA) or triphenylphosphine (PPh3) and exposed to a CO atmosphere. This study sheds some light on the interactions between CO and phosphine molecules as well as on their binding geometries on the surface of the RuNPs. As information on the ligand location and mobility is precious for the understanding of the chemical and catalytic properties of nanoparticles, these results support the interest of using sophisticated NMR tools to investigate their surface chemistry. PMID:24022656

Gutmann, Torsten; Bonnefille, Eric; Breitzke, Hergen; Debouttière, Pierre-Jean; Philippot, Karine; Poteau, Romuald; Buntkowsky, Gerd; Chaudret, Bruno

2013-10-28

363

Determination of the average degree of quaternization of N, N, N-trimethylchitosan by solid state 13C NMR  

Microsoft Academic Search

A novel method in which the quaternary salt of chitosan, N,N,N-trimethylchitosan (TMC) was synthesized using dimethylsulfate as the methylant agent is described. Although the synthesis of chitosan quaternary salts has been reported extensively, there remains some uncertainty in determining the resultant average degree of quaternization, DQ¯, in the final products. Here we used CP-MAS 13C NMR spectroscopy, that was able

Douglas de Britto; Lucimara Aparecida Forato; Odílio B. G. Assis

2008-01-01

364

Solid-state NMR studies of the effects of pharmaceutical processing on relaxation dynamics and implications to solidstate drug stability  

E-print Network

? 1 H T 1 of cryoground material significantly les than control ?DSC showed melting point of cryoground material (13.97 ?C) les than that of control (137.02 ?C) ?Water vapor sorption at 90% RH showed weight gain of 9.1% for cryoground material, while...-State Drug Stability ?Lactose and acetylsalicylic acid (aspirin) were subjected to various formulation and procesing conditions, and the efects upon CPMAS NMR spectra and relaxation dynamics were investigated. ?Relaxation dynamics can provide valuable insight...

Lubach, J. W.; Sperger, D. M.; Schieber, L. J.; Munson, E. J.

2006-10-25

365

Evolution of crystalline aluminates from hybrid gel-derived precursors studied by XRD and multinuclear solid-state MAS NMR  

Microsoft Academic Search

Hybrid gels of celsian composition were prepared from Al alkoxide, tetrathylorthosilicate (TEOS) and Ba acetate and their structure evolution was studied up to 1300°C by thermal analysis and X-ray diffraction. Information on their pre-crystallization behaviour was also provided by 27Al, 29Si and 137Ba MAS NMR spectroscopy. Apart from some excess Ba acetate which decomposed to traces of BaCO3 and BaO

K. J. D MacKenzie; T Kemmitt

1999-01-01

366

Evolution of crystalline aluminates from hybrid gel-derived precursors studied by XRD and multinuclear solid-state MAS NMR  

Microsoft Academic Search

The thermal evolution of structure in a hybrid gel of YAG composition (Y3Al5O12) prepared from aluminum alkoxide and yttrium acetate was studied up to 1250°C. XRD indicates that the gels are amorphous <900°C, when they abruptly crystallize to YAG and hexagonal YAlO3. The latter exists only briefly, being fully converted to YAG by 1000°C. 27Al MAS NMR shows that after

K. J. D MacKenzie; T Kemmitt

1999-01-01

367

Environmental Weathering of Aluminosilicate Clay Minerals: Solid-State NMR Studies of Transformations Leading to Radionuclide Sequestration  

SciTech Connect

Mobilities of radionuclides (such as 137Cs and 90Sr) are governed by their interactions with natural soil particles in the saturated and unsaturated zones at Department of Energy sites. High surface area aluminosilicate clay minerals are a component of the natural soils beneath the leaking waste tanks at these sites and serve as possible radionuclide sorbents. However, due to the characteristics of the contaminant medium (high pH, high Al and high ionic strength), clay minerals are susceptible to transformations during exposure to tank waste leachates. We are currently studying the transformation of clays under specific chemical conditions that mimic the composition of known contaminant solutions. In these studies, specimen clay samples are reacted for varying time periods (up to one year) with simulated tank waste leachate solutions. Mineral dissolution and transformation are followed with solution analysis, x-ray diffraction and a number of other analytical methods. We report here results from 27Al MAS NMR at variable magnetic field strengths (up to 18.8 T), 29Si MAS NMR and 1H/29Si CPMAS NMR and evaluate these results along with those of other parallel analytic studies.

Mueller, Karl T.; Crosson, Garry; Chorover, Jon; Choi, Sunkyung

2004-03-28

368

Functional and shunt states of bacteriorhodopsin resolved by 250 GHz dynamic nuclear polarization-enhanced solid-state NMR  

PubMed Central

Observation and structural studies of reaction intermediates of proteins are challenging because of the mixtures of states usually present at low concentrations. Here, we use a 250 GHz gyrotron (cyclotron resonance maser) and cryogenic temperatures to perform high-frequency dynamic nuclear polarization (DNP) NMR experiments that enhance sensitivity in magic-angle spinning NMR spectra of cryo-trapped photocycle intermediates of bacteriorhodopsin (bR) by a factor of ?90. Multidimensional spectroscopy of U-13C,15N-labeled samples resolved coexisting states and allowed chemical shift assignments in the retinylidene chromophore for several intermediates not observed previously. The correlation spectra reveal unexpected heterogeneity in dark-adapted bR, distortion in the K state, and, most importantly, 4 discrete L substates. Thermal relaxation of the mixture of L's showed that 3 of these substates revert to bR568 and that only the 1 substate with both the strongest counterion and a fully relaxed 13-cis bond is functional. These definitive observations of functional and shunt states in the bR photocycle provide a preview of the mechanistic insights that will be accessible in membrane proteins via sensitivity-enhanced DNP NMR. These observations would have not been possible absent the signal enhancement available from DNP. PMID:19474298

Bajaj, Vikram S.; Mak-Jurkauskas, Melody L.; Belenky, Marina; Herzfeld, Judith; Griffin, Robert G.

2009-01-01

369

Connectivity and proximity between quadrupolar nuclides in oxide glasses: insights from through-bond and through-space correlations in solid-state NMR.  

PubMed

The connectivity and proximity among framework cations and anions in covalent oxide glasses yields unique information whereby their various transport and thermodynamic properties can be predicted. Recent developments and advances in the reconstruction of anisotropic spin interactions among quadrupolar nuclides (spin > (1)/(2)) in solid-state NMR shed light on a new opportunity to explore local connectivity and proximity in amorphous solids. Here, we report the 2D through-bond (J-coupling) and through-space (dipolar coupling) correlation NMR spectra for oxide glasses where previously unknown structural details about the connectivity and proximity among quadrupolar nuclides ((27)Al, (17)O) are determined. Nonbridging oxygen peaks in Ca-aluminosilicate glasses with distinct connectivity, such as Ca-O-Al and Al-O-(Al, Si) are well distinguished in {(17)O}(27)Al solid HMQC NMR spectra. Both peaks shift to a lower frequency in direct and indirect dimensions upon the addition of Si to the Ca-aluminate glasses. The 2D (27)Al double quantum magic angle spinning NMR spectra for Mg-aluminoborate glasses indicate the preferential proximity between ([4])Al and ([5])Al leading to the formation of correlations peaks such as ([4])Al-([4])Al, ([4])Al-([5])Al, and ([5])Al-O-([5])Al. A fraction of the ([6])Al-([6])Al correlation peak is also noticeable while that of ([4,5])Al-([6])Al is missing. These results suggest that ([6])Al is likely to be isolated from the ([4])Al and ([5])Al species, forming ([6])Al clusters. The experimental realization of through-bond and through-space correlations among quadrupolar nuclides in amorphous materials suggests a significant deviation from the random distribution among framework cations and a spatial heterogeneity due to possible clustering of framework cations in the model oxide glasses. PMID:19296644

Lee, Sung Keun; Deschamps, Michael; Hiet, Julien; Massiot, Dominique; Park, Sun Young

2009-04-16

370

Solid-state 13C NMR analysis of size and density fractions of marine sediments: Insight into organic carbon sources and preservation mechanisms  

NASA Astrophysics Data System (ADS)

Burial of organic carbon (OC) in ocean sediments acts as the ultimate long-term sink for both terrestrial and marine carbon, however, the mechanisms controlling the preservation of this carbon are poorly understood. To better understand these mechanisms, we applied solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, along with elemental, stable carbon isotopic (? 13C) and lignin phenol analyses, to size and density fractions of sediments influenced by either mixed terrestrial and marine OC inputs (Washington Coast slope) or dominantly marine inputs (Mexican Margin). Elemental, isotopic and lignin analyses all reveal that within the Washington Coast sediment, the OC mixes linearly between nitrogen-poor and 13C-depleted, lignin-rich OC in the large and light fractions and nitrogen-rich and 13C-enriched, lignin-poor OC in the small and dense fractions, suggesting that this sediment contains a two-component mixture of terrestrial vascular plant- and marine-derived OC. The integral areas of each of seven NMR spectral regions in the different samples trend linearly when plotted versus ? 13C signature, with most R2 values of 0.78 or greater, demonstrating that the NMR spectra of the two sources of carbon also mix linearly between the two endmembers. The terrestrial endmember in this sediment appears to be dominated by lignin and black carbon whereas the source of the marine endmember is less clear from the NMR spectra. In contrast, all of the analyses indicate that OC in the Mexican Margin sediment fractions is homogenous and derives almost exclusively from marine sources. It appears that selective preservation of (bio)chemically recalcitrant lignin and black carbon is the primary mechanism of preservation of terrestrial OC, whereas mineral-protection is the dominant mechanism preserving marine OC in the Washington coast sediment. There is little evidence showing that either preservation mechanism functions in the Mexican Margin sediments.

Dickens, Angela F.; Baldock, Jeffrey A.; Smernik, Ronald J.; Wakeham, Stuart G.; Arnarson, Thórarinn S.; Gélinas, Yves; Hedges, John I.

2006-02-01

371

Solid-state 13C NMR studies of dissolved organic matter in pore waters from different depositional environments  

USGS Publications Warehouse

Dissolved organic matter (DOM) in pore waters from sediments of a number of different depositional environments was isolated by ultrafiltration using membranes with a nominal molecular weight cutoff of 500. This > 500 molecular weight DOM represents 70-98% of the total DOM in these pore waters. We determined the gross chemical structure of this material using both solid-state 13C nuclear magnetic resonance spectroscopy and elemental analysis. Our results show that the DOM in these pore waters appears to exist as two major types: one type dominated by carbohydrates and paraffinic structures and the second dominated by paraffinic and aromatic structures. We suggest that the dominance of one or the other structural type of DOM in the pore water depends on the relative oxidizing/reducing nature of the sediments as well as the source of the detrital organic matter. Under dominantly anaerobic conditions carbohydrates in the sediments are degraded by bacteria and accumulate in the pore water as DOM. However, little or no degradation of lignin occurs under these conditions. In contrast, sediments thought to be predominantly aerobic in character have DOM with diminished carbohydrate and enhanced aromatic character. The aromatic structures in the DOM from these sediments are thought to arise from the degradation of lignin. The large amounts of paraffinic structures in both types of DOM may be due to the degradation of unidentified paraffinic materials in algal or bacterial remains. ?? 1987.

Orem, W.H.; Hatcher, P.G.

1987-01-01

372

Structure and dynamics of zirconocene complexes in the solid state studied by sup 13 C CP/MAS NMR spectroscopy  

SciTech Connect

High-resolution one- and two-dimensional solid-state CP/MAS spectra of microcrystalline bent metallocene complexes of the type ({eta}{sup 5}-{sup R}Cp){sub 2}ZrL{sub 2} have been obtained at various temperatures (L = Cl, R = H (1), Me (2), Et (3), {sup t}Bu (4); L{sub 2} = s-cis-{eta}{sup 4}-C{sub 4}H{sub 6}, R = {sup t}Bu (8); L{sub 2} = s-cis-{eta}{sup 4}-C{sub 4}H{sub 6}, R = 1,1-dimethylpentyl (9); L{sub 2} = s-cis-{eta}{sup 4}-C{sub 4}H{sub 5}Me, R = {sup t}Bu (10)). Complexes 1-4 possess C{sub 2} molecular symmetry, while the overall symmetry of complexes 5 and 6 is close to C{sub s}. In 7-9 there is no element of symmetry, and 10 yields diastereoisomers (95:5).

Benn, R.; Grondey, H. (Max-Planck-Inst. fuer Kohlenforschung, Muelheim an der Ruhr (West Germany)); Erker, G.; Aul, R.; Nolte, R. (Univ. Wuerzburg (West Germany))

1990-09-01

373

Microslot NMR Probe for Metabolomics Studies Hans Georg Krojanski,  

E-print Network

by practical problems. Therefore, planar microcoils, which are easier to scale down, were tested. Additionally microcoils were used for high- resolution 1 H NMR, which are based on planar, electromagnetic waveguides can be obtained with this probe in a few seconds. The planar geometry of the probe is easily adaptable

Suter, Dieter

374

Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments  

USGS Publications Warehouse

13C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra. ?? 1980.

Hatcher, P.G.; VanderHart, D.L.; Earl, W.L.

1980-01-01

375

Application of static microcoils and WURST pulses for solid-state ultra-wideline NMR spectroscopy of quadrupolar nuclei  

NASA Astrophysics Data System (ADS)

The uses of microcoils and WURST pulses for acquiring ultra-wideline (UW) NMR spectra of half-integer quadrupolar nuclei are explored. Using large rf field strengths or frequency-swept pulses, UW spectra (breadth > 300 kHz) can be acquired without changing the transmitter frequency. The efficiency of UWNMR spectroscopy improves for both microcoil and WURST pulse experiments compared to rectangular-pulse experiments using a 4.0 mm coil. Microcoils are also used to acquire UW spectra of an unreceptive nucleus ( 91Zr) and a spectrum comprised of both central and satellite transitions ( 59Co).

Tang, Joel A.; O'Dell, Luke A.; Aguiar, Pedro M.; Lucier, Bryan E. G.; Sakellariou, Dimitris; Schurko, Robert W.

2008-12-01

376

Determination of the Average Aromatic Cluster Size of Fossil Fuels by Solid-State NMR at High Magnetic Field  

SciTech Connect

We show that the average aromatic cluster size in complex carbonaceous materials can be accurately determined using fast magic-angle spinning (MAS) NMR at a high magnetic field. To accurately quantify the nonprotonated aromatic carbon, we edited the 13C spectra using the recently reported MAS-synchronized spin–echo, which alleviated the problem of rotational recoupling of 1H-13C dipolar interactions associated with traditional dipolar dephasing experiments. The dependability of this approach was demonstrated on selected Argonne Premium coal standards, for which full sets of basic structural parameters were determined with high accuracy.

Mao, Kanmi [ExxonMobile Research and Engineering Co.; Kennedy, Gordon J. [ExxonMobile Research and Engineering Co.; Althaus, Stacey M. [Ames Laboratory; Pruski, Marek [Ames Laboratory

2013-01-07

377

Determining the effects of lipophilic drugs on membrane structure by solid-state NMR spectroscopy: the case of the antioxidant curcumin.  

PubMed

Curcumin is the active ingredient of turmeric powder, a natural spice used for generations in traditional medicines. Curcumin's broad spectrum of antioxidant, anticarcinogenic, antimutagenic, and anti-inflammatory properties makes it particularly interesting for the development of pharmaceutical compounds. Because of curcumin's various effects on the function of numerous unrelated membrane proteins, it has been suggested that it affects the properties of the bilayer itself. However, a detailed atomic-level study of the interaction of curcumin with membranes has not been attempted. A combination of solid-state NMR and differential scanning calorimetry experiments shows curcumin has a strong effect on membrane structure at low concentrations. Curcumin inserts deep into the membrane in a transbilayer orientation, anchored by hydrogen bonding to the phosphate group of lipids in a manner analogous to cholesterol. Like cholesterol, curcumin induces segmental ordering in the membrane. Analysis of the concentration dependence of the order parameter profile derived from NMR results suggests curcumin forms higher order oligomeric structures in the membrane that span and likely thin the bilayer. Curcumin promotes the formation of the highly curved inverted hexagonal phase, which may influence exocytotic and membrane fusion processes within the cell. The experiments outlined here show promise for understanding the action of other drugs such as capsaicin in which drug-induced alterations of membrane structure have strong pharmacological effects. PMID:19256547

Barry, Jeffrey; Fritz, Michelle; Brender, Jeffrey R; Smith, Pieter E S; Lee, Dong-Kuk; Ramamoorthy, Ayyalusamy

2009-04-01

378

Concentration-Dependent Realignment of the Antimicrobial Peptide PGLa in Lipid Membranes Observed by Solid-State 19F-NMR  

PubMed Central

The membrane-disruptive antimicrobial peptide PGLa is found to change its orientation in a dimyristoyl-phosphatidylcholine bilayer when its concentration is increased to biologically active levels. The alignment of the ?-helix was determined by highly sensitive solid-state NMR measurements of 19F dipolar couplings on CF3-labeled side chains, and supported by a nonperturbing 15N label. At a low peptide/lipid ratio of 1:200 the amphiphilic peptide resides on the membrane surface in the so-called S-state, as expected. However, at high peptide concentration (?1:50 molar ratio) the helix axis changes its tilt angle from ?90° to ?120°, with the C-terminus pointing toward the bilayer interior. This tilted “T-state” represents a novel feature of antimicrobial peptides, which is distinct from a membrane-inserted I-state. At intermediate concentration, PGLa is in exchange between the S- and T-state in the timescale of the NMR experiment. In both states the peptide molecules undergo fast rotation around the membrane normal in liquid crystalline bilayers; hence, large peptide aggregates do not form. Very likely the obliquely tilted T-state represents an antiparallel dimer of PGLa that is formed in the membrane at increasing concentration. PMID:15695635

Glaser, Ralf W.; Sachse, Carsten; Durr, Ulrich H. N.; Wadhwani, Parvesh; Afonin, Sergii; Strandberg, Erik; Ulrich, Anne S.

2005-01-01

379

Solid state NMR strategies for the structural characterization of new hybrid materials based on the intercalation of nitroxide radicals into CdPS3.  

PubMed

The radical cations 2-(3-N-butylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide (m-BuPYNN) and 4-(ethylammonium)-2,2,6,6-tetramethylpiperidin-1-oxide (EATEP) are successfully intercalated into the layered host structure of CdPS(3) via ion exchange. The reaction proceeds either directly from ethanolic solutions of the radical iodide salt or via a two-stage process involving first the formation of an intermediate tetramethylammonium intercalate. The resulting materials, which are described by the compositional formula Cd(1-x)PS(3){Rad}(2x), are characterized by chemical analysis, X-ray powder diffraction, bulk susceptibility measurements and EPR spectroscopy. Modern single and double resonance solid state NMR techniques are introduced successfully to study the structural modifications of the host lattice and the details of the intermolecular guest/host interactions. (1)H MAS-NMR spectra reveal substantial differences in the unpaired electron spin density distributions within the radical ions intercalated into the host lattice compared to those obtained for the pure radical ion salts, leading to different bulk magnetic properties. The results of (1)H/(31)P double resonance experiments indicate that the orientation of the guest molecules is dominated by Columbic interactions between the radical cations and the negatively charged cadmium vacancies in the host lattice. PMID:21543192

Hemme, Wilhelm L; Fujita, Wataru; Awaga, Kunio; Eckert, Hellmut

2011-01-01

380

Protocols for the sequential solid-state NMR spectroscopic assignment of a uniformly labeled 25 kDa protein: HET-s(1-227).  

PubMed

The sequence-specific resonance assignment of a protein forms the basis for studies of molecular structure and dynamics, as well as to functional assay studies by NMR spectroscopy. Here we present a protocol for the sequential 13C and 15N resonance assignment of uniformly [15N,13C]-labeled proteins, based on a suite of complementary three-dimensional solid-state NMR spectroscopy experiments. It is directed towards the application to proteins with more than about 100 amino acid residues. The assignments rely on a walk along the backbone by using a combination of three experiments that correlate nitrogen and carbon spins, including the well-dispersed Cbeta resonances. Supplementary spectra that correlate further side-chain resonances can be important for identifying the amino acid type, and greatly assist the assignment process. We demonstrate the application of this assignment protocol for a crystalline preparation of the N-terminal globular domain of the HET-s prion, a 227-residue protein. PMID:20572250

Schuetz, Anne; Wasmer, Christian; Habenstein, Birgit; Verel, René; Greenwald, Jason; Riek, Roland; Böckmann, Anja; Meier, Beat H

2010-07-26

381

Modifications under irradiation of a self-assembled monolayer grafted on a nano-porous silica glass: a solid-state NMR characterization  

SciTech Connect

Controlled pore glasses with a pore size of 8 nm are grafted with chlorodimethylsilane (ClSi(CH{sub 3}){sub 2}H). The surface of the glass is carefully characterized before and after irradiation with 10 MeV electrons by solid-state NMR measurements. {sup 1}H MAS NMR experiments in one and two dimensions (2D double quantum and 2D exchange) have been used to reveal the grafting of the chlorodimethylsilane at the silica surface and evidence the formation of a homogeneous layer on the surface. Irradiation leads to a high H{sub 2} yield (3.3 * 10{sup -7} mol/J) due to the efficient cleavage of the Si H bond. Methane is detected in smaller quantities (5.5 * 10{sup -8} mol/J), indicating that the Si-H bond is preferentially cleaved over the Si-C bond. The H{sub 2} production arising from OH groups on the surface is very minor in comparison to the S- H and Si-C radiolysis. (authors)

Le Caer, S.; Chatelain, C.; Renault, J.Ph. [CEA, CNRS, Inst Rayonnement Mat Saclay, Lab Radiolyse, SIS2M, Serv Interdisciplinaire Syst Mol et Mat, UMR 3299, F-91191 Gif Sur Yvette, (France); Brunet, F.; Charpentier, T. [CEA, Lab Struct et Dynam Resonance Magnet, CNRS, Inst Rayonnement Mat Saclay, SIS2M, Serv Interdisciplinaire Syst Mol et Mat, UMR 3299, F-91191 Gif Sur Yvette, (France); Durand, D.; Dauvois, V. [CEA Saclay, DEN, DANS, DPC, SECR, LSRM, F-91191 Gif Sur Yvette, (France)

2012-02-15

382

Proton diffusion in hybrid materials of CsHSO 4 and silica nanoparticles as studied by 1H solid-state NMR  

NASA Astrophysics Data System (ADS)

Hybrid materials of CsHSO 4 and silica nanoparticles were prepared by mechanical milling, and hydrogen bond states and proton dynamics were studied by means of 1H solid-state NMR. 1H MAS NMR spectra demonstrated that three types of domains are present in the milled materials. Domain A has hydrogen bond states similar to those in the bulk compound. With respect to hydrogen bonds, domains A-II and A-III are similar to phases II and III of CsHSO 4, respectively. Protons in domain A-II undergo translational diffusion, and the diffusion is faster than in phase II of bulk CsHSO 4. Domain B is originated by mixing of CsHSO 4 with silica nanoparticles, presumably locating at the boundary region. Protons in this domain also undergo translational diffusion. The motional rate is faster than in phase II of bulk CsHSO 4 but is slower than in domain A-II. In domain C protons are contained as OH groups on the surface of silica nanoparticles. Protons are immobile in this domain.

Jimura, Keiko; Hayashi, Shigenobu

2012-01-01

383

Solid state {sup 31}P/{sup 27}Al and {sup 31}P/{sup 23}Na MAS NMR dipolar dephasing investigations of connectivity in sodium aluminophosphate glasses  

SciTech Connect

Solid state {sup 31}P/{sup 27}Al and {sup 31}P/{sup 23}Na MAS NMR dipolar dephasing experiments have been used to investigate the spatial distribution of aluminum and sodium cations with respect to the phosphate backbone for a series of sodium aluminophosphate glasses, xAl{sub 2}O{sub 3}{center_dot}50Na{sub 2}O{center_dot}(50{minus}x)P{sub 2}O{sub 5} (0{le} x {le} 17.5). From the {sup 31}P/{sup 27}Al and {sup 31}P/{sup 23}Na connectivity data gathered, information about the medium range order in these glasses is obtained. The expanded connectivity data allows for better identification and interpretation of the new resonances observed in the {sup 31}P MAS NMR spectra with the addition of alumina. The results of the dipolar dephasing experiments show that the sodium-phosphate distribution remains relatively unchanged for the glass series, and that the addition of aluminum occurs primarily through the depolymerization of the phosphate tetrahedral backbone.

LANG,DAVID P.; ALAM,TODD M.; BENCOE,DENISE N.

2000-05-01

384

High-resolution solid-state NMR study of the occurrence and thermal transformations of silicon-containing species in biomass materials  

SciTech Connect

The occurrence of silicon in two kinds of biomass (rice hulls and endocarp of babassu coconut) and the thermal transformations taking place in these materials under heat treatments are studied here. The authors report also the production, characterization, and study of carbonaceous materials with high SiC content through the carbothermal reduction of silica, using these natural precursors. X-ray diffraction, scanning electron microscopy, and {sup 13}C and {sup 29}Si room temperature high-resolution solid-state NMR measurements are used in the characterization and study of the materials as well as the process of SiC formation. Important conclusions about the nature of silicon in these types of biomass and the effects of heat treatments on the structure of silicon-containing species are derived from the results presented. It is shown that silicon in these materials occurs in two distinct forms: amorphous hydrated silica and organically bound silicon species. The influence of spin-lattice relaxation dynamics on the NMR spectra is discussed, evidencing the role played by the paramagnetic defects produced in the materials through pyrolysis.

Freitas, J.C.C.; Emmerich, F.G.; Bonagamba, T.J.

2000-03-01

385

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

SciTech Connect

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.

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

2003-03-04

386

Solid-state NMR studies of the shape-selective catalytic conversion of methanol into gasoline on zeolite ZSM-5  

SciTech Connect

{sup 13}C Magic angle spinning (MAS)-NMR of thermally treated samples of zeolite H-ZSM-5 with adsorbed methanol identifies the organic species present in the adsorbed phase, monitors their fate, and distinguishes between mobile and attached species. Only MeOH is present at room temperature; in samples treated at 150{degree}C dimethyl ether (DME) is also found. At 250{degree}C and above a new signal, due to CO intermediate, appears. A number of aliphatic and aromatic compounds form at 300{degree}C and above, and the role of CO in this process is discussed. Neither 1,2,3- or 1,3,5-trimethylbenzene is found in the products, but both are present in the adsorbed phase, which is the first direct experimental demonstration of product selectivity. Tetramethylbenzenes have not been found in the products of the reaction at 300{degree}C, but all three are present in the adsorbed phase in considerable concentrations. Their distribution (tetramethylbenzenes are not formed in the thermodynamic equilibrium distribution) reveals the presence of a new kind of shape selectivity. At 370{degree}C the shape-selective action is still present but is different because of the increased effective channel diameters. MAS-NMR has a considerable potential for monitoring and prediction of the course of catalytic reactions directly at the active centers in molecular sieves and will assist the design of shape-selective solids.

Anderson, M.W.; Klinowski, J. (Univ. of Cambridge (England))

1990-01-03

387

Spin-transfer pathways in paramagnetic lithium transition-metal phosphates from combined broadband isotropic solid-state MAS NMR spectroscopy and DFT calculations.  

PubMed

Substituted lithium transition-metal (TM) phosphate LiFe(x)Mn(1-x)PO(4) materials with olivine-type structures are among the most promising next generation lithium ion battery cathodes. However, a complete atomic-level description of the structure of such phases is not yet available. Here, a combined experimental and theoretical approach to the detailed assignment of the (31)P NMR spectra of the LiFe(x)Mn(1-x)PO(4) (x = 0, 0.25, 0.5, 0.75, 1) pure and mixed TM phosphates is developed and applied. Key to the present work is the development of a new NMR experiment enabling the characterization of complex paramagnetic materials via the complete separation of the individual isotropic chemical shifts, along with solid-state hybrid DFT calculations providing the separate hyperfine contributions of all distinct Mn-O-P and Fe-O-P bond pathways. The NMR experiment, referred to as aMAT, makes use of short high-powered adiabatic pulses (SHAPs), which can achieve 100% inversion over a range of isotropic shifts on the order of 1 MHz and with anisotropies greater than 100 kHz. In addition to complete spectral assignments of the mixed phases, the present study provides a detailed insight into the differences in electronic structure driving the variations in hyperfine parameters across the range of materials. A simple model delimiting the effects of distortions due to Mn/Fe substitution is also proposed and applied. The combined approach has clear future applications to TM-bearing battery cathode phases in particular and for the understanding of complex paramagnetic phases in general. PMID:23004936

Clément, Raphaële J; Pell, Andrew J; Middlemiss, Derek S; Strobridge, Fiona C; Miller, Joel K; Whittingham, M Stanley; Emsley, Lyndon; Grey, Clare P; Pintacuda, Guido

2012-10-17

388

Characterization of Dispersed Heteropoly Acid on Mesoporous Zeolite Using Solid-State P-31 NMR Spin-Lattice Relaxation  

SciTech Connect

Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H3PW12O40 (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including 31P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support.

Zhu, Kake; Hu, Jian Z.; She, Xiaoyan; Liu, Jun; Nie, Zimin; Wang, Yong; Peden, Char