Cryogenic sample exchange NMR probe for magic angle spinning dynamic nuclear polarization

PubMed Central

Barnes, Alexander B.; Mak-Jurkauskas, Melody L.; Matsuki, Yoh; Bajaj, Vikram S.; van der Wel, Patrick C. A.; DeRocher, Ronald; Bryant, Jeffrey; Sirigiri, Jagadishwar R.; Temkin, Richard J.; Lugtenburg, Johan; Herzfeld, Judith; Griffin, Robert G.

2009-01-01

We describe a cryogenic sample exchange system that dramatically improves the efficiency of magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments by reducing the time required to change samples and by improving long-term instrument stability. Changing samples in conventional cryogenic MAS DNP/NMR experiments involves warming the probe to room temperature, detaching all cryogenic, RF, and microwave connections, removing the probe from the magnet, replacing the sample, and reversing all the previous steps, with the entire cycle requiring a few hours. The sample exchange system described here — which relies on an eject pipe attached to the front of the MAS stator and a vacuum jacketed dewar with a bellowed hole — circumvents these procedures. To demonstrate the excellent sensitivity, resolution, and stability achieved with this quadruple resonance sample exchange probe, we have performed high precision distance measurements on the active site of the membrane protein bacteriorhodopsin. We also include a spectrum of the tripeptide N-f-MLF-OH at 100 K which shows 30 Hz linewidths. PMID:19356957

Devices and process for high-pressure magic angle spinning nuclear magnetic resonance

DOEpatents

Hoyt, David W; Sears, Jr., Jesse A; Turcu, Romulus V.F.; Rosso, Kevin M; Hu, Jian Zhi

2014-04-08

A high-pressure magic angle spinning (MAS) rotor is detailed that includes a high-pressure sample cell that maintains high pressures exceeding 150 bar. The sample cell design minimizes pressure losses due to penetration over an extended period of time.

Devices and process for high-pressure magic angle spinning nuclear magnetic resonance

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

Hoyt, David W.; Sears, Jesse A.; Turcu, Romulus V. F.

A high-pressure magic angle spinning (MAS) rotor is detailed that includes a high-pressure sample cell that maintains high pressures exceeding 150 bar. The sample cell design minimizes pressure losses due to penetration over an extended period of time.

Fast passage dynamic nuclear polarization on rotating solids.

PubMed

Mentink-Vigier, Frederic; Akbey, Umit; Hovav, Yonatan; Vega, Shimon; Oschkinat, Hartmut; Feintuch, Akiva

2012-11-01

Magic Angle Spinning (MAS) Dynamic Nuclear Polarization (DNP) has proven to be a very powerful way to improve the signal to noise ratio of NMR experiments on solids. The experiments have in general been interpreted considering the Solid-Effect (SE) and Cross-Effect (CE) DNP mechanisms while ignoring the influence of sample spinning. In this paper, we show experimental data of MAS-DNP enhancements of (1)H and (13)C in proline and SH3 protein in glass forming water/glycerol solvent containing TOTAPOL. We also introduce a theoretical model that aims at explaining how the nuclear polarization is built in MAS-DNP experiments. By using Liouville space based simulations to include relaxation on two simple spin models, {electron-nucleus} and {electron-electron-nucleus}, we explain how the basic MAS-SE-DNP and MAS-CE-DNP processes work. The importance of fast energy passages and short level anti-crossing is emphasized and the differences between static DNP and MAS-DNP is explained. During a single rotor cycle the enhancement in the {electron-electron-nucleus} system arises from MAS-CE-DNP involving at least three kinds of two-level fast passages: an electron-electron dipolar anti-crossing, a single quantum electron MW encounter and an anti-crossing at the CE condition inducing nuclear polarization in- or decrements. Numerical, powder-averaged, simulations were performed in order to check the influence of the experimental parameters on the enhancement efficiencies. In particular we show that the spinning frequency dependence of the theoretical MAS-CE-DNP enhancement compares favorably with the experimental (1)H and (13)C MAS-DNP enhancements of proline and SH3. Copyright © 2012 Elsevier Inc. All rights reserved.

Satellite transitions acquired in real time by magic angle spinning (STARTMAS): ``Ultrafast'' high-resolution MAS NMR spectroscopy of spin I =3/2 nuclei

NASA Astrophysics Data System (ADS)

Thrippleton, Michael J.; Ball, Thomas J.; Wimperis, Stephen

2008-01-01

The satellite transitions acquired in real time by magic angle spinning (STARTMAS) NMR experiment combines a train of pulses with sample rotation at the magic angle to refocus the first- and second-order quadrupolar broadening of spin I =3/2 nuclei in a series of echoes, while allowing the isotropic chemical and quadrupolar shifts to evolve. The result is real-time isotropic NMR spectra at high spinning rates using conventional MAS equipment. In this paper we describe in detail how STARTMAS data can be acquired and processed with ease on commercial equipment. We also discuss the advantages and limitations of the approach and illustrate the discussion with numerical simulations and experimental data from four different powdered solids.

Structure of Ancient Glass by 29 Si Magic Angle Spinning NMR Spectroscopy.

PubMed

Bradford, Henry; Ryder, Amy; Henderson, Julian; Titman, Jeremy J

2018-05-23

29 Si magic angle spinning (MAS) NMR spectroscopy has been applied for the first time to the structural analysis of ancient glass samples obtained from archaeological excavations. The results show that it is possible to establish the distribution of Si environments in ancient glass by 29 Si MAS NMR, so long as the concentrations of magnetic impurities, such as Mn and Fe oxides, are low. In general, good agreement has been obtained with compositions determined by means of electron probe microanalysis. In addition, the 29 Si MAS NMR data reveal structural differences between glasses manufactured at separate ancient sites. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Setting the magic angle for fast magic-angle spinning probes.

PubMed

Penzel, Susanne; Smith, Albert A; Ernst, Matthias; Meier, Beat H

2018-06-15

Fast magic-angle spinning, coupled with 1 H detection is a powerful method to improve spectral resolution and signal to noise in solid-state NMR spectra. Commercial probes now provide spinning frequencies in excess of 100 kHz. Then, one has sufficient resolution in the 1 H dimension to directly detect protons, which have a gyromagnetic ratio approximately four times larger than 13 C spins. However, the gains in sensitivity can quickly be lost if the rotation angle is not set precisely. The most common method of magic-angle calibration is to optimize the number of rotary echoes, or sideband intensity, observed on a sample of KBr. However, this typically uses relatively low spinning frequencies, where the spinning of fast-MAS probes is often unstable, and detection on the 13 C channel, for which fast-MAS probes are typically not optimized. Therefore, we compare the KBr-based optimization of the magic angle with two alternative approaches: optimization of the splitting observed in 13 C-labeled glycine-ethylester on the carbonyl due to the Cα-C' J-coupling, or optimization of the H-N J-coupling spin echo in the protein sample itself. The latter method has the particular advantage that no separate sample is necessary for the magic-angle optimization. Copyright © 2018. Published by Elsevier Inc.

A nuclear magnetic resonance spectrometer concept for hermetically sealed magic angle spinning investigations on highly toxic, radiotoxic, or air sensitive materials.

PubMed

Martel, L; Somers, J; Berkmann, C; Koepp, F; Rothermel, A; Pauvert, O; Selfslag, C; Farnan, I

2013-05-01

A concept to integrate a commercial high-resolution, magic angle spinning nuclear magnetic resonance (MAS-NMR) probe capable of very rapid rotation rates (70 kHz) in a hermetically sealed enclosure for the study of highly radiotoxic materials has been developed and successfully demonstrated. The concept centres on a conventional wide bore (89 mm) solid-state NMR magnet operating with industry standard 54 mm diameter probes designed for narrow bore magnets. Rotor insertion and probe tuning take place within a hermetically enclosed glovebox, which extends into the bore of the magnet, in the space between the probe and the magnet shim system. Oxygen-17 MAS-NMR measurements demonstrate the possibility of obtaining high quality spectra from small sample masses (~10 mg) of highly radiotoxic material and the need for high spinning speeds to improve the spectral resolution when working with actinides. The large paramagnetic susceptibility arising from actinide paramagnetism in (Th(1-x)U(x))O2 solid solutions gives rise to extensive spinning sidebands and poor resolution at 15 kHz, which is dramatically improved at 55 kHz. The first (17)O MAS-NMR measurements on NpO(2+x) samples spinning at 55 kHz are also reported. The glovebox approach developed here for radiotoxic materials can be easily adapted to work with other hazardous or even air sensitive materials.

Multiple-rotor-cycle 2D PASS experiments with applications to (207)Pb NMR spectroscopy.

PubMed

Vogt, F G; Gibson, J M; Aurentz, D J; Mueller, K T; Benesi, A J

2000-03-01

Thetwo-dimensional phase-adjusted spinning sidebands (2D PASS) experiment is a useful technique for simplifying magic-angle spinning (MAS) NMR spectra that contain overlapping or complicated spinning sideband manifolds. The pulse sequence separates spinning sidebands by their order in a two-dimensional experiment. The result is an isotropic/anisotropic correlation experiment, in which a sheared projection of the 2D spectrum effectively yields an isotropic spectrum with no sidebands. The original 2D PASS experiment works best at lower MAS speeds (1-5 kHz). At higher spinning speeds (8-12 kHz) the experiment requires higher RF power levels so that the pulses do not overlap. In the case of nuclei such as (207)Pb, a large chemical shift anisotropy often yields too many spinning sidebands to be handled by a reasonable 2D PASS experiment unless higher spinning speeds are used. Performing the experiment at these speeds requires fewer 2D rows and a correspondingly shorter experimental time. Therefore, we have implemented PASS pulse sequences that occupy multiple MAS rotor cycles, thereby avoiding pulse overlap. These multiple-rotor-cycle 2D PASS sequences are intended for use in high-speed MAS situations such as those required by (207)Pb. A version of the multiple-rotor-cycle 2D PASS sequence that uses composite pulses to suppress spectral artifacts is also presented. These sequences are demonstrated on (207)Pb test samples, including lead zirconate, a perovskite-phase compound that is representative of a large class of interesting materials. Copyright 2000 Academic Press.

Field-cycling NMR with high-resolution detection under magic-angle spinning: determination of field-window for nuclear hyperpolarization in a photosynthetic reaction center.

PubMed

Gräsing, Daniel; Bielytskyi, Pavlo; Céspedes-Camacho, Isaac F; Alia, A; Marquardsen, Thorsten; Engelke, Frank; Matysik, Jörg

2017-09-21

Several parameters in NMR depend on the magnetic field strength. Field-cycling NMR is an elegant way to explore the field dependence of these properties. The technique is well developed for solution state and in relaxometry. Here, a shuttle system with magic-angle spinning (MAS) detection is presented to allow for field-dependent studies on solids. The function of this system is demonstrated by exploring the magnetic field dependence of the solid-state photochemically induced nuclear polarization (photo-CIDNP) effect. The effect allows for strong nuclear spin-hyperpolarization in light-induced spin-correlated radical pairs (SCRPs) under solid-state conditions. To this end, 13 C MAS NMR is applied to a photosynthetic reaction center (RC) of the purple bacterium Rhodobacter (R.) sphaeroides wildtype (WT). For induction of the effect in the stray field of the magnet and its subsequent observation at 9.4 T under MAS NMR conditions, the sample is shuttled by the use of an aerodynamically driven sample transfer technique. In the RC, we observe the effect down to 0.25 T allowing to determine the window for the occurrence of the effect to be between about 0.2 and 20 T.

Solvent signal suppression for high-resolution MAS-DNP

NASA Astrophysics Data System (ADS)

Lee, Daniel; Chaudhari, Sachin R.; De Paëpe, Gaël

2017-05-01

Dynamic nuclear polarization (DNP) has become a powerful tool to substantially increase the sensitivity of high-field magic angle spinning (MAS) solid-state NMR experiments. The addition of dissolved hyperpolarizing agents usually results in the presence of solvent signals that can overlap and obscure those of interest from the analyte. Here, two methods are proposed to suppress DNP solvent signals: a Forced Echo Dephasing experiment (FEDex) and TRAnsfer of Populations in DOuble Resonance Echo Dephasing (TRAPDORED) NMR. These methods reintroduce a heteronuclear dipolar interaction that is specific to the solvent, thereby forcing a dephasing of recoupled solvent spins and leaving acquired NMR spectra free of associated resonance overlap with the analyte. The potency of these methods is demonstrated on sample types common to MAS-DNP experiments, namely a frozen solution (of L-proline) and a powdered solid (progesterone), both containing deuterated glycerol as a DNP solvent. The proposed methods are efficient, simple to implement, compatible with other NMR experiments, and extendable past spectral editing for just DNP solvents. The sensitivity gains from MAS-DNP in conjunction with FEDex or TRAPDORED then permits rapid and uninterrupted sample analysis.

Pulsed field gradient magic angle spinning NMR self-diffusion measurements in liquids

NASA Astrophysics Data System (ADS)

Viel, Stéphane; Ziarelli, Fabio; Pagès, Guilhem; Carrara, Caroline; Caldarelli, Stefano

2008-01-01

Several investigations have recently reported the combined use of pulsed field gradient (PFG) with magic angle spinning (MAS) for the analysis of molecular mobility in heterogeneous materials. In contrast, little attention has been devoted so far to delimiting the role of the extra force field induced by sample rotation on the significance and reliability of self-diffusivity measurements. The main purpose of this work is to examine this phenomenon by focusing on pure liquids for which its impact is expected to be largest. Specifically, we show that self-diffusion coefficients can be accurately determined by PFG MAS NMR diffusion measurements in liquids, provided that specific experimental conditions are met. First, the methodology to estimate the gradient uniformity and to properly calibrate its absolute strength is briefly reviewed and applied on a MAS probe equipped with a gradient coil aligned along the rotor spinning axis, the so-called 'magic angle gradient' coil. Second, the influence of MAS on the outcome of PFG MAS diffusion measurements in liquids is investigated for two distinct typical rotors of different active volumes, 12 and 50 μL. While the latter rotor led to totally unreliable results, especially for low viscosity compounds, the former allowed for the determination of accurate self-diffusion coefficients both for fast and slowly diffusing species. Potential implications of this work are the possibility to measure accurate self-diffusion coefficients of sample-limited mixtures or to avoid radiation damping interferences in NMR diffusion measurements. Overall, the outlined methodology should be of interest to anyone who strives to improve the reliability of MAS diffusion studies, both in homogeneous and heterogeneous media.

Effective combined water and sideband suppression for low-speed tissue and in vivo MAS NMR.

PubMed

Mobarhan, Yalda Liaghati; Struppe, Jochem; Fortier-McGill, Blythe; Simpson, André J

2017-08-01

High-resolution magic angle spinning (HR-MAS) NMR is a powerful technique that can provide metabolic profiles and structural constraints on intact biological and environmental samples such as cells, tissues and living organisms. However, centripetal force from fast spinning can lead to a loss of sample integrity. In analyses focusing on structural organization, metabolite compartmentalization or in vivo studies, it is critical to keep the sample intact. As such, there is growing interest in slow spinning studies that preserve sample longevity. In this study, for example, reducing the spinning rate from 2500 to 500 Hz during the analysis of a living freshwater shrimp increased the 100% survivability threshold from ~14 to 40 h. Unfortunately, reducing spinning rate decreases the intensity of the isotropic signals and increases both the intensity and number of spinning sidebands, which mask spectral information. Interestingly, water suppression approaches such as excitation sculpting and W5 WATERGATE, which are effective at higher spinning rates, fail at lower spinning rates (<2500 Hz) while simpler approaches such as presaturation are not able to effectively suppress water when the ratio of water to biomass is very high, as is the case in vivo. As such there is a considerable gap in NMR approaches which can be used to suppress water signals and sidebands in biological samples at lower spinning rates. This research presents simple but practically important sequences that combine PURGE water suppression with both phase-adjusted spinning sidebands and an analogue of TOSS termed TOSS.243. The result is simple and effective water and sideband suppression even in extremely dilute samples in pure water down to ~100 Hz spinning rate. The approach is introduced, described and applied to a range of samples including, ex vivo worm tissue, Daphnia magna (water fleas), and in vivo Hyalella azteca (shrimp).

Instrumentation for cryogenic magic angle spinning dynamic nuclear polarization using 90 L of liquid nitrogen per day

NASA Astrophysics Data System (ADS)

Albert, Brice J.; Pahng, Seong Ho; Alaniva, Nicholas; Sesti, Erika L.; Rand, Peter W.; Saliba, Edward P.; Scott, Faith J.; Choi, Eric J.; Barnes, Alexander B.

2017-10-01

Cryogenic sample temperatures can enhance NMR sensitivity by extending spin relaxation times to improve dynamic nuclear polarization (DNP) and by increasing Boltzmann spin polarization. We have developed an efficient heat exchanger with a liquid nitrogen consumption rate of only 90 L per day to perform magic-angle spinning (MAS) DNP experiments below 85 K. In this heat exchanger implementation, cold exhaust gas from the NMR probe is returned to the outer portion of a counterflow coil within an intermediate cooling stage to improve cooling efficiency of the spinning and variable temperature gases. The heat exchange within the counterflow coil is calculated with computational fluid dynamics to optimize the heat transfer. Experimental results using the novel counterflow heat exchanger demonstrate MAS DNP signal enhancements of 328 ± 3 at 81 ± 2 K, and 276 ± 4 at 105 ± 2 K.

High-pressure, high-temperature magic angle spinning nuclear magnetic resonance devices and processes for making and using same

DOEpatents

Hu, Jian Zhi; Hu, Mary Y.; Townsend, Mark R.; Lercher, Johannes A.; Peden, Charles H. F.

2015-10-06

Re-usable ceramic magic angle spinning (MAS) NMR rotors constructed of high-mechanic strength ceramics are detailed that include a sample compartment that maintains high pressures up to at least about 200 atmospheres (atm) and high temperatures up to about least about 300.degree. C. during operation. The rotor designs minimize pressure losses stemming from penetration over an extended period of time. The present invention makes possible a variety of in-situ high pressure, high temperature MAS NMR experiments not previously achieved in the prior art.

Exploring high-resolution magic angle spinning (HR-MAS) NMR spectroscopy for metabonomic analysis of apples.

PubMed

Vermathen, Martina; Marzorati, Mattia; Vermathen, Peter

2012-01-01

Classical liquid-state high-resolution (HR) NMR spectroscopy has proved a powerful tool in the metabonomic analysis of liquid food samples like fruit juices. In this paper the application of (1)H high-resolution magic angle spinning (HR-MAS) NMR spectroscopy to apple tissue is presented probing its potential for metabonomic studies. The (1)H HR-MAS NMR spectra are discussed in terms of the chemical composition of apple tissue and compared to liquid-state NMR spectra of apple juice. Differences indicate that specific metabolic changes are induced by juice preparation. The feasibility of HR-MAS NMR-based multivariate analysis is demonstrated by a study distinguishing three different apple cultivars by principal component analysis (PCA). Preliminary results are shown from subsequent studies comparing three different cultivation methods by means of PCA and partial least squares discriminant analysis (PLS-DA) of the HR-MAS NMR data. The compounds responsible for discriminating organically grown apples are discussed. Finally, an outlook of our ongoing work is given including a longitudinal study on apples.

Powder-XRD and (14) N magic angle-spinning solid-state NMR spectroscopy of some metal nitrides.

PubMed

Kempgens, Pierre; Britton, Jonathan

2016-05-01

Some metal nitrides (TiN, ZrN, InN, GaN, Ca3 N2 , Mg3 N2 , and Ge3 N4 ) have been studied by powder X-ray diffraction (XRD) and (14) N magic angle-spinning (MAS) solid-state NMR spectroscopy. For Ca3 N2 , Mg3 N2 , and Ge3 N4 , no (14) N NMR signal was observed. Low speed (νr  = 2 kHz for TiN, ZrN, and GaN; νr  = 1 kHz for InN) and 'high speed' (νr  = 15 kHz for TiN; νr  = 5 kHz for ZrN; νr  = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder-XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their (14) N MAS solid-state NMR spectrum matches perfectly well with the number of nitrogen-containing phases identified by powder-XRD. The (14) N MAS solid-state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Qcc 's arising from structural defects in the compounds studied. Copyright © 2015 John Wiley & Sons, Ltd.

Direct determination of phosphate sugars in biological material by (1)H high-resolution magic-angle-spinning NMR spectroscopy.

PubMed

Diserens, Gaëlle; Vermathen, Martina; Gjuroski, Ilche; Eggimann, Sandra; Precht, Christina; Boesch, Chris; Vermathen, Peter

2016-08-01

The study aim was to unambiguously assign nucleotide sugars, mainly UDP-X that are known to be important in glycosylation processes as sugar donors, and glucose-phosphates that are important intermediate metabolites for storage and transfer of energy directly in spectra of intact cells, as well as in skeletal muscle biopsies by (1)H high-resolution magic-angle-spinning (HR-MAS) NMR. The results demonstrate that sugar phosphates can be determined quickly and non-destructively in cells and biopsies by HR-MAS, which may prove valuable considering the importance of phosphate sugars in cell metabolism for nucleic acid synthesis. As proof of principle, an example of phosphate-sugar reaction and degradation kinetics after unfreezing the sample is shown for a cardiac muscle, suggesting the possibility to follow by HR-MAS NMR some metabolic pathways. Graphical abstract Glucose-phosphate sugars (Glc-1P and Glc-6P) detected in muscle by 1H HR-MAS NMR.

Systematic evaluation of heteronuclear spin decoupling in solid-state NMR at the rotary-resonance conditions in the regime of fast magic-angle spinning

NASA Astrophysics Data System (ADS)

Sharma, Kshama; Madhu, P. K.; Agarwal, Vipin

2016-09-01

The performance of heteronuclear spin decoupling sequences in solid-state NMR severely degrades when the proton radiofrequency (RF) nutation frequencies (ν1) are close to or at multiples of magic-angle spinning (MAS) frequency (νr) that are referred to as rotary-resonance recoupling conditions (ν1 = n · νr). Recently, two schemes, namely, PISSARRO and rCWApA, have been shown to be less affected by the problem of MAS and RF interference, specifically at the n = 2 rotary-resonance recoupling condition, especially in the fast MAS regime. Here, we systematically evaluate the loss in intensity of several heteronuclear spin decoupling sequences at the n = 1, 2 conditions compared to high-power decoupling in the fast-MAS regime. We propose that in the fast-MAS regime (above 40 kHz) the entire discussion about RF and MAS interference can be avoided by using appropriate low-power decoupling sequences which give comparable performance to decoupling sequences with high-power 1H irradiation of ca.195 kHz.

Sensitivity enhancement by multiple-contact cross-polarization under magic-angle spinning.

PubMed

Raya, J; Hirschinger, J

2017-08-01

Multiple-contact cross-polarization (MC-CP) is applied to powder samples of ferrocene and l-alanine under magic-angle spinning (MAS) conditions. The method is described analytically through the density matrix formalism. The combination of a two-step memory function approach and the Anderson-Weiss approximation is found to be particularly useful to derive approximate analytical solutions for single-contact Hartmann-Hahn CP (HHCP) and MC-CP dynamics under MAS. We show that the MC-CP sequence requiring no pulse-shape optimization yields higher polarizations at short contact times than optimized adiabatic passage through the HH condition CP (APHH-CP) when the MAS frequency is comparable to the heteronuclear dipolar coupling, i.e., when APHH-CP through a single sideband matching condition is impossible or difficult to perform. It is also shown that the MC-CP sideband HH conditions are generally much broader than for single-contact HHCP and that efficient polarization transfer at the centerband HH condition can be reintroduced by rotor-asynchronous multiple equilibrations-re-equilibrations with the proton spin bath. Boundary conditions for the successful use of the MC-CP experiment when relying on spin-lattice relaxation for repolarization are also examined. Copyright © 2017 Elsevier Inc. All rights reserved.

Sensitivity enhancement by multiple-contact cross-polarization under magic-angle spinning

NASA Astrophysics Data System (ADS)

Raya, J.; Hirschinger, J.

2017-08-01

Multiple-contact cross-polarization (MC-CP) is applied to powder samples of ferrocene and L-alanine under magic-angle spinning (MAS) conditions. The method is described analytically through the density matrix formalism. The combination of a two-step memory function approach and the Anderson-Weiss approximation is found to be particularly useful to derive approximate analytical solutions for single-contact Hartmann-Hahn CP (HHCP) and MC-CP dynamics under MAS. We show that the MC-CP sequence requiring no pulse-shape optimization yields higher polarizations at short contact times than optimized adiabatic passage through the HH condition CP (APHH-CP) when the MAS frequency is comparable to the heteronuclear dipolar coupling, i.e., when APHH-CP through a single sideband matching condition is impossible or difficult to perform. It is also shown that the MC-CP sideband HH conditions are generally much broader than for single-contact HHCP and that efficient polarization transfer at the centerband HH condition can be reintroduced by rotor-asynchronous multiple equilibrations-re-equilibrations with the proton spin bath. Boundary conditions for the successful use of the MC-CP experiment when relying on spin-lattice relaxation for repolarization are also examined.

1H line width dependence on MAS speed in solid state NMR - Comparison of experiment and simulation

NASA Astrophysics Data System (ADS)

Sternberg, Ulrich; Witter, Raiker; Kuprov, Ilya; Lamley, Jonathan M.; Oss, Andres; Lewandowski, Józef R.; Samoson, Ago

2018-06-01

Recent developments in magic angle spinning (MAS) technology permit spinning frequencies of ≥100 kHz. We examine the effect of such fast MAS rates upon nuclear magnetic resonance proton line widths in the multi-spin system of β-Asp-Ala crystal. We perform powder pattern simulations employing Fokker-Plank approach with periodic boundary conditions and 1H-chemical shift tensors calculated using the bond polarization theory. The theoretical predictions mirror well the experimental results. Both approaches demonstrate that homogeneous broadening has a linear-quadratic dependency on the inverse of the MAS spinning frequency and that, at the faster end of the spinning frequencies, the residual spectral line broadening becomes dominated by chemical shift distributions and susceptibility effects even for crystalline systems.

Low-temperature dynamic nuclear polarization with helium-cooled samples and nitrogen-driven magic-angle spinning.

PubMed

Thurber, Kent; Tycko, Robert

2016-03-01

We describe novel instrumentation for low-temperature solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS), focusing on aspects of this instrumentation that have not been described in detail in previous publications. We characterize the performance of an extended interaction oscillator (EIO) microwave source, operating near 264 GHz with 1.5 W output power, which we use in conjunction with a quasi-optical microwave polarizing system and a MAS NMR probe that employs liquid helium for sample cooling and nitrogen gas for sample spinning. Enhancement factors for cross-polarized (13)C NMR signals in the 100-200 range are demonstrated with DNP at 25K. The dependences of signal amplitudes on sample temperature, as well as microwave power, polarization, and frequency, are presented. We show that sample temperatures below 30K can be achieved with helium consumption rates below 1.3 l/h. To illustrate potential applications of this instrumentation in structural studies of biochemical systems, we compare results from low-temperature DNP experiments on a calmodulin-binding peptide in its free and bound states. Published by Elsevier Inc.

Multiple-quantum spin counting in magic-angle-spinning NMR via low-power symmetry-based dipolar recoupling

NASA Astrophysics Data System (ADS)

Teymoori, Gholamhasan; Pahari, Bholanath; Viswanathan, Elumalai; Edén, Mattias

2013-11-01

By using a symmetry-based R281R28-1 double-quantum (2Q) dipolar recoupling sequence, we demonstrate high-order multiple-quantum coherence (MQC) excitation at fast magic-angle spinning (MAS) frequencies up to 34 kHz. This scheme combines several attractive features, such as a relatively high dipolar scaling factor, good compensation to rf-errors, isotropic and anisotropic chemical shifts, as well as an ultra-low radio-frequency (rf) power requirement. The latter translates into nutation frequencies below 30 kHz for MAS rates up to 60 kHz, thereby permitting rf application for very long excitation periods without risk of damaging the NMR probehead or sample, while the compensation to chemical shifts improves as the MAS rate increases. 31P MQC spin counting is demonstrated on powders of calcium hydroxyapatite (Ca5(PO4)3OH) and anhydrous sodium diphosphate (Na4P2O7), from which all even coherence orders up to 30 and 14 were detected, respectively, over the respective MAS ranges of 15-24 kHz and 20-34 kHz. The amplitude distributions among the 31P MQC orders depend on the precise nutation frequency during recoupling, despite that the highest detected order was relatively insensitive to this parameter. An observed gradual transition from a Gaussian to exponential functionality of the MQC amplitude-profile is discussed in relation to the prevailing approach to derive spin-cluster sizes by fitting the MQC amplitude-distribution to a Gaussian decay, where minor systematic deviations between the model and experimental data are frequently reported.

NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

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

Shmyreva, Anna A.; Safdari, Majid; Furó, István

2016-06-14

Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancementmore » is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.« less

Solid-state dynamic nuclear polarization at 263 GHz: spectrometer design and experimental results†

PubMed Central

Rosay, Melanie; Tometich, Leo; Pawsey, Shane; Bader, Reto; Schauwecker, Robert; Blank, Monica; Borchard, Philipp M.; Cauffman, Stephen R.; Felch, Kevin L.; Weber, Ralph T.; Temkin, Richard J.; Griffin, Robert G.; Maas, Werner E.

2015-01-01

Dynamic Nuclear Polarization (DNP) experiments transfer polarization from electron spins to nuclear spins with microwave irradiation of the electron spins for enhanced sensitivity in nuclear magnetic resonance (NMR) spectroscopy. Design and testing of a spectrometer for magic angle spinning (MAS) DNP experiments at 263 GHz microwave frequency, 400 MHz 1H frequency is described. Microwaves are generated by a novel continuous-wave gyrotron, transmitted to the NMR probe via a transmission line, and irradiated on a 3.2 mm rotor for MAS DNP experiments. DNP signal enhancements of up to 80 have been measured at 95 K on urea and proline in water–glycerol with the biradical polarizing agent TOTAPOL. We characterize the experimental parameters affecting the DNP efficiency: the magnetic field dependence, temperature dependence and polarization build-up times, microwave power dependence, sample heating effects, and spinning frequency dependence of the DNP signal enhancement. Stable system operation, including DNP performance, is also demonstrated over a 36 h period. PMID:20449524

Verdazyl-ribose: A new radical for solid-state dynamic nuclear polarization at high magnetic field

NASA Astrophysics Data System (ADS)

Thurber, Kent R.; Le, Thanh-Ngoc; Changcoco, Victor; Brook, David J. R.

2018-04-01

Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants.

An efficient method and device for transfer of semisolid materials into solid-state NMR spectroscopy rotors.

PubMed

Hisao, Grant S; Harland, Michael A; Brown, Robert A; Berthold, Deborah A; Wilson, Thomas E; Rienstra, Chad M

2016-04-01

The study of mass-limited biological samples by magic angle spinning (MAS) solid-state NMR spectroscopy critically relies upon the high-yield transfer of material from a biological preparation into the MAS rotor. This issue is particularly important for maintaining biological activity and hydration of semi-solid samples such as membrane proteins in lipid bilayers, pharmaceutical formulations, microcrystalline proteins and protein fibrils. Here we present protocols and designs for rotor-packing devices specifically suited for packing hydrated samples into Pencil-style 1.6 mm, 3.2 mm standard, and 3.2 mm limited speed MAS rotors. The devices are modular and therefore readily adaptable to other rotor and/or ultracentrifugation tube geometries. Copyright © 2016 Elsevier Inc. All rights reserved.

High-resolution magic angle spinning 1H-NMR spectroscopy studies on the renal biochemistry in the bank vole (Clethrionomys glareolus) and the effects of arsenic (As3+) toxicity.

PubMed

Griffin, J L; Walker, L; Shore, R F; Nicholson, J K

2001-06-01

1. High-resolution magic angle spinning (MAS) 1H-NMR spectroscopy was used to study renal metabolism and the toxicity of As3+, a common environmental contaminant, in the bank vole (Clethrionomys glareolus), a wild species of rodent. 2. Following a 14-day exposure to an environmentally relevant dose of As2O3 (28 mg kg(-1) feed), voles displayed tissue damage at autopsy. MAS 1H spectra indicated abnormal lipid profiles in these samples. 3. Tissue necrosis was also evident from measurements of the apparent diffusion coefficient of water in the intact tissue using MAS 1H diffusion-weighted spectroscopy, its first application to toxicology. 4. Comparison of renal tissue from the wood mouse (Apodemus sylvaticus) exposed to identical exposure levels of As3+ suggested that the bank vole is particularly vulnerable to As3+ toxicity.

Studying Dynamics by Magic-Angle Spinning Solid-State NMR Spectroscopy: Principles and Applications to Biomolecules

PubMed Central

Schanda, Paul; Ernst, Matthias

2016-01-01

Magic-angle spinning solid-state NMR spectroscopy is an important technique to study molecular structure, dynamics and interactions, and is rapidly gaining importance in biomolecular sciences. Here we provide an overview of experimental approaches to study molecular dynamics by MAS solid-state NMR, with an emphasis on the underlying theoretical concepts and differences of MAS solid-state NMR compared to solution-state NMR. The theoretical foundations of nuclear spin relaxation are revisited, focusing on the particularities of spin relaxation in solid samples under magic-angle spinning. We discuss the range of validity of Redfield theory, as well as the inherent multi-exponential behavior of relaxation in solids. Experimental challenges for measuring relaxation parameters in MAS solid-state NMR and a few recently proposed relaxation approaches are discussed, which provide information about time scales and amplitudes of motions ranging from picoseconds to milliseconds. We also discuss the theoretical basis and experimental measurements of anisotropic interactions (chemical-shift anisotropies, dipolar and quadrupolar couplings), which give direct information about the amplitude of motions. The potential of combining relaxation data with such measurements of dynamically-averaged anisotropic interactions is discussed. Although the focus of this review is on the theoretical foundations of dynamics studies rather than their application, we close by discussing a small number of recent dynamics studies, where the dynamic properties of proteins in crystals are compared to those in solution. PMID:27110043

Spin-locking of half-integer quadrupolar nuclei in nuclear magnetic resonance of solids: creation and evolution of coherences.

PubMed

Ashbrook, Sharon E; Wimperis, Stephen

2004-02-08

Spin-locking of half-integer quadrupolar nuclei, such as 23Na (I=3/2) and 27Al (I=5/2), is of renewed interest owing to the development of variants of the multiple-quantum and satellite-transition magic angle spinning (MAS) nuclear magnetic resonance experiments that either utilize spin-locking directly or offer the possibility that spin-locked states may arise. However, the large magnitude and, under MAS, the time dependence of the quadrupolar interaction often result in complex spin-locking phenomena that are not widely understood. Here we show that, following the application of a spin-locking pulse, a variety of coherence transfer processes occur on a time scale of approximately 1/omegaQ before the spin system settles down into a spin-locked state which may itself be time dependent if MAS is performed. We show theoretically for both spin I=3/2 and 5/2 nuclei that the spin-locked state created by this initial rapid dephasing typically consists of a variety of single- and multiple-quantum coherences and nonequilibrium population states and we discuss the subsequent evolution of these under MAS. In contrast to previous work, we consider spin-locking using a wide range of radio frequency field strengths, i.e., a range that covers both the "strong-field" (omega1 > omegaQPAS and "weak-field" (omega1 < omegaQPAS limits. Single- and multiple-quantum filtered spin-locking experiments on NaNO2, NaNO3, and Al(acac)3, under both static and MAS conditions, are used to illustrate and confirm the results of the theoretical discussion.

Spin-echo based diagonal peak suppression in solid-state MAS NMR homonuclear chemical shift correlation spectra

NASA Astrophysics Data System (ADS)

Wang, Kaiyu; Zhang, Zhiyong; Ding, Xiaoyan; Tian, Fang; Huang, Yuqing; Chen, Zhong; Fu, Riqiang

2018-02-01

The feasibility of using the spin-echo based diagonal peak suppression method in solid-state MAS NMR homonuclear chemical shift correlation experiments is demonstrated. A complete phase cycling is designed in such a way that in the indirect dimension only the spin diffused signals are evolved, while all signals not involved in polarization transfer are refocused for cancellation. A data processing procedure is further introduced to reconstruct this acquired spectrum into a conventional two-dimensional homonuclear chemical shift correlation spectrum. A uniformly 13C, 15N labeled Fmoc-valine sample and the transmembrane domain of a human protein, LR11 (sorLA), in native Escherichia coli membranes have been used to illustrate the capability of the proposed method in comparison with standard 13C-13C chemical shift correlation experiments.

Radiofrequency fields in MAS solid state NMR probes

NASA Astrophysics Data System (ADS)

Tošner, Zdeněk; Purea, Armin; Struppe, Jochem O.; Wegner, Sebastian; Engelke, Frank; Glaser, Steffen J.; Reif, Bernd

2017-11-01

We present a detailed analysis of the radiofrequency (RF) field over full volume of a rotor that is generated in a solenoid coil. On top of the usually considered static distribution of amplitudes along the coil axis we describe dynamic radial RF inhomogeneities induced by sample rotation. During magic angle spinning (MAS), the mechanical rotation of the sample about the magic angle, a spin packet travels through areas of different RF fields and experiences periodical modulations of both the RF amplitude and the phase. These modulations become particularly severe at the end regions of the coil where the relative RF amplitude varies up to ±25% and the RF phase changes within ±30°. Using extensive numerical simulations we demonstrate effects of RF inhomogeneity on pulse calibration and for the ramped CP experiment performed at a wide range of MAS rates. In addition, we review various methods to map RF fields using a B0 gradient along the sample (rotor axis) for imaging purposes. Under such a gradient, a nutation experiment provides directly the RF amplitude distribution, a cross polarization experiment images the correlation of the RF fields on the two channels according to the Hartmann-Hahn matching condition, while a spin-lock experiment allows to calibrate the RF amplitude employing the rotary resonance recoupling condition. Knowledge of the RF field distribution in a coil provides key to understand its effects on performance of a pulse sequence at the spectrometer and enables to set robustness requirements in the experimental design.

1H MAS NMR (magic-angle spinning nuclear magnetic resonance) techniques for the quantitative determination of hydrogen types in solid catalysts and supports.

PubMed

Kennedy, Gordon J; Afeworki, Mobae; Calabro, David C; Chase, Clarence E; Smiley, Randolph J

2004-06-01

Distinct hydrogen species are present in important inorganic solids such as zeolites, silicoaluminophosphates (SAPOs), mesoporous materials, amorphous silicas, and aluminas. These H species include hydrogens associated with acidic sites such as Al(OH)Si, non-framework aluminum sites, silanols, and surface functionalities. Direct and quantitative methodology to identify, measure, and monitor these hydrogen species are key to monitoring catalyst activity, optimizing synthesis conditions, tracking post-synthesis structural modifications, and in the preparation of novel catalytic materials. Many workers have developed several techniques to address these issues, including 1H MAS NMR (magic-angle spinning nuclear magnetic resonance). 1H MAS NMR offers many potential advantages over other techniques, but care is needed in recognizing experimental limitations and developing sample handling and NMR methodology to obtain quantitatively reliable data. A simplified approach is described that permits vacuum dehydration of multiple samples simultaneously and directly in the MAS rotor without the need for epoxy, flame sealing, or extensive glovebox use. We have found that careful optimization of important NMR conditions, such as magnetic field homogeneity and magic angle setting are necessary to acquire quantitative, high-resolution spectra that accurately measure the concentrations of the different hydrogen species present. Details of this 1H MAS NMR methodology with representative applications to zeolites, SAPOs, M41S, and silicas as a function of synthesis conditions and post-synthesis treatments (i.e., steaming, thermal dehydroxylation, and functionalization) are presented.

Magic angle spinning NMR below 6 K with a computational fluid dynamics analysis of fluid flow and temperature gradients

NASA Astrophysics Data System (ADS)

Sesti, Erika L.; Alaniva, Nicholas; Rand, Peter W.; Choi, Eric J.; Albert, Brice J.; Saliba, Edward P.; Scott, Faith J.; Barnes, Alexander B.

2018-01-01

We report magic angle spinning (MAS) up to 8.5 kHz with a sample temperature below 6 K using liquid helium as a variable temperature fluid. Cross polarization 13C NMR spectra exhibit exquisite sensitivity with a single transient. Remarkably, 1H saturation recovery experiments show a 1H T1 of 21 s with MAS below 6 K in the presence of trityl radicals in a glassy matrix. Leveraging the thermal spin polarization available at 4.2 K versus 298 K should result in 71 times higher signal intensity. Taking the 1H longitudinal relaxation into account, signal averaging times are therefore predicted to be expedited by a factor of >500. Computer assisted design (CAD) and finite element analysis were employed in both the design and diagnostic stages of this cryogenic MAS technology development. Computational fluid dynamics (CFD) models describing temperature gradients and fluid flow are presented. The CFD models bearing and drive gas maintained at 100 K, while a colder helium variable temperature fluid stream cools the center of a zirconia rotor. Results from the CFD were used to optimize the helium exhaust path and determine the sample temperature. This novel cryogenic experimental platform will be integrated with pulsed dynamic nuclear polarization and electron decoupling to interrogate biomolecular structure within intact human cells.

Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: the importance of level crossings.

PubMed

Thurber, Kent R; Tycko, Robert

2012-08-28

We present theoretical calculations of dynamic nuclear polarization (DNP) due to the cross effect in nuclear magnetic resonance under magic-angle spinning (MAS). Using a three-spin model (two electrons and one nucleus), cross effect DNP with MAS for electron spins with a large g-anisotropy can be seen as a series of spin transitions at avoided crossings of the energy levels, with varying degrees of adiabaticity. If the electron spin-lattice relaxation time T(1e) is large relative to the MAS rotation period, the cross effect can happen as two separate events: (i) partial saturation of one electron spin by the applied microwaves as one electron spin resonance (ESR) frequency crosses the microwave frequency and (ii) flip of all three spins, when the difference of the two ESR frequencies crosses the nuclear frequency, which transfers polarization to the nuclear spin if the two electron spins have different polarizations. In addition, adiabatic level crossings at which the two ESR frequencies become equal serve to maintain non-uniform saturation across the ESR line. We present analytical results based on the Landau-Zener theory of adiabatic transitions, as well as numerical quantum mechanical calculations for the evolution of the time-dependent three-spin system. These calculations provide insight into the dependence of cross effect DNP on various experimental parameters, including MAS frequency, microwave field strength, spin relaxation rates, hyperfine and electron-electron dipole coupling strengths, and the nature of the biradical dopants.

1H magic-angle spinning NMR evolves as a powerful new tool for membrane proteins

NASA Astrophysics Data System (ADS)

Schubeis, Tobias; Le Marchand, Tanguy; Andreas, Loren B.; Pintacuda, Guido

2018-02-01

Building on a decade of continuous advances of the community, the recent development of very fast (60 kHz and above) magic-angle spinning (MAS) probes has revolutionised the field of solid-state NMR. This new spinning regime reduces the 1H-1H dipolar couplings, so that direct detection of the larger magnetic moment available from 1H is now possible at high resolution, not only in deuterated molecules but also in fully-protonated substrates. Such capabilities allow rapid "fingerprinting" of samples with a ten-fold reduction of the required sample amounts with respect to conventional approaches, and permit extensive, robust and expeditious assignment of small-to-medium sized proteins (up to ca. 300 residues), and the determination of inter-nuclear proximities, relative orientations of secondary structural elements, protein-cofactor interactions, local and global dynamics. Fast MAS and 1H detection techniques have nowadays been shown to be applicable to membrane-bound systems. This paper reviews the strategies underlying this recent leap forward in sensitivity and resolution, describing its potential for the detailed characterization of membrane proteins.

Development of DNP-Enhanced High-Resolution Solid-State NMR System for the Characterization of the Surface Structure of Polymer Materials

NASA Astrophysics Data System (ADS)

Horii, Fumitaka; Idehara, Toshitaka; Fujii, Yutaka; Ogawa, Isamu; Horii, Akifumi; Entzminger, George; Doty, F. David

2012-07-01

A dynamic nuclear polarization (DNP)-enhanced cross-polarization/magic-angle spinning (DNP/CP/MAS) NMR system has been developed by combining a 200 MHz Chemagnetics CMX-200 spectrometer operating at 4.7 T with a high-power 131.5 GHz Gyrotron FU CW IV. The 30 W sub-THz wave generated in a long pulse TE _{{41}}^{{(1)}} mode with a frequency of 5 Hz was successfully transmitted to the modified Doty Scientific low-temperature CP/MAS probe through copper smooth-wall circular waveguides. Since serious RF noises on NMR signals by arcing in the electric circuit of the probe and undesired sample heating were induced by the continuous sub-THz wave pulse irradiation with higher powers, the on-off sub-THz wave pulse irradiation synchronized with the NMR detection was developed and the appropriate setting of the irradiation time and the cooling time corresponding to the non-irradiation time was found to be very effective for the suppression of the arcing and the sample heating. The attainable maximum DNP enhancement was more than 30 folds for C1 13 C-enriched D-glucose dissolved in the frozen medium containing mono-radical 4-amino-TEMPO. The first DNP/CP/MAS 13 C NMR spectra of poly(methyl methacrylate) (PMMA) sub-micron particles were obtained at the dispersed state in the same frozen medium, indicating that DNP-enhanced 1H spins effectively diffuse from the medium to the PMMA particles through their surface and are detected as high-resolution 13 C spectra in the surficial region to which the 1H spins reach. On the basis of these results, the possibility of the DNP/CP/MAS NMR characterization of the surface structure of nanomaterials including polymer materials was discussed.

Verdazyl-ribose: A new radical for solid-state dynamic nuclear polarization at high magnetic field.

PubMed

Thurber, Kent R; Le, Thanh-Ngoc; Changcoco, Victor; Brook, David J R

2018-04-01

Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13 C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T 1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14 N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants. Published by Elsevier Inc.

Spatial reorientation experiments for NMR of solids and partially oriented liquids.

PubMed

Martin, Rachel W; Kelly, John E; Collier, Kelsey A

2015-11-01

Motional reorientation experiments are extensions of Magic Angle Spinning (MAS) where the rotor axis is changed in order to average out, reintroduce, or scale anisotropic interactions (e.g. dipolar couplings, quadrupolar interactions or chemical shift anisotropies). This review focuses on Variable Angle Spinning (VAS), Switched Angle Spinning (SAS), and Dynamic Angle Spinning (DAS), all of which involve spinning at two or more different angles sequentially, either in successive experiments or during a multidimensional experiment. In all of these experiments, anisotropic terms in the Hamiltonian are scaled by changing the orientation of the spinning sample relative to the static magnetic field. These experiments vary in experimental complexity and instrumentation requirements. In VAS, many one-dimensional spectra are collected as a function of spinning angle. In SAS, dipolar couplings and/or chemical shift anisotropies are reintroduced by switching the sample between two different angles, often 0° or 90° and the magic angle, yielding a two-dimensional isotropic-anisotropic correlation spectrum. Dynamic Angle Spinning (DAS) is a related experiment that is used to simultaneously average out the first- and second-order quadrupolar interactions, which cannot be accomplished by spinning at any unique rotor angle in physical space. Although motional reorientation experiments generally require specialized instrumentation and data analysis schemes, some are accessible with only minor modification of standard MAS probes. In this review, the mechanics of each type of experiment are described, with representative examples. Current and historical probe and coil designs are discussed from the standpoint of how each one accomplishes the particular objectives of the experiment(s) it was designed to perform. Finally, applications to inorganic materials and liquid crystals, which present very different experimental challenges, are discussed. The review concludes with perspectives on how motional reorientation experiments can be applied to current problems in chemistry, molecular biology, and materials science, given the many advances in high-field NMR magnets, fast spinning, and sample preparation realized in recent years. Copyright © 2015 Elsevier B.V. All rights reserved.

Radiofrequency fields in MAS solid state NMR probes.

PubMed

Tošner, Zdeněk; Purea, Armin; Struppe, Jochem O; Wegner, Sebastian; Engelke, Frank; Glaser, Steffen J; Reif, Bernd

2017-11-01

We present a detailed analysis of the radiofrequency (RF) field over full volume of a rotor that is generated in a solenoid coil. On top of the usually considered static distribution of amplitudes along the coil axis we describe dynamic radial RF inhomogeneities induced by sample rotation. During magic angle spinning (MAS), the mechanical rotation of the sample about the magic angle, a spin packet travels through areas of different RF fields and experiences periodical modulations of both the RF amplitude and the phase. These modulations become particularly severe at the end regions of the coil where the relative RF amplitude varies up to ±25% and the RF phase changes within ±30°. Using extensive numerical simulations we demonstrate effects of RF inhomogeneity on pulse calibration and for the ramped CP experiment performed at a wide range of MAS rates. In addition, we review various methods to map RF fields using a B 0 gradient along the sample (rotor axis) for imaging purposes. Under such a gradient, a nutation experiment provides directly the RF amplitude distribution, a cross polarization experiment images the correlation of the RF fields on the two channels according to the Hartmann-Hahn matching condition, while a spin-lock experiment allows to calibrate the RF amplitude employing the rotary resonance recoupling condition. Knowledge of the RF field distribution in a coil provides key to understand its effects on performance of a pulse sequence at the spectrometer and enables to set robustness requirements in the experimental design. Copyright © 2017 Elsevier Inc. All rights reserved.

An HR-MAS MR Metabolomics Study on Breast Tissues Obtained with Core Needle Biopsy

PubMed Central

Cho, Nariya; Chang, Jung Min; Koo, Hye Ryoung; Yi, Ann; Kim, Hyeonjin; Park, Sunghyouk; Moon, Woo Kyung

2011-01-01

Background Much research has been devoted to the development of new breast cancer diagnostic measures, including those involving high-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopic techniques. Previous HR-MAS MR results have been obtained from post-surgery samples, which limits their direct clinical applicability. Methodology/Principal Findings In the present study, we performed HR-MAS MR spectroscopic studies on 31 breast tissue samples (13 cancer and 18 non-cancer) obtained by percutaneous core needle biopsy. We showed that cancer and non-cancer samples can be discriminated very well with Orthogonal Projections to Latent Structure-Discriminant Analysis (OPLS-DA) multivariate model on the MR spectra. A subsequent blind test showed 69% sensitivity and 94% specificity in the prediction of the cancer status. A spectral analysis showed that in cancer cells, taurine- and choline-containing compounds are elevated. Our approach, additionally, could predict the progesterone receptor statuses of the cancer patients. Conclusions/Significance HR-MAS MR metabolomics on intact breast tissues obtained by core needle biopsy may have a potential to be used as a complement to the current diagnostic and prognostic measures for breast cancers. PMID:22028780

Singularities in the lineshape of a second-order perturbed quadrupolar nucleus. The magic-angle spinning case.

PubMed

Field, Timothy R; Bain, Alex D

2014-01-01

For a nucleus with a half-integral spin and a strong quadrupole coupling, the central transition (from magnetic quantum number -1/2 to +1/2) in the spectrum shows a characteristic lineshape. By strong coupling, we mean an interaction strong enough so that second-order perturbation theory is needed, yet still sufficient. The spectrum of a static sample is well-known and the magic-angle-spinning (MAS spectrum) is different, but still can be calculated. The important features of both these spectra are singularities and steps in the lineshape, since these are the main tools in fitting the calculated spectrum to experimental data. A useful tool in this investigation is a plot of the frequency as a function of orientation over the surface of the unit sphere. These plots have maxima, minima and saddle points, and these correspond to the features of the spectrum. We used these plots to define both the positions and derive new formulae for the heights of the features and we now extend this to the magic-angle spinning case. For the first time, we identify the orientations corresponding to the features of the MAS spectra and derive formulae for the heights. We then compare the static and MAS cases and show the relationships between the features in the two spectra. Copyright © 2014 Elsevier Inc. All rights reserved.

35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients

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

Hirsh, David A.; Rossini, Aaron J.; Emsley, Lyndon

In this paper, we show how to obtain efficient dynamic nuclear polarization (DNP) enhanced 35Cl solid-state NMR (SSNMR) spectra at 9.4 T and demonstrate how they can be used to characterize the molecular-level structure of hydrochloride salts of active pharmaceutical ingredients (APIs) in both bulk and low wt% API dosage forms. 35Cl SSNMR central-transition powder patterns of chloride ions are typically tens to hundreds of kHz in breadth, and most cannot be excited uniformly with high-power rectangular pulses or acquired under conditions of magic-angle spinning (MAS). Herein, we demonstrate the combination of DNP and 1H– 35Cl broadband adiabatic inversion crossmore » polarization (BRAIN-CP) experiments for the acquisition of high quality wideline spectra of APIs under static sample conditions, and obtain signals up to 50 times greater than in spectra acquired without the use of DNP at 100 K. We report a new protocol, called spinning-on spinning-off (SOSO) acquisition, where MAS is applied during part of the polarization delay to increase the DNP enhancements and then the MAS rotation is stopped so that a wideline 35Cl NMR powder pattern free from the effects of spinning sidebands can be acquired under static conditions. This method provides an additional two-fold signal enhancement compared to DNP-enhanced SSNMR spectra acquired under purely static conditions. DNP-enhanced 35Cl experiments are used to characterize APIs in bulk and dosage forms with Cl contents as low as 0.45 wt%. These results are compared to DNP-enhanced 1H– 13C CP/MAS spectra of APIs in dosage forms, which are often hindered by interfering signals arising from the binders, fillers and other excipient materials.« less

35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients

DOE PAGES

Hirsh, David A.; Rossini, Aaron J.; Emsley, Lyndon; ...

2016-08-24

In this paper, we show how to obtain efficient dynamic nuclear polarization (DNP) enhanced 35Cl solid-state NMR (SSNMR) spectra at 9.4 T and demonstrate how they can be used to characterize the molecular-level structure of hydrochloride salts of active pharmaceutical ingredients (APIs) in both bulk and low wt% API dosage forms. 35Cl SSNMR central-transition powder patterns of chloride ions are typically tens to hundreds of kHz in breadth, and most cannot be excited uniformly with high-power rectangular pulses or acquired under conditions of magic-angle spinning (MAS). Herein, we demonstrate the combination of DNP and 1H– 35Cl broadband adiabatic inversion crossmore » polarization (BRAIN-CP) experiments for the acquisition of high quality wideline spectra of APIs under static sample conditions, and obtain signals up to 50 times greater than in spectra acquired without the use of DNP at 100 K. We report a new protocol, called spinning-on spinning-off (SOSO) acquisition, where MAS is applied during part of the polarization delay to increase the DNP enhancements and then the MAS rotation is stopped so that a wideline 35Cl NMR powder pattern free from the effects of spinning sidebands can be acquired under static conditions. This method provides an additional two-fold signal enhancement compared to DNP-enhanced SSNMR spectra acquired under purely static conditions. DNP-enhanced 35Cl experiments are used to characterize APIs in bulk and dosage forms with Cl contents as low as 0.45 wt%. These results are compared to DNP-enhanced 1H– 13C CP/MAS spectra of APIs in dosage forms, which are often hindered by interfering signals arising from the binders, fillers and other excipient materials.« less

Natural abundance high-resolution solid state 2 H NMR spectroscopy

NASA Astrophysics Data System (ADS)

Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

1994-08-01

We report for the first time an approach for natural abundance solid state 2 H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1 H decoupling (HPPD) and 1 H- 2 H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2 H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2 H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1 H to 2 H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

Natural abundance high-resolution solid state 2 H NMR spectroscopy

NASA Astrophysics Data System (ADS)

Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

1994-08-01

We report for the first time an approach for natural abundance solid state 2H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1H decoupling (HPPD) and 1H- 2H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1H to 2H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

Fluid flow dynamics in MAS systems

NASA Astrophysics Data System (ADS)

Wilhelm, Dirk; Purea, Armin; Engelke, Frank

2015-08-01

The turbine system and the radial bearing of a high performance magic angle spinning (MAS) probe with 1.3 mm-rotor diameter has been analyzed for spinning rates up to 67 kHz. We focused mainly on the fluid flow properties of the MAS system. Therefore, computational fluid dynamics (CFD) simulations and fluid measurements of the turbine and the radial bearings have been performed. CFD simulation and measurement results of the 1.3 mm-MAS rotor system show relatively low efficiency (about 25%) compared to standard turbo machines outside the realm of MAS. However, in particular, MAS turbines are mainly optimized for speed and stability instead of efficiency. We have compared MAS systems for rotor diameter of 1.3-7 mm converted to dimensionless values with classical turbomachinery systems showing that the operation parameters (rotor diameter, inlet mass flow, spinning rate) are in the favorable range. This dimensionless analysis also supports radial turbines for low speed MAS probes and diagonal turbines for high speed MAS probes. Consequently, a change from Pelton type MAS turbines to diagonal turbines might be worth considering for high speed applications. CFD simulations of the radial bearings have been compared with basic theoretical values proposing considerably smaller frictional loss values. The discrepancies might be due to the simple linear flow profile employed for the theoretical model. Frictional losses generated inside the radial bearings result in undesired heat-up of the rotor. The rotor surface temperature distribution computed by CFD simulations show a large temperature gradient over the rotor.

Frequency swept microwaves for hyperfine decoupling and time domain dynamic nuclear polarization

PubMed Central

Hoff, Daniel E.M.; Albert, Brice J.; Saliba, Edward P.; Scott, Faith J.; Choi, Eric J.; Mardini, Michael; Barnes, Alexander B.

2015-01-01

Hyperfine decoupling and pulsed dynamic nuclear polarization (DNP) are promising techniques to improve high field DNP NMR. We explore experimental and theoretical considerations to implement them with magic angle spinning (MAS). Microwave field simulations using the high frequency structural simulator (HFSS) software suite are performed to characterize the inhomogeneous phase independent microwave field throughout a 198 GHz MAS DNP probe. Our calculations show that a microwave power input of 17 W is required to generate an average EPR nutation frequency of 0.84 MHz. We also present a detailed calculation of microwave heating from the HFSS parameters and find that 7.1% of the incident microwave power contributes to dielectric sample heating. Voltage tunable gyrotron oscillators are proposed as a class of frequency agile microwave sources to generate microwave frequency sweeps required for the frequency modulated cross effect, electron spin inversions, and hyperfine decoupling. Electron spin inversions of stable organic radicals are simulated with SPINEVOLUTION using the inhomogeneous microwave fields calculated by HFSS. We calculate an electron spin inversion efficiency of 56% at a spinning frequency of 5 kHz. Finally, we demonstrate gyrotron acceleration potentials required to generate swept microwave frequency profiles for the frequency modulated cross effect and electron spin inversions. PMID:26482131

Frequency swept microwaves for hyperfine decoupling and time domain dynamic nuclear polarization.

PubMed

Hoff, Daniel E M; Albert, Brice J; Saliba, Edward P; Scott, Faith J; Choi, Eric J; Mardini, Michael; Barnes, Alexander B

2015-11-01

Hyperfine decoupling and pulsed dynamic nuclear polarization (DNP) are promising techniques to improve high field DNP NMR. We explore experimental and theoretical considerations to implement them with magic angle spinning (MAS). Microwave field simulations using the high frequency structural simulator (HFSS) software suite are performed to characterize the inhomogeneous phase independent microwave field throughout a 198GHz MAS DNP probe. Our calculations show that a microwave power input of 17W is required to generate an average EPR nutation frequency of 0.84MHz. We also present a detailed calculation of microwave heating from the HFSS parameters and find that 7.1% of the incident microwave power contributes to dielectric sample heating. Voltage tunable gyrotron oscillators are proposed as a class of frequency agile microwave sources to generate microwave frequency sweeps required for the frequency modulated cross effect, electron spin inversions, and hyperfine decoupling. Electron spin inversions of stable organic radicals are simulated with SPINEVOLUTION using the inhomogeneous microwave fields calculated by HFSS. We calculate an electron spin inversion efficiency of 56% at a spinning frequency of 5kHz. Finally, we demonstrate gyrotron acceleration potentials required to generate swept microwave frequency profiles for the frequency modulated cross effect and electron spin inversions. Copyright © 2015 Elsevier Inc. All rights reserved.

Dynamic Nuclear Polarization and other magnetic ideas at EPFL.

PubMed

Bornet, Aurélien; Milani, Jonas; Wang, Shutao; Mammoli, Daniele; Buratto, Roberto; Salvi, Nicola; Segaw, Takuya F; Vitzthum, Veronika; Miéville, Pascal; Chinthalapalli, Srinivas; Perez-Linde, Angel J; Carnevale, Diego; Jannin, Sami; Caporinia, Marc; Ulzega, Simone; Rey, Martial; Bodenhausen, Geoffrey

2012-01-01

Although nuclear magnetic resonance (NMR) can provide a wealth of information, it often suffers from a lack of sensitivity. Dynamic Nuclear Polarization (DNP) provides a way to increase the polarization and hence the signal intensities in NMR spectra by transferring the favourable electron spin polarization of paramagnetic centres to the surrounding nuclear spins through appropriate microwave irradiation. In our group at EPFL, two complementary DNP techniques are under investigation: the combination of DNP with magic angle spinning at temperatures near 100 K ('MAS-DNP'), and the combination of DNP at 1.2 K with rapid heating followed by the transfer of the sample to a high-resolution magnet ('dissolution DNP'). Recent applications of MAS-DNP to surfaces, as well as new developments of magnetization transfer of (1)H to (13)C at 1.2 K prior to dissolution will illustrate the work performed in our group. A second part of the paper will give an overview of some 'non-enhanced' activities of our laboratory in liquid- and solid-state NMR.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

19F and 31P magic-angle spinning nuclear magnetic resonance of antimony(III)-doped fluorapatite phosphors: Dopant sites and spin diffusion

NASA Astrophysics Data System (ADS)

Moran, Liam B.; Berkowitz, Jeffery K.; Yesinowski, James P.

1992-03-01

Phosphors based on calcium fluorapatite [Ca5F(PO4)3] doped with small amounts of Sb3+ as an activator are used in most fluorescent lamps. We have used quantitative 19F and 31P magic-angle spinning nuclear magnetic resonance (MAS-NMR) to study seven samples of calcium fluorapatite containing 0.0-3.0 wt % Sb3+ in order to determine the site of antimony substitution. The 31P MAS-NMR spectra of fluorapatite containing 3.0, 2.1, and 1.3 wt % antimony contain a single sharp peak at 2.8 ppm indistinguishable from undoped fluorapatite, and show no additional peaks attributable to the influence of antimony. The 31P MAS-NMR spectra of the model compounds SbPO4, Sr1.03Ca8.97F2(PO4)6, Sr5F(PO4)3, and Ba5F(PO4)3 were also obtained. The 19F MAS-NMR spectra of the antimony-doped samples exhibit, in addition to the main peak at 64.0 ppm (downfield from C6F6) arising from unperturbed fluorapatite, a shoulder at 65.6 ppm, and a sharp peak at 68.6 ppm. The measured spin-lattice relaxation times T1 of these antimony-related peaks are equal in all cases to that of the main peak in a given sample, and vary from 129 to 378 sec, indicating that these peaks arise from apatitic fluoride ions perturbed by antimony. Quantitative studies reveal that the 68.6-ppm peak arises from two fluoride ions and the 65.6-ppm shoulder from one fluoride ion per Sb3+ ion incorporated into the lattice. The selective population anti-z and rate of transfer to adjacent nuclei (SPARTAN) pulse sequence used to measure spin diffusion by selectively inverting the 68.6-ppm peak reveals the presence of cross-relaxation to the main peak at 64.0 ppm, but not to the shoulder at 65.6 ppm. Each Sb3+ ion thus appears to be perturbing fluoride ions in at least two different chains. An additional peak at 73.1 ppm observed in some samples is assigned to a second type of antimony(III) substitution, with a single fluoride ion perturbed by each antimony ion. The results in total provide detailed support for a substitution model in which antimony(III) occupies a phosphate site in the apatite lattice, with a SbO3-3 group replacing a PO3-4 group. Two types of substitution at this site appear to occur, depending upon which oxygen atom is replaced by the antimony lone electron pair.

Size dependence of magnetization switching and its dispersion of Co/Pt nanodots under the assistance of radio frequency fields

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

Furuta, Masaki, E-mail: furutam@mail.tagen.tohoku.ac.jp; Okamoto, Satoshi; Kikuchi, Nobuaki

2014-04-07

We have studied the dot size dependence of microwave assisted magnetization switching (MAS) on perpendicular magnetic Co/Pt multilayer dot array. The significant microwave assistance effect has been observed over the entire dot size D ranging from 50 nm to 330 nm examined in the present study. The MAS behavior, however, critically depends on D. The excitation frequency dependence of the switching field is well consistent with the spin wave theory, indicating that the magnetization precession in MAS is in accordance with the well defined eigenmodes depending on the dot diameter. The lowest order spin wave is only excited for D ≤ 100 nm, and thenmore » the MAS effect is well consistent with that of the single macrospin prediction. On the other hand, higher order spin waves are excited for D > 100 nm, giving rise to the significant enhancement of the MAS effect. The dispersion of MAS effect also depends on D and is significantly reduced for the region of D > 100 nm. This significant reduction of the dispersion is attributed to the essential feature of the MAS effect which is insensitive to the local fluctuation of anisotropy field, such as defect, damaged layer, and so on.« less

Fluid flow dynamics in MAS systems.

PubMed

Wilhelm, Dirk; Purea, Armin; Engelke, Frank

2015-08-01

The turbine system and the radial bearing of a high performance magic angle spinning (MAS) probe with 1.3mm-rotor diameter has been analyzed for spinning rates up to 67kHz. We focused mainly on the fluid flow properties of the MAS system. Therefore, computational fluid dynamics (CFD) simulations and fluid measurements of the turbine and the radial bearings have been performed. CFD simulation and measurement results of the 1.3mm-MAS rotor system show relatively low efficiency (about 25%) compared to standard turbo machines outside the realm of MAS. However, in particular, MAS turbines are mainly optimized for speed and stability instead of efficiency. We have compared MAS systems for rotor diameter of 1.3-7mm converted to dimensionless values with classical turbomachinery systems showing that the operation parameters (rotor diameter, inlet mass flow, spinning rate) are in the favorable range. This dimensionless analysis also supports radial turbines for low speed MAS probes and diagonal turbines for high speed MAS probes. Consequently, a change from Pelton type MAS turbines to diagonal turbines might be worth considering for high speed applications. CFD simulations of the radial bearings have been compared with basic theoretical values proposing considerably smaller frictional loss values. The discrepancies might be due to the simple linear flow profile employed for the theoretical model. Frictional losses generated inside the radial bearings result in undesired heat-up of the rotor. The rotor surface temperature distribution computed by CFD simulations show a large temperature gradient over the rotor. Copyright © 2015 Elsevier Inc. All rights reserved.

Solid state nuclear magnetic resonance investigation of polymer backbone dynamics in poly(ethylene oxide) based lithium and sodium polyether-ester-sulfonate ionomers.

PubMed

Roach, David J; Dou, Shichen; Colby, Ralph H; Mueller, Karl T

2013-05-21

Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T(g)) have been investigated using solid-state nuclear magnetic resonance. Experiments detecting (13)C with (1)H decoupling under magic angle spinning (MAS) conditions identified the different components of the polymer backbone (PEO spacer and isophthalate groups) and their relative mobilities for a suite of lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) (1)H-(13)C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content and identity. Each of the main backbone components exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and (1)H spin-lattice relaxation rate measurements. Previous (1)H and (7)Li spin-lattice relaxation measurements focused on both the polymer backbone and cation motion on the nanosecond timescale. The studies presented here assess the slower timescale motion of the polymer backbone allowing for a more comprehensive understanding of the polymer dynamics. The temperature dependences of (13)C linewidths were used to both qualitatively and quantitatively examine the effects of cation content and identity on PEO spacer mobility. Variable contact time (1)H-(13)C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, reported via the rate of magnetization transfer from (1)H to (13)C nuclei, becomes similar for T≳1.1 T(g) in all ionic samples, indicating that at similar elevated reduced temperatures the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results present an improved picture, beyond those of previous findings, for the dependence of backbone dynamics on cation density (and here, cation identity as well) in these amorphous PEO-based ionomer systems.

Indirect detection of infinite-speed MAS solid-state NMR spectra

NASA Astrophysics Data System (ADS)

Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; Goh, Tian Wei; Huang, Wenyu; Rossini, Aaron J.; Pruski, Marek

2017-03-01

Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic "infinite-MAS" spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.

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

PubMed

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

2015-11-01

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

RNA Characterization by Solid-State NMR Spectroscopy.

PubMed

Yang, Yufei; Wang, Shenlin

2018-06-21

The structures of RNAs, which play critical roles in various biological processes, provide important clues and insights into the biological functions of these molecules. However, RNA structure determination remains a challenging topic. In recent years, magic-angle-spinning solid-state NMR (MAS SSNMR) has emerged as an alternative technique for structural and dynamic characterization of RNA. MAS SSNMR has been successfully applied to provide atomic-level structural information about several RNA molecules and RNA-protein complexes. In this Minireview, we give an overview of recent progress in the field of MAS SSNMR based RNA structural characterization, and introduce sample preparation strategies and SSNMR spectroscopic techniques that have been incorporated to identify RNA structural elements. We also highlight a few impressive examples of RNAs that have been investigated extensively by SSNMR. Finally, we briefly discuss future technical trends in the use of MAS SSNMR to facilitate RNA structure determination. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of HR MAS MR spectroscopic profiles of breast cancer tissue with clinical parameters.

PubMed

Sitter, Beathe; Lundgren, Steinar; Bathen, Tone F; Halgunset, Jostein; Fjosne, Hans E; Gribbestad, Ingrid S

2006-02-01

Breast cancer is the most frequent form of cancer in women and improved diagnostic methods are desirable. Malignant cells have altered metabolism and metabolic mapping might become a tool in cancer diagnostics. High-resolution magic angle spinning (HR MAS) MR spectroscopy of tissue biopsies provides detailed information on metabolic composition. The 600 MHz 1H HR MAS spectra were acquired of breast cancer tissue from 85 patients and adjacent non-involved tissue from 18 of these patients. Tissue specimens were investigated by microscopy after MR analysis. The resulting spectra were examined by three different approaches. Relative intensities of glycerophosphocholine (GPC), phosphocholine (PC) and choline were compared for cancerous and non-involved specimens. Eight metabolites, choline, creatine, beta-glucose, GPC, glycine, myo-inositol, PC and taurine, were quantified from the recorded spectra and compared with tumor histological type and size, patient's lymph node status and tissue composition of sample. The spectra were also compared with tumor histological type and size, lymph node status and tissue composition of samples using principal component analysis (PCA). Tumor samples could be distinguished from non-involved samples (82% sensitivity, 100% specificity) based on relative intensities of signals from GPC, PC and choline in 1H HR MAS spectra. Tissue concentrations of metabolites showed few differences between groups of samples, which can be caused by limitations in the quantification procedure. Choline and glycine concentrations were found to be significantly higher in tumors larger than 2 cm compared with smaller tumors. PCA of MAS spectra from patients with invasive ductal carcinomas indicated a possible prediction of spread to axillary lymph nodes. Metabolite estimates and PCA of MAS spectra were influenced by the percentage of tumor cells in the investigated specimens. 2006 John Wiley & Sons, Ltd.

A LOW-E MAGIC ANGLE SPINNING PROBE FOR BIOLOGICAL SOLID STATE NMR AT 750 MHz

PubMed Central

McNeill, Seth A.; Gor’kov, Peter L.; Shetty, Kiran; Brey, William W.; Long, Joanna R.

2009-01-01

Crossed-coil NMR probes are a useful tool for reducing sample heating for biological solid state NMR. In a crossed-coil probe, the higher frequency 1H field, which is the primary source of sample heating in conventional probes, is produced by a separate low-inductance resonator. Because a smaller driving voltage is required, the electric field across the sample and the resultant heating is reduced. In this work we describe the development of a magic angle spinning (MAS) solid state NMR probe utilizing a dual resonator. This dual resonator approach, referred to as “Low-E,” was originally developed to reduce heating in samples of mechanically aligned membranes. The study of inherently dilute systems, such as proteins in lipid bilayers, via MAS techniques requires large sample volumes at high field to obtain spectra with adequate signal-to-noise ratio under physiologically relevant conditions. With the Low-E approach, we are able to obtain homogeneous and sufficiently strong radiofrequency fields for both 1H and 13C frequencies in a 4 mm probe with a 1H frequency of 750 MHz. The performance of the probe using windowless dipolar recoupling sequences is demonstrated on model compounds as well as membrane embedded peptides. PMID:19138870

Heteronuclear Correlation SSNMR Spectroscopy with Indirect Detection under Fast Magic-Angle Spinning [Book Chapter

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

Kobayshi, Takeshi; Nishiyama, Yusuke; Pruski, Marek

The main focus of this chapter is to address experimental strategies on the subject by providing a hands-on guide to fast MAS experiments, with a particular focus on indirect detection. Although our experience is limited to our respective laboratories in Ames and Yokohama, we hope that our descriptions of experimental setups and optimization procedures are sufficiently general to be applicable to all modern instruments. The chapter is organized as follows. Section 2 below introduces briefly the fast MAS technology and its main advantages. In Section 3, we describe the hardware associated with this remarkable technology and provide practical advices onmore » its use, including procedures for loading and unloading the samples, maintaining the probe, reducing t 1 noise, etc. In Section 4, we describe the principles and hands-on aspects of experiments involving the indirect detection of spin-1/2 and 14N nuclei« less

Ramped-Amplitude Cross Polarization in Magic-Angle-Spinning NMR

NASA Astrophysics Data System (ADS)

Metz, G.; Wu, X. L.; Smith, S. O.

The Hartmann-Hahn matching profile in CP-MAS NMR shows a strong mismatch dependence if the MAS frequency is on the order of the dipolar couplings in the sample. Under these conditions, the profile breaks down into a series of narrow matching bands separated by the spinning speed, and it becomes difficult to establish and maintain an efficient matching condition. Variable-amplitude CP (VACP), as introduced previously (Peersen et al., J. Magn. Reson. A104, 334, 1993), has been proven to be effective for restoring flat profiles at high spinning speeds. Here, a refined implementation of VACP using a ramped-amplitude cross-polarization sequence (RAMP-CP) is described. The order of the amplitude modulation is shown to be of importance for the cross-polarization process. The new pulse sequence with a linear amplitude ramp is not only easier to set up but also improves the performance of the variable-amplitude experiment in that it produces flat profiles over a wider range of matching conditions even with short total contact times. An increase in signal intensity is obtained compared to both con ventional CP and the originally proposed VACP sequence.

Sealed rotors for in situ high temperature high pressure MAS NMR

DOE PAGES

Hu, Jian Z.; Hu, Mary Y.; Zhao, Zhenchao; ...

2015-07-06

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) investigations on heterogeneous samples containing solids, semi-solids, liquid and gases or a mixture of them under non-conventional conditions of a combined high pressure and high temperature, or cold temperature suffer from the unavailability of a perfectly sealed rotor. Here, we report the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are easy to use and are suitable for operation temperatures from below 0 to 250 °C and pressures up to 100 bar. As an example of potential applications we performed in situ MAS NMR investigations of AlPO₄-5 molecular sieve crystallization,more » a kinetic study of the cyclohexanol dehydration reaction using 13C MAS NMR, and an investigation of the metabolomics of intact biological tissue at low temperature using 1H HR-MAS NMR spectroscopy. The in situ MAS NMR experiments performed using the reported rotors allowed reproduction of the results from traditional batch reactions, while offering more detailed quantitative information at the molecular level, as demonstrated for the molecular sieve synthesis and activation energy measurements for cyclohexanol dehydration. The perfectly sealed rotor also shows promising application for metabolomics studies using 1H HR-MAS NMR.« less

Sealed rotors for in situ high temperature high pressure MAS NMR

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

Hu, Jian Z.; Hu, Mary Y.; Zhao, Zhenchao

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) investigations on heterogeneous samples containing solids, semi-solids, liquid and gases or a mixture of them under non-conventional conditions of a combined high pressure and high temperature, or cold temperature suffer from the unavailability of a perfectly sealed rotor. Here, we report the design of reusable and perfectly-sealed all-zircornia MAS rotors. The rotors are easy to use and are suitable for operation temperatures from below 0 to 250 °C and pressures up to 100 bar. As an example of potential applications we performed in situ MAS NMR investigations of AlPO₄-5 molecular sieve crystallization,more » a kinetic study of the cyclohexanol dehydration reaction using 13C MAS NMR, and an investigation of the metabolomics of intact biological tissue at low temperature using 1H HR-MAS NMR spectroscopy. The in situ MAS NMR experiments performed using the reported rotors allowed reproduction of the results from traditional batch reactions, while offering more detailed quantitative information at the molecular level, as demonstrated for the molecular sieve synthesis and activation energy measurements for cyclohexanol dehydration. The perfectly sealed rotor also shows promising application for metabolomics studies using 1H HR-MAS NMR.« less

(1)H-(13)C Hetero-nuclear dipole-dipole couplings of methyl groups in stationary and magic angle spinning solid-state NMR experiments of peptides and proteins.

PubMed

Wu, Chin H; Das, Bibhuti B; Opella, Stanley J

2010-02-01

(13)C NMR of isotopically labeled methyl groups has the potential to combine spectroscopic simplicity with ease of labeling for protein NMR studies. However, in most high resolution separated local field experiments, such as polarization inversion spin exchange at the magic angle (PISEMA), that are used to measure (1)H-(13)C hetero-nuclear dipolar couplings, the four-spin system of the methyl group presents complications. In this study, the properties of the (1)H-(13)C hetero-nuclear dipolar interactions of (13)C-labeled methyl groups are revealed through solid-state NMR experiments on a range of samples, including single crystals, stationary powders, and magic angle spinning of powders, of (13)C(3) labeled alanine alone and incorporated into a protein. The spectral simplifications resulting from proton detected local field (PDLF) experiments are shown to enhance resolution and simplify the interpretation of results on single crystals, magnetically aligned samples, and powders. The complementarity of stationary sample and magic angle spinning (MAS) measurements of dipolar couplings is demonstrated by applying polarization inversion spin exchange at the magic angle and magic angle spinning (PISEMAMAS) to unoriented samples. Copyright 2009 Elsevier Inc. All rights reserved.

Ibuprofen in mesopores of Mobil Crystalline Material 41 (MCM-41): a deeper understanding.

PubMed

Skorupska, Ewa; Jeziorna, Agata; Paluch, Piotr; Potrzebowski, Marek J

2014-05-05

In this work, we compared two methods (incipient wetness and melting) for the encapsulation of ibuprofen in the pores of Mobil Crystalline Material 41 (MCM-41) through NMR (nuclear magnetic resonance) spectroscopy. (1)H NMR spectra were recorded under very fast MAS (sample spinning 60 kHz) conditions in both 1D and 2D mode (NOESY sequence). We also performed (13)C cross-polarization magic angle spinning (CP/MAS) experiments, (13)C single pulse experiments (SPE), and (1)H-(13)C HSQC HR/MAS (heteronuclear single quantum coherence high resolution) HR/MAS correlations. Evaluation of the encapsulation methods included an analysis of the filling factor of the drug into the pores. The stability of Ibu/MCM in an environment of ethanol or water vapor was tested. Our study showed that melting a mixture of Ibu and MCM is a much more efficient method of confining the drug in the pores compared to incipient wetness. The optimal experiments for the former method achieved a filling factor of approximately 60%. We concluded that the major limitation to the applicability of the incipient wetness method (filling factor ca. 20%) is the high affinity of solvent (typically ethanol) for MCM-41. We found that even ethanol vapor can remove Ibu from the pores. When a sample of Ibu/MCM was stored for a few hours in a closed vessel with ethanol vapor, Ibu was transported from the pores to the outer walls of MCM. We observed a similar phenomenon with water vapor, although this process is slower compared to the analogous procedure using ethanol. Our study clearly demonstrates that existing methods used to encapsulate drugs in mesoporous silica nanoparticles (MSNs) require reevaluation.

Solid State NMR Studies of the Aluminum Hydride Phases

NASA Technical Reports Server (NTRS)

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

2006-01-01

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.

Principal component analysis for the comparison of metabolic profiles from human rectal cancer biopsies and colorectal xenografts using high-resolution magic angle spinning 1H magnetic resonance spectroscopy

PubMed Central

Seierstad, Therese; Røe, Kathrine; Sitter, Beathe; Halgunset, Jostein; Flatmark, Kjersti; Ree, Anne H; Olsen, Dag Rune; Gribbestad, Ingrid S; Bathen, Tone F

2008-01-01

Background This study was conducted in order to elucidate metabolic differences between human rectal cancer biopsies and colorectal HT29, HCT116 and SW620 xenografts by using high-resolution magnetic angle spinning (MAS) magnetic resonance spectroscopy (MRS) and for determination of the most appropriate human rectal xenograft model for preclinical MR spectroscopy studies. A further aim was to investigate metabolic changes following irradiation of HT29 xenografts. Methods HR MAS MRS of tissue samples from xenografts and rectal biopsies were obtained with a Bruker Avance DRX600 spectrometer and analyzed using principal component analysis (PCA) and partial least square (PLS) regression analysis. Results and conclusion HR MAS MRS enabled assignment of 27 metabolites. Score plots from PCA of spin-echo and single-pulse spectra revealed separate clusters of the different xenografts and rectal biopsies, reflecting underlying differences in metabolite composition. The loading profile indicated that clustering was mainly based on differences in relative amounts of lipids, lactate and choline-containing compounds, with HT29 exhibiting the metabolic profile most similar to human rectal cancers tissue. Due to high necrotic fractions in the HT29 xenografts, radiation-induced changes were not detected when comparing spectra from untreated and irradiated HT29 xenografts. However, PLS calibration relating spectral data to the necrotic fraction revealed a significant correlation, indicating that necrotic fraction can be assessed from the MR spectra. PMID:18439252

Intratumoral Agreement of High-Resolution Magic Angle Spinning Magnetic Resonance Spectroscopic Profiles in the Metabolic Characterization of Breast Cancer

PubMed Central

Park, Vivian Youngjean; Yoon, Dahye; Koo, Ja Seung; Kim, Eun-Kyung; Kim, Seung Il; Choi, Ji Soo; Park, Seho; Park, Hyung Seok; Kim, Suhkmann; Kim, Min Jung

2016-01-01

Abstract High-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopy data may serve as a biomarker for breast cancer, with only a small volume of tissue sample required for assessment. However, previous studies utilized only a single tissue sample from each patient. The aim of this study was to investigate whether intratumoral location and biospecimen type affected the metabolic characterization of breast cancer assessed by HR-MAS MR spectroscopy This prospective study was approved by the institutional review board and informed consent was obtained. Preoperative core-needle biopsies (CNBs), central, and peripheral surgical tumor specimens were prospectively collected under ultrasound (US) guidance in 31 patients with invasive breast cancer. Specimens were assessed with HR-MAS MR spectroscopy. The reliability of metabolite concentrations was evaluated and multivariate analysis was performed according to intratumoral location and biospecimen type. There was a moderate or higher agreement between the relative concentrations of 94.3% (33 of 35) of metabolites in the center and periphery, 80.0% (28 of 35) of metabolites in the CNB and central surgical specimens, and 82.9% (29 of 35) of metabolites between all 3 specimen types. However, there was no significant agreement between the concentrations of phosphocholine (PC) and phosphoethanolamine (PE) in the center and periphery. The concentrations of several metabolites (adipate, arginine, fumarate, glutamate, PC, and PE) had no significant agreement between the CNB and central surgical specimens. In conclusion, most HR-MAS MR spectroscopic data do not differ based on intratumoral location or biospecimen type. However, some metabolites may be affected by specimen-related variables, and caution is recommended in decision-making based solely on metabolite concentrations, particularly PC and PE. Further validation through future studies is needed for the clinical implementation of these biomarkers based on data from a single tissue sample. PMID:27082613

Efficient heteronuclear decoupling in MAS solid-state NMR using non-rotor-synchronized rCW irradiation.

PubMed

Equbal, Asif; Paul, Subhradip; Mithu, Venus Singh; Madhu, P K; Nielsen, Niels Chr

2014-09-01

We present new non-rotor-synchronized variants of the recently introduced refocused continuous wave (rCW) heteronuclear decoupling method significantly improving the performance relative to the original rotor-synchronized variants. Under non-rotor-synchronized conditions the rCW decoupling sequences provide more efficient decoupling, are easier to setup, and prove more robust towards experimental parameters such as radio frequency (rf) field amplitude and spinning frequency. This is demonstrated through numerical simulations substantiated with experimental results under different sample spinning and rf field amplitude conditions for powder samples of U-(13)C-glycine and U-(13)C-L-histidine·HCl·H2O. Copyright © 2014 Elsevier Inc. All rights reserved.

Novel NMR tools to study structure and dynamics of biomembranes.

PubMed

Gawrisch, Klaus; Eldho, Nadukkudy V; Polozov, Ivan V

2002-06-01

Nuclear magnetic resonance (NMR) studies on biomembranes have benefited greatly from introduction of magic angle spinning (MAS) NMR techniques. Improvements in MAS probe technology, combined with the higher magnetic field strength of modern instruments, enables almost liquid-like resolution of lipid resonances. The cross-relaxation rates measured by nuclear Overhauser enhancement spectroscopy (NOESY) provide new insights into conformation and dynamics of lipids with atomic-scale resolution. The data reflect the tremendous motional disorder in the lipid matrix. Transfer of magnetization by spin diffusion along the proton network of lipids is of secondary relevance, even at a long NOESY mixing time of 300 ms. MAS experiments with re-coupling of anisotropic interactions, like the 13C-(1)H dipolar couplings, benefit from the excellent resolution of 13C shifts that enables assignment of the couplings to specific carbon atoms. The traditional 2H NMR experiments on deuterated lipids have higher sensitivity when conducted on oriented samples at higher magnetic field strength. A very large number of NMR parameters from lipid bilayers is now accessible, providing information about conformation and dynamics for every lipid segment. The NMR methods have the sensitivity and resolution to study lipid-protein interaction, lateral lipid organization, and the location of solvents and drugs in the lipid matrix.

Hexagonal ice in pure water and biological NMR samples.

PubMed

Bauer, Thomas; Gath, Julia; Hunkeler, Andreas; Ernst, Matthias; Böckmann, Anja; Meier, Beat H

2017-01-01

Ice, in addition to "liquid" water and protein, is an important component of protein samples for NMR spectroscopy at subfreezing temperatures but it has rarely been observed spectroscopically in this context. We characterize its spectroscopic behavior in the temperature range from 100 to 273 K, and find that it behaves like pure water ice. The interference of magic-angle spinning (MAS) as well as rf multiple-pulse sequences with Bjerrum-defect motion greatly influences the ice spectra.

Observation of NMR noise from solid samples.

PubMed

Schlagnitweit, Judith; Dumez, Jean-Nicolas; Nausner, Martin; Jerschow, Alexej; Elena-Herrmann, Bénédicte; Müller, Norbert

2010-11-01

We demonstrate that proton NMR noise signals, i.e. NMR spectra without excitation by radio frequency, can be obtained from solid samples. Experimental results are shown for static and magic-angle spinning conditions. In addition, a tuning procedure based on the probes' NMR noise characteristics and similar to the one described previously for liquids probes can also be used to optimize signal-to-noise ratios in ¹H-MAS experiments. Copyright © 2010 Elsevier Inc. All rights reserved.

NMR at Low and Ultra-Low Temperatures

PubMed Central

Tycko, Robert

2017-01-01

Conspectus Solid state nuclear magnetic resonance (NMR) measurements at low temperatures have been common in physical sciences for many years, and are becoming increasingly important in studies of biomolecular systems. This article reviews a diverse set of projects from my laboratory, dating back to the early 1990s, that illustrate the motivations for low-temperature solid state NMR, the types of information that are available from the measurements, and likely directions for future research. These projects include NMR studies of both physical and biological systems, performed at low (cooled with nitrogen, down to 77 K) and very low (cooled with helium, below 77 K) temperatures, and performed with and without magic-angle spinning (MAS). In NMR studies of physical systems, the main motivation is to study phenomena that occur only at low temperatures. Two examples from my laboratory are studies of molecular rotation and an orientational ordering in solid C60 at low temperatures and studies of unusual electronic states, called skyrmions, in two-dimensionally confined electron systems within semiconductor quantum wells. NMR measurements on quantum wells were facilitated by optical pumping of nuclear spin polarizations, a signal enhancement phenomenon that exists at very low temperatures. In studies of biomolecular systems, motivations for low-temperature NMR include suppression of molecular tumbling (thereby permitting solid state NMR measurements on soluble proteins), suppression of conformational exchange (thereby permitting quantitation of conformational distributions), and trapping of transient intermediate states in a non-equilibrium kinetic process (by rapid freeze-quenching). Solid state NMR measurements on AIDS-related peptide/antibody complexes, chemically denatured states of the model protein HP35, and a transient intermediate in the rapid folding pathway of HP35 illustrate these motivations. NMR sensitivity generally increases with decreasing sample temperature. It is therefore advantageous to go as cold as possible, particularly in studies of biomolecular systems in frozen solutions. However, solid state NMR studies of biomolecular systems generally require rapid MAS. A novel MAS NMR probe design that uses nitrogen gas for sample spinning and cold helium only for sample cooling allows a wide variety of solid state NMR measurements to be performed on biomolecular systems at 20-25 K, where signals are enhanced by factors of 12-15 relative to measurements at room temperature. MAS NMR at very low temperatures also facilitates dynamic nuclear polarization (DNP), allowing sizeable additional signal enhancements and large absolute NMR signal amplitudes to be achieved with relatively low microwave powers. Current research in my laboratory seeks to develop and exploit DNP-enhanced MAS NMR at very low temperatures, for example in studies of transient intermediates in protein folding and aggregation processes and studies of peptide/protein complexes that can be prepared only at low concentrations. PMID:23470028

Indirect detection of infinite-speed MAS solid-state NMR spectra

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

Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.

Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. In order to address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic “infinite-MAS” spectra of heavy spin-1/2more » nuclides. Furthermore, for these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.« less

Indirect detection of infinite-speed MAS solid-state NMR spectra

DOE PAGES

Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; ...

2017-01-18

Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. In order to address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic “infinite-MAS” spectra of heavy spin-1/2more » nuclides. Furthermore, for these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.« less

Dynamic Nuclear Polarization NMR in Human Cells Using Fluorescent Polarizing Agents.

PubMed

Albert, Brice J; Gao, Chukun; Sesti, Erika L; Saliba, Edward P; Alaniva, Nicholas; Scott, Faith J; Sigurdsson, Snorri Th; Barnes, Alexander B

2018-06-20

Solid-state nuclear magnetic resonance (NMR) enables atomic resolution characterization of molecular structure and dynamics within complex heterogeneous samples, but it is typically insensitive. Dynamic nuclear polarization (DNP) increases NMR signal intensity by orders of magnitude and can be performed in combination with magic angle spinning (MAS) for sensitive, high-resolution spectroscopy. Here we report MAS DNP experiments, for the first time, within intact human cells with >40-fold DNP enhancement and a sample temperature below 6 K. In addition to cryogenic MAS results below 6 K, we also show in-cell DNP enhancements of 57-fold at 90 K. In-cell DNP is demonstrated using biradicals and sterically-shielded monoradicals as polarizing agents. A novel trimodal polarizing agent is introduced for DNP, which contains a nitroxide biradical, a targeting peptide for cell penetration, and a fluorophore for subcellular localization with confocal microscopy. The fluorescent polarizing agent provides in-cell DNP enhancements of 63-fold at a concentration of 2.7 mM. These experiments pave the way for structural characterization of biomolecules in an endogenous cellular context.

Spin-locking of half-integer quadrupolar nuclei in nuclear magnetic resonance of solids: second-order quadrupolar and resonance offset effects.

PubMed

Ashbrook, Sharon E; Wimperis, Stephen

2009-11-21

Spin-locking of spin I=3/2 and I=5/2 nuclei in the presence of small resonance offset and second-order quadrupolar interactions has been investigated using both exact and approximate theoretical and experimental nuclear magnetic resonance (NMR) approaches. In the presence of second-order quadrupolar interactions, we show that the initial rapid dephasing that arises from the noncommutation of the state prepared by the first pulse and the spin-locking Hamiltonian gives rise to tensor components of the spin density matrix that are antisymmetric with respect to inversion, in addition to those symmetric with respect to inversion that are found when only a first-order quadrupolar interaction is considered. We also find that spin-locking of multiple-quantum coherence in a static solid is much more sensitive to resonance offset than that of single-quantum coherence and show that good spin-locking of multiple-quantum coherence can still be achieved if the resonance offset matches the second-order shift of the multiple-quantum coherence in the appropriate reference frame. Under magic angle spinning (MAS) conditions, and in the "adiabatic" limit, we demonstrate that rotor-driven interconversion of central-transition single- and three-quantum coherences for a spin I=3/2 nucleus can be best achieved by performing the spin-locking on resonance with the three-quantum coherence in the three-quantum frame. Finally, in the "sudden" MAS limit, we show that spin I=3/2 spin-locking behavior is generally similar to that found in static solids, except when the central-transition nutation rate matches a multiple of the MAS rate and a variety of rotary resonance phenomena are observed depending on the internal spin interactions present. This investigation should aid in the application of spin-locking techniques to multiple-quantum NMR of quadrupolar nuclei and of cross-polarization and homonuclear dipolar recoupling experiments to quadrupolar nuclei such as (7)Li, (11)B, (17)O, (23)Na, and (27)Al.

Improved background suppression in ¹H MAS NMR using composite pulses.

PubMed

Odedra, Smita; Wimperis, Stephen

2012-08-01

A well known feature of ¹H MAS NMR spectroscopy, particularly of solids where the concentration of ¹H nuclei is low, is the presence in the spectrum of a significant broad "background" signal arising from ¹H nuclei that are outside the MAS rotor and radiofrequency coil, probably located on the surfaces of the static components of the probehead. A popular method of suppressing this unwanted signal is the "depth pulse" method, consisting of a 90° pulse followed by one or two 180° pulses that are phase cycled according to the "Exorcycle" scheme, which removes signal associated with imperfect 180° pulses. Consequently, only spins in the centre of the radiofrequency coil contribute to the ¹H MAS spectrum, while those experiencing a low B₁ field outside the coil are suppressed. Although very effective at removing background signal from the spectrum, one drawback with this approach is that significant loss of the desired signal from the sample also occurs. Here we investigate the ¹H background suppression problem and, in particular, the use of novel antisymmetric passband composite pulses to replace the simple pulses in a depth pulse experiment. We show that it is possible to improve the intensity of the ¹H signals of interest while still maintaining effective background suppression. We expect that these results will be relevant to ¹H MAS NMR studies of, for example, nominally perdeuterated biological samples or nominally anhydrous inorganic materials. Copyright © 2012 Elsevier Inc. All rights reserved.

Improved background suppression in 1H MAS NMR using composite pulses

NASA Astrophysics Data System (ADS)

Odedra, Smita; Wimperis, Stephen

2012-08-01

A well known feature of 1H MAS NMR spectroscopy, particularly of solids where the concentration of 1H nuclei is low, is the presence in the spectrum of a significant broad "background" signal arising from 1H nuclei that are outside the MAS rotor and radiofrequency coil, probably located on the surfaces of the static components of the probehead. A popular method of suppressing this unwanted signal is the "depth pulse" method, consisting of a 90° pulse followed by one or two 180° pulses that are phase cycled according to the "Exorcycle" scheme, which removes signal associated with imperfect 180° pulses. Consequently, only spins in the centre of the radiofrequency coil contribute to the 1H MAS spectrum, while those experiencing a low B1 field outside the coil are suppressed. Although very effective at removing background signal from the spectrum, one drawback with this approach is that significant loss of the desired signal from the sample also occurs. Here we investigate the 1H background suppression problem and, in particular, the use of novel antisymmetric passband composite pulses to replace the simple pulses in a depth pulse experiment. We show that it is possible to improve the intensity of the 1H signals of interest while still maintaining effective background suppression. We expect that these results will be relevant to 1H MAS NMR studies of, for example, nominally perdeuterated biological samples or nominally anhydrous inorganic materials.

Optimized Spectral Editing of 13C MAS NMR Spectra of Rigid Solids Using Cross-Polarization Methods

NASA Astrophysics Data System (ADS)

Sangill, R.; Rastrupandersen, N.; Bildsoe, H.; Jakobsen, H. J.; Nielsen, N. C.

Combinations of 13C magic-angle spinning (MAS) NMR experiments employing cross polarization (CP), cross polarization-depolarization (CPD), and cross polarization-depolarization-repolarization are analyzed quantitatively to derive simple and general procedures for optimized spectral editing of 13C CP/MAS NMR spectra of rigid solids by separation of the 13C resonances into CH n subspectra ( n = 0, 1, 2, and 3). Special attention is devoted to a differentiation by CPD/MAS of CH and CH 2 resonances since these groups behave quite similarly during spin lock under Hartmann-Hahn match and are therefore generally difficult to distinguish unambiguously. A general procedure for the design of subexperiments and linear combinations of their spectra to provide optimized signal-to-noise ratios for the edited subspectra is described. The technique is illustrated by a series of edited 13C CP/MAS spectra for a number of rigid solids ranging from simple organic compounds (sucrose and l-menthol) to complex pharmaceutical products (calcipotriol monohydrate and vitamin D 3) and polymers (polypropylene, polyvinyl alcohol, polyvinyl chloride, and polystyrene).

Structural Biology of Supramolecular Assemblies by Magic Angle Spinning NMR Spectroscopy

PubMed Central

Quinn, Caitlin M.; Polenova, Tatyana

2017-01-01

In recent years, exciting developments in instrument technology and experimental methodology have advanced the field of magic angle spinning (MAS) NMR to new heights. Contemporary MAS NMR yields atomic-level insights into structure and dynamics of an astounding range of biological systems, many of which cannot be studied by other methods. With the advent of fast magic angle spinning, proton detection, and novel pulse sequences, large supramolecular assemblies, such as cytoskeletal proteins and intact viruses, are now accessible for detailed analysis. In this review, we will discuss the current MAS NMR methodologies that enable characterization of complex biomolecular systems and will present examples of applications to several classes of assemblies comprising bacterial and mammalian cytoskeleton as well as HIV-1 and bacteriophage viruses. The body of work reviewed herein is representative of the recent advancements in the field, with respect to the complexity of the systems studied, the quality of the data, and the significance to the biology. PMID:28093096

Double cross-polarization MAS NMR in the assignment of abundant-spin resonances: ¹⁹F-{²⁹Si}-¹⁹F FBCP/MAS NMR of fluoride ions incorporated in calcium silicate hydrate (C-S-H) phases.

PubMed

Tran, Thuan T; Bildsøe, Henrik; Jakobsen, Hans J; Skibsted, Jørgen

2012-08-01

A new version of the double cross-polarization MAS NMR experiment, which transfers polarization Forth and Back (FBCP) between high- and low-γ spin nuclei, is presented. The pulse sequence is demonstrated by ¹⁹F-{²⁹Si}-¹⁹F and ¹⁹F-{¹³C}-¹⁹F FBCP NMR spectra of a mixture of cuspidine (Ca₄Si₂O₇F₂) and Teflon (-CF₂-)(n). The experiment is useful for assignment of the high-γ spin resonances, as demonstrated by ¹⁹F-{²⁹Si}-¹⁹F FBCP NMR of a fluoride-containing calcium-silicate-hydrate (C-S-H) phase, where the ¹⁹F resonance from fluoride ions incorporated in the interlayer structure of the C-S-H phase is identified. Copyright © 2012 Elsevier Inc. All rights reserved.

Characterization of metabolic profile of intact non-tumor and tumor breast cells by high-resolution magic angle spinning nuclear magnetic resonance spectroscopy.

PubMed

Maria, Roberta M; Altei, Wanessa F; Andricopulo, Adriano D; Becceneri, Amanda B; Cominetti, Márcia R; Venâncio, Tiago; Colnago, Luiz A

2015-11-01

(1)H high-resolution magic angle spinning nuclear magnetic resonance ((1)H HR-MAS NMR) spectroscopy was used to analyze the metabolic profile of an intact non-tumor breast cell line (MCF-10A) and intact breast tumor cell lines (MCF-7 and MDA-MB-231). In the spectra of MCF-10A cells, six metabolites were assigned, with glucose and ethanol in higher concentrations. Fifteen metabolites were assigned in MCF-7 and MDA-MB-231 (1)H HR-MAS NMR spectra. They did not show glucose and ethanol, and the major component in both tumor cells was phosphocholine (higher in MDA-MB-231 than in MCF-7), which can be considered as a tumor biomarker of breast cancer malignant transformation. These tumor cells also show acetone signal that was higher in MDA-MB-231 cells than in MCF-7 cells. The high acetone level may be an indication of high demand for energy in MDA-MB-231 to maintain cell proliferation. The higher acetone and phosphocholine levels in MDA-MB-231 cells indicate the higher malignance of the cell line. Therefore, HR-MAS is a rapid reproducible method to study the metabolic profile of intact breast cells, with minimal sample preparation and contamination, which are critical in the analyses of slow-growth cells. Copyright © 2015 Elsevier Inc. All rights reserved.

Transport Properties of Ibuprofen Encapsulated in Cyclodextrin Nanosponge Hydrogels: A Proton HR-MAS NMR Spectroscopy Study.

PubMed

Ferro, Monica; Castiglione, Franca; Punta, Carlo; Melone, Lucio; Panzeri, Walter; Rossi, Barbara; Trotta, Francesco; Mele, Andrea

2016-08-15

The chemical cross-linking of β-cyclodextrin (β-CD) with ethylenediaminetetraacetic dianhydride (EDTA) led to branched polymers referred to as cyclodextrin nanosponges (CDNSEDTA). Two different preparations are described with 1:4 and 1:8 CD-EDTA molar ratios. The corresponding cross-linked polymers were contacted with 0.27 M aqueous solution of ibuprofen sodium salt (IP) leading to homogeneous, colorless, drug loaded hydrogels. The systems were characterized by high resolution magic angle spinning (HR-MAS) NMR spectroscopy. Pulsed field gradient spin echo (PGSE) NMR spectroscopy was used to determine the mean square displacement (MSD) of IP inside the polymeric gel at different observation times td. The data were further processed in order to study the time dependence of MSD: MSD = f(td). The proposed methodology is useful to characterize the different diffusion regimes that, in principle, the solute may experience inside the hydrogel, namely normal or anomalous diffusion. The full protocols including the polymer preparation and purification, the obtainment of drug-loaded hydrogels, the NMR sample preparation, the measurement of MSD by HR-MAS NMR spectroscopy and the final data processing to achieve the time dependence of MSD are here reported and discussed. The presented experiments represent a paradigmatic case and the data are discussed in terms of innovative approach to the characterization of the transport properties of an encapsulated guest within a polymeric host of potential application for drug delivery.

Acceleration of natural-abundance solid-state MAS NMR measurements on bone by paramagnetic relaxation from gadolinium-DTPA

NASA Astrophysics Data System (ADS)

Mroue, Kamal H.; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

2014-07-01

Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA = Diethylene triamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the 1H T1 values were calculated from data collected by 1H spin-inversion recovery method detected in natural-abundance 13C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the 1H T1 values can be successfully reduced by a factor of 3.5 using as low as 10 mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the 13C CPMAS spectra. These results obtained from 13C-detected CPMAS experiments were further confirmed using 1H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans.

Acceleration of natural-abundance solid-state MAS NMR measurements on bone by paramagnetic relaxation from gadolinium-DTPA.

PubMed

Mroue, Kamal H; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H; Morris, Michael D; Ramamoorthy, Ayyalusamy

2014-07-01

Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA=Diethylene triamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the (1)H T1 values were calculated from data collected by (1)H spin-inversion recovery method detected in natural-abundance (13)C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the (1)H T1 values can be successfully reduced by a factor of 3.5 using as low as 10mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the (13)C CPMAS spectra. These results obtained from (13)C-detected CPMAS experiments were further confirmed using (1)H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans. Copyright © 2014 Elsevier Inc. All rights reserved.

Metabolic profiling of apples from different production systems before and after controlled atmosphere (CA) storage studied by 1H high resolution-magic angle spinning (HR-MAS) NMR.

PubMed

Vermathen, Martina; Marzorati, Mattia; Diserens, Gaëlle; Baumgartner, Daniel; Good, Claudia; Gasser, Franz; Vermathen, Peter

2017-10-15

Determination of metabolic alterations in apples induced by such processes as different crop protection strategies or storage, are of interest to assess correlations with fruit quality or fruit disorders. Preliminary results proposed the metabolic discrimination of apples from organic (BIO), integrated (IP) and low-input (LI) production. To determine contributions of temporal metabolic developments and to define the type of metabolic changes during storage, 1 H high resolution-magic angle spinning (HR-MAS) NMR spectroscopy of apple pulp was performed before and after two time points of controlled atmosphere storage. Statistical analysis revealed similar metabolic changes over time for IP-, LI- and BIO-samples, mainly decreasing lipid and sucrose, and increasing fructose, glucose and acetaldehyde levels, which are potential contributors to fruit aroma. Across the production systems, BIO apples had consistently higher levels of fructose and monomeric phenolic compounds but lower levels of condensed polyphenols than LI and IP apples, while the remaining metabolites assimilated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of a 1H high-resolution magic angle spinning NMR spectroscopy procedure for free sugars quantification in intact plant tissue.

PubMed

Delgado-Goñi, Teresa; Campo, Sonia; Martín-Sitjar, Juana; Cabañas, Miquel E; San Segundo, Blanca; Arús, Carles

2013-08-01

In most plants, sucrose is the primary product of photosynthesis, the transport form of assimilated carbon, and also one of the main factors determining sweetness in fresh fruits. Traditional methods for sugar quantification (mainly sucrose, glucose and fructose) require obtaining crude plant extracts, which sometimes involve substantial sample manipulation, making the process time-consuming and increasing the risk of sample degradation. Here, we describe and validate a fast method to determine sugar content in intact plant tissue by using high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (HR-MAS NMR). The HR-MAS NMR method was used for quantifying sucrose, glucose and fructose in mesocarp tissues from melon fruits (Cucumis melo var. reticulatus and Cucumis melo var. cantalupensis). The resulting sugar content varied among individual melons, ranging from 1.4 to 7.3 g of sucrose, 0.4-2.5 g of glucose; and 0.73-2.83 g of fructose (values per 100 g fw). These values were in agreement with those described in the literature for melon fruit tissue, and no significant differences were found when comparing them with those obtained using the traditional, enzymatic procedure, on melon tissue extracts. The HR-MAS NMR method offers a fast (usually <30 min) and sensitive method for sugar quantification in intact plant tissues, it requires a small amount of tissue (typically 50 mg fw) and avoids the interferences and risks associated with obtaining plant extracts. Furthermore, this method might also allow the quantification of additional metabolites detectable in the plant tissue NMR spectrum.

CP/MAS /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

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

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1983-09-01

Solid-state cross-polarization, magic-angle sample spinning carbon-13 nuclear magnetic resonance 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.

High Frequency Dynamic Nuclear Polarization

PubMed Central

Ni, Qing Zhe; Daviso, Eugenio; Can, Thach V.; Markhasin, Evgeny; Jawla, Sudheer K.; Swager, Timothy M.; Temkin, Richard J.; Herzfeld, Judith; Griffin, Robert G.

2013-01-01

Conspectus During the three decades 1980–2010, magic angle spinning (MAS) NMR developed into the method of choice to examine many chemical, physical and biological problems. In particular, a variety of dipolar recoupling methods to measure distances and torsion angles can now constrain molecular structures to high resolution. However, applications are often limited by the low sensitivity of the experiments, due in large part to the necessity of observing spectra of low-γ nuclei such as the I = ½ species 13C or 15N. The difficulty is still greater when quadrupolar nuclei, like 17O or 27Al, are involved. This problem has stimulated efforts to increase the sensitivity of MAS experiments. A particularly powerful approach is dynamic nuclear polarization (DNP) which takes advantage of the higher equilibrium polarization of electrons (which conventionally manifests in the great sensitivity advantage of EPR over NMR). In DNP, the sample is doped with a stable paramagnetic polarizing agent and irradiated with microwaves to transfer the high polarization in the electron spin reservoir to the nuclei of interest. The idea was first explored by Overhauser and Slichter in 1953. However, these experiments were carried out on static samples, at magnetic fields that are low by current standards. To be implemented in contemporary MAS NMR experiments, DNP requires microwave sources operating in the subterahertz regime — roughly 150–660 GHz — and cryogenic MAS probes. In addition, improvements were required in the polarizing agents, because the high concentrations of conventional radicals that are required to produce significant enhancements compromise spectral resolution. In the last two decades scientific and technical advances have addressed these problems and brought DNP to the point where it is achieving wide applicability. These advances include the development of high frequency gyrotron microwave sources operating in the subterahertz frequency range. In addition, low temperature MAS probes were developed that permit in-situ microwave irradiation of the samples. And, finally, biradical polarizing agents were developed that increased the efficiency of DNP experiments by factors of ~4 at considerably lower paramagnet concentrations. Collectively these developments have made it possible to apply DNP on a routine basis to a number of different scientific endeavors, most prominently in the biological and material sciences. This Account reviews these developments, including the primary mechanisms used to transfer polarization in high frequency DNP, and the current choice of microwave sources and biradical polarizing agents. In addition, we illustrate the utility of the technique with a description of applications to membrane and amyloid proteins that emphasizes the unique structural information that is available in these two cases. PMID:23597038

MAS NMR of HIV-1 protein assemblies

NASA Astrophysics Data System (ADS)

Suiter, Christopher L.; Quinn, Caitlin M.; Lu, Manman; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

2015-04-01

The negative global impact of the AIDS pandemic is well known. In this perspective article, the utility of magic angle spinning (MAS) NMR spectroscopy to answer pressing questions related to the structure and dynamics of HIV-1 protein assemblies is examined. In recent years, MAS NMR has undergone major technological developments enabling studies of large viral assemblies. We discuss some of these evolving methods and technologies and provide a perspective on the current state of MAS NMR as applied to the investigations into structure and dynamics of HIV-1 assemblies of CA capsid protein and of Gag maturation intermediates.

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

NASA Astrophysics Data System (ADS)

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

2000-12-01

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.

SIMPSON: A general simulation program for solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Transient NOE enhancement in solid-state MAS NMR of mobile systems

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Metabolic Portraits of Breast Cancer by HR MAS MR Spectroscopy of Intact Tissue Samples.

PubMed

Haukaas, Tonje H; Euceda, Leslie R; Giskeødegård, Guro F; Bathen, Tone F

2017-05-16

Despite progress in early detection and therapeutic strategies, breast cancer remains the second leading cause of cancer-related death among women globally. Due to the heterogeneity and complexity of tumor biology, breast cancer patients with similar diagnosis might have different prognosis and response to treatment. Thus, deeper understanding of individual tumor properties is necessary. Cancer cells must be able to convert nutrients to biomass while maintaining energy production, which requires reprogramming of central metabolic processes in the cells. This phenomenon is increasingly recognized as a potential target for treatment, but also as a source for biomarkers that can be used for prognosis, risk stratification and therapy monitoring. Magnetic resonance (MR) metabolomics is a widely used approach in translational research, aiming to identify clinically relevant metabolic biomarkers or generate novel understanding of the molecular biology in tumors. Ex vivo proton high-resolution magic angle spinning (HR MAS) MR spectroscopy is widely used to study central metabolic processes in a non-destructive manner. Here we review the current status for HR MAS MR spectroscopy findings in breast cancer in relation to glucose, amino acid and choline metabolism.

Quartz Crystal Temperature Sensor for MAS NMR

NASA Astrophysics Data System (ADS)

Simon, Gerald

1997-10-01

Quartz crystal temperature sensors (QCTS) were tested for the first time as wireless thermometers in NMR MAS rotors utilizing the NMR RF technique itself for exiting and receiving electro-mechanical quartz resonances. This new tool in MAS NMR has a high sensitivity, linearity, and precision. When compared to the frequently used calibration of the variable temperature in the NMR system by a solid state NMR chemical shift thermometer (CST), such as lead nitrate, QCTS shows a number of advantages. It is an inert thermometer in close contact with solid samples operating parallel to the NMR experiment. QCTS can be manufactured for any frequency to be near a NMR frequency of interest (typically 1 to 2 MHz below or above). Due to the strong response of the crystal, signal detection is possible without changing the tuning of the MAS probe. The NMR signal is not influenced due to the relative sharp crystal resonance, restricted excitation by finite pulses, high probeQvalues, and commonly used audio filters. The quadratic dependence of the temperature increase on spinning speed is the same for the QCTS and for the CST lead nitrate and is discussed in terms of frictional heat in accordance with the literature about lead nitrate and with the results of a simple rotor speed jump experiment with differently radial located lead nitrate in the rotor.

Proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

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

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu; Nishiyama, Yusuke

2015-10-28

A proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of {sup 13}C-{sup 1}H connectivities, and proximities of {sup 13}C-{sup 1}H and {sup 1}H-{sup 1}H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including {sup 1}H-{sup 1}H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protonsmore » and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) {sup 1}H/{sup 1}H and 2D {sup 13}C/{sup 1}H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of {sup 1}H-{sup 1}H proximity and {sup 13}C-{sup 1}H connectivity. In addition, the 2D (F1/F2) {sup 1}H/{sup 13}C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of {sup 1}H-{sup 1}H dipolar couplings, enables the measurement of proximities between {sup 13}C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of {sup 1}H-{sup 1}H-{sup 13}C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H{sub 2}O ⋅ HCl demonstrate the efficiency of the 3D experiment.« less

3D Double-Quantum/Double-Quantum Exchange Spectroscopy of Protons under 100 kHz Magic Angle Spinning.

PubMed

Zhang, Rongchun; Duong, Nghia Tuan; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

2017-06-22

Solid-state 1 H NMR spectroscopy has attracted much attention in the recent years due to the remarkable spectral resolution improvement by ultrafast magic-angle-spinning (MAS) as well as due to the sensitivity enhancement rendered by proton detection. Although these developments have enabled the investigation of a variety of challenging chemical and biological solids, the proton spectral resolution is still poor for many rigid solid systems owing to the presence of conformational heterogeneity and the unsuppressed residual proton-proton dipolar couplings even with the use of the highest currently feasible sample spinning speed of ∼130 kHz. Although a further increase in the spinning speed of the sample could be beneficial to some extent, there is a need for alternate approaches to enhance the spectral resolution. Herein, by fully utilizing the benefits of double-quantum (DQ) coherences, we propose a single radio frequency channel proton-based 3D pulse sequence that correlates double-quantum (DQ), DQ, and single-quantum (SQ) chemical shifts of protons. In addition to the two-spin homonuclear proximity information, the proposed 3D DQ/DQ/SQ experiment also enables the extraction of three-spin and four-spin proximities, which could be beneficial for revealing the dipolar coupled proton network in the solid state. Besides, the 2D DQ/DQ spectrum sliced at different isotropic SQ chemical shift values of the 3D DQ/DQ/SQ spectrum will also facilitate the identification of DQ correlation peaks and improve the spectral resolution, as it only provides the local homonuclear correlation information associated with the specific protons selected by the SQ chemical shift frequency. The 3D pulse sequence and its efficiency are demonstrated experimentally on small molecular compounds in the solid state. We expect that this approach would create avenues for further developments by suitably combining the benefits of partial deuteration of samples, selective excitation/decoupling pulses, heteronuclear spins for spectral editing, and nonuniform sampling.

SIMPSON: a general simulation program for solid-state NMR spectroscopy.

PubMed

Bak, M; Rasmussen, J T; Nielsen, N C

2000-12-01

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. Basically, 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. Copyright 2000 Academic Press.

Mechanism studies of the conversion of 13C-labeled n-butane on zeolite H-ZSM-5 by using 13C magic angle spinning NMR spectroscopy and GC-MS analysis.

PubMed

Luzgin, Mikhail V; Stepanov, Alexander G; Arzumanov, Sergei S; Rogov, Vladimir A; Parmon, Valentin N; Wang, Wei; Hunger, Michael; Freude, Dieter

2005-12-23

By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.

IN SITU MAGIC ANGLE SPINNING NMR FOR STUDYING GEOLOGICAL CO(2) SEQUESTRATION

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

Hoyt, David W.; Turcu, Romulus VF; Sears, Jesse A.

2011-03-27

Geological carbon sequestration (GCS) is one of the most promising ways of mitigating atmospheric greenhouse gases (1-3). Mineral carbonation reactions are potentially important to the long-term sealing effectiveness of caprock but remain poorly predictable, particularly in low-water supercritical CO2 (scCO2)-dominated environments where the chemistry has not been adequately explored. In situ probes that provide molecular-level information is desirable for investigating mechanisms and rates of GCS mineral carbonation reactions. MAS-NMR is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, or a supercritical state,more » or a mixture thereof (4,5). However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS rotor (6,7), where non-metal materials must be used. In this work, we report development of a unique high pressure MAS NMR capability, and its application to mineral carbonation chemistry in scCO2 under geologically relevant temperatures and pressures.« less

PRESTO polarization transfer to quadrupolar nuclei: Implications for dynamic nuclear polarization

DOE PAGES

Perras, Frederic A.; Kobayashi, Takeshi; Pruski, Marek

2015-08-04

In this study, we show both experimentally and numerically on a series of model systems that in experiments involving transfer of magnetization from 1H to the quadrupolar nuclei under magic-angle-spinning (MAS), the PRESTO technique consistently outperforms traditionally used cross polarization (CP), affording more quantitative intensities, improved lineshapes, better overall sensitivity, and straightforward optimization. This advantage derives from the fact that PRESTO circumvents the convoluted and uncooperative spin dynamics during the CP transfer under MAS, by replacing the spin-locking of quadrupolar nuclei with a single central transition selective 90° pulse and using a symmetry-based recoupling sequence in the 1H channel. Thismore » is important in the context of dynamic nuclear polarization (DNP) NMR of quadrupolar nuclei, where the efficient transfer of enhanced 1H polarization is desired to obtain the highest sensitivity.« less

Sine-squared shifted pulses for recoupling interactions in solid-state NMR

NASA Astrophysics Data System (ADS)

Jain, Mukul G.; Rajalakshmi, G.; Equbal, Asif; Mote, Kaustubh R.; Agarwal, Vipin; Madhu, P. K.

2017-06-01

Rotational-Echo DOuble-Resonance (REDOR) is a versatile experiment for measuring internuclear distance between two heteronuclear spins in solid-state NMR. At slow to intermediate magic-angle spinning (MAS) frequencies, the measurement of distances between strongly coupled spins is challenging due to rapid dephasing of magnetisation. This problem can be remedied by employing the pulse-shifted version of REDOR known as Shifted-REDOR (S-REDOR) that scales down the recoupled dipolar coupling. In this study, we propose a new variant of the REDOR sequence where the positions of the π pulses are determined by a sine-squared function. This new variant has scaling properties similar to S-REDOR. We use theory, numerical simulations, and experiments to compare the dipolar recoupling efficiencies and the experimental robustness of the three REDOR schemes. The proposed variant has advantages in terms of radiofrequency field requirements at fast MAS frequencies.

Study of the ferroelastic phase transition in the tetraethylammonium compound [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}ZnBr{sub 4} by magic-angle spinning and static NMR

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

Lim, Ae Ran, E-mail: aeranlim@hanmail.net, E-mail: arlim@jj.ac.kr

The ferroelastic phase transition of tetraethylammonium compound [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}ZnBr{sub 4} at the phase transition temperature (T{sub C}) = 283 K was characterized by magic-angle spinning (MAS) and static nuclear magnetic resonance (NMR), and confirmed by optical polarizing spectroscopy. The structural geometry near T{sub C} was studied in terms of the chemical shifts and the spin-lattice relaxation times T{sub 1ρ} in the rotating frame for {sup 1}H MAS NMR and {sup 13}C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups were distinguishable in the {sup 13}C NMR spectrum, and the T{sub 1ρ} results indicate that they undergo tumblingmore » motion above T{sub C} in a coupled manner. From the {sup 14}N NMR results, the two nitrogen nuclei in the N(C{sub 2}H{sub 5}){sub 4}{sup +} ions were distinguishable above T{sub C}, and the splitting in the spectra below T{sub C} was related to the ferroelastic domains with different orientations.« less

Investigation of metabolite changes in the transition from pre-invasive to invasive cervical cancer measured using (1)H and (31)P magic angle spinning MRS of intact tissue.

PubMed

De Silva, Sonali S; Payne, Geoffrey S; Thomas, Valerie; Carter, Paul G; Ind, Thomas E J; deSouza, Nandita M

2009-02-01

The aim of this study was to determine the metabolic changes in the transition from pre-invasive to invasive cervical cancer using high-resolution magic angle spinning (HR-MAS) MRS. Biopsy specimens were obtained from women with histologically normal cervix (n = 5), cervical intraepithelial neoplasia (CIN; mild, n = 5; moderate/severe, n = 40), and invasive cancer (n = 23). (1)H HR-MAS MRS data were acquired using a Bruker Avance 11.74 T spectrometer (Carr-Purcell-Meiboom-Gill sequence; TR = 4.8 s; TE = 135 ms; 512 scans; 41 min acquisition). (31)P HR-MAS spectra were obtained from the normal subjects and cancer patients only (as acetic acid applied before tissue sampling in patients with CIN impaired spectral quality) using a (1)H-decoupled pulse-acquire sequence (TR = 2.82 s; 2048 scans; 96 min acquisition). Peak assignments were based on values reported in the literature. Peak areas were measured using the AMARES algorithm. Estimated metabolite concentrations were compared between patient diagnostic categories and tissue histology using independent samples t tests. Comparisons based on patient category at diagnosis showed significantly higher estimated concentrations of choline (P = 0.0001) and phosphocholine (P = 0.002) in tissue from patients with cancer than from patients with high-grade dyskaryosis, but no differences between non-cancer groups. Division by histology of the sample also showed increases in choline (P = 0.002) and phosphocholine (P = 0.002) in cancer compared with high-grade CIN tissue. Phosphoethanolamine was increased in cancer compared with normal tissue (P = 0.0001). Estimated concentrations of alanine (P = 0.01) and creatine (P = 0.008) were significantly reduced in normal tissue from cancer patients compared with normal tissue from non-cancer patients. The estimated concentration of choline was significantly increased in CIN tissue from cancer patients compared with CIN tissue from non-cancer patients (P = 0.0001). Estimated concentrations of choline-containing metabolites increased from pre-invasive to invasive cervical cancer. Concurrent metabolite depletion occurs in normal tissue adjacent to cancer tissue. Copyright (c) 2008 John Wiley & Sons, Ltd.

Timing irregularities of PSR J1705-1906

NASA Astrophysics Data System (ADS)

Liu, Y. L.; Yuan, J. P.; Wang, J. B.; Liu, X. W.; Wang, N.; Yuen, R.

2018-05-01

Timing analysis of PSR J1705-1906 using data from Nanshan 25-m and Parkes 64-m radio telescopes, which span over fourteen years, shows that the pulsar exhibits significant proper motion, and rotation instability. We updated the astrometry parameters and the spin parameters of the pulsar. In order to minimize the effect of timing irregularities on measuring its position, we employ the Cholesky method to analyse the timing noise. We obtain the proper motion of -77(3) mas yr-1 in right ascension and -38(29) mas yr-1 in declination. The power spectrum of timing noise is analyzed for the first time, which gives the spectral exponent α =-5.2 for the power-law model indicating that the fluctuations in spin frequency and spin-down rate dominate the red noise. We detect two small glitches from this pulsar with fractional jump in spin frequency of Δ ν /ν ˜ 2.9 × 10^{-10} around MJD 55199 and Δ ν /ν ˜ 2.7× 10^{-10} around MJD 55953. Investigations of pulse profile at different time segments suggest no significant changes in the pulse profiles around the two glitches.

Proton-Based Ultrafast Magic Angle Spinning Solid-State NMR Spectroscopy.

PubMed

Zhang, Rongchun; Mroue, Kamal H; Ramamoorthy, Ayyalusamy

2017-04-18

Protons are vastly abundant in a wide range of exciting macromolecules and thus can be a powerful probe to investigate the structure and dynamics at atomic resolution using solid-state NMR (ssNMR) spectroscopy. Unfortunately, the high signal sensitivity, afforded by the high natural-abundance and high gyromagnetic ratio of protons, is greatly compromised by severe line broadening due to the very strong 1 H- 1 H dipolar couplings. As a result, protons are rarely used, in spite of the desperate need for enhancing the sensitivity of ssNMR to study a variety of systems that are not amenable for high resolution investigation using other techniques including X-ray crystallography, cryo-electron microscopy, and solution NMR spectroscopy. Thanks to the remarkable improvement in proton spectral resolution afforded by the significant advances in magic-angle-spinning (MAS) probe technology, 1 H ssNMR spectroscopy has recently attracted considerable attention in the structural and dynamics studies of various molecular systems. However, it still remains a challenge to obtain narrow 1 H spectral lines, especially from proteins, without resorting to deuteration. In this Account, we review recent proton-based ssNMR strategies that have been developed in our laboratory to further improve proton spectral resolution without resorting to chemical deuteration for the purposes of gaining atomistic-level insights into molecular structures of various crystalline solid systems, using small molecules and peptides as illustrative examples. The proton spectral resolution enhancement afforded by the ultrafast MAS frequencies up to 120 kHz is initially discussed, followed by a description of an ensemble of multidimensional NMR pulse sequences, all based on proton detection, that have been developed to obtain in-depth information from dipolar couplings and chemical shift anisotropy (CSA). Simple single channel multidimensional proton NMR experiments could be performed to probe the proximity of protons for structure determination using 1 H- 1 H dipolar couplings and to evaluate the changes in chemical environments as well as the relative orientation to the external magnetic field using proton CSA. Due to the boost in signal sensitivity enabled by proton detection under ultrafast MAS, by virtue of high proton natural abundance and gyromagnetic ratio, proton-detected multidimensional experiments involving low-γ nuclei can now be accomplished within a reasonable time, while the higher dimension also offers additional resolution enhancement. In addition, the application of proton-based ssNMR spectroscopy under ultrafast MAS in various challenging and crystalline systems is also presented. Finally, we briefly discuss the limitations and challenges pertaining to proton-based ssNMR spectroscopy under ultrafast MAS conditions, such as the presence of high-order dipolar couplings, friction-induced sample heating, and limited sample volume. Although there are still a number of challenges that must be circumvented by further developments in radio frequency pulse sequences, MAS probe technology and approaches to prepare NMR-friendly samples, proton-based ssNMR has already gained much popularity in various research domains, especially in proteins where uniform or site-selective deuteration can be relatively easily achieved. In addition, implementation of the recently developed fast data acquisition approaches would also enable further developments in the design and applications of proton-based ultrafast MAS multidimensional ssNMR techniques.

Metabolic profiles of placenta in preeclampsia using HR-MAS MRS metabolomics.

PubMed

Austdal, Marie; Thomsen, Liv Cecilie Vestrheim; Tangerås, Line Haugstad; Skei, Bente; Mathew, Seema; Bjørge, Line; Austgulen, Rigmor; Bathen, Tone Frost; Iversen, Ann-Charlotte

2015-12-01

Preeclampsia is a heterogeneous gestational disease characterized by maternal hypertension and proteinuria, affecting 2-7% of pregnancies. The disorder is initiated by insufficient placental development, but studies characterizing the placental disease components are lacking. Our aim was to phenotype the preeclamptic placenta using high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (HR-MAS MRS). Placental samples collected after delivery from women with preeclampsia (n = 19) and normotensive pregnancies (n = 15) were analyzed for metabolic biomarkers including amino acids, osmolytes, and components of the energy and phospholipid metabolism. The metabolic biomarkers were correlated to clinical characteristics and inflammatory biomarkers in the maternal sera. Principal component analysis showed inherent differences in placental metabolic profiles between preeclamptic and normotensive pregnancies. Significant differences in metabolic profiles were found between placentas from severe and non-severe preeclampsia, but not between preeclamptic pregnancies with fetal growth restricted versus normal weight neonates. The placental metabolites correlated with the placental stress marker sFlt-1 and triglycerides in maternal serum, suggesting variation in placental stress signaling between different placental phenotypes. HR-MAS MRS is a sensitive method for defining the placental disease component of preeclampsia, identifying several altered metabolic pathways. Placental HR-MAS MRS analysis may improve insight into processes affected in the preeclamptic placenta, and represents a novel long-required tool for a sensitive placental phenotyping of this heterogeneous disease. Copyright © 2015 Elsevier Ltd. All rights reserved.

13C-13C dipolar recoupling under very fast magic angle spinning in solid-state nuclear magnetic resonance: Applications to distance measurements, spectral assignments, and high-throughput secondary-structure determination

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka

2001-05-01

A technique is presented to recouple homonuclear dipolar couplings between dilute spin pairs such as 13C-13C systems under very fast magic angle spinning (MAS) in solid-state nuclear magnetic resonance (NMR) spectroscopy. The presented technique, finite pulse rf driven recoupling (fpRFDR), restores homonuclear dipolar interactions based on constructive usage of finite pulse-width effects in a phase- and symmetry-cycled π-pulse train in which a rotor-synchronous π pulse is applied every rotation period. The restored effective dipolar interaction has the form of a zero-quantum dipolar Hamiltonian for static solids, whose symmetry in spin space is different from that obtained by conventional rf driven recoupling (RFDR) techniques. It is demonstrated that the efficiency of recoupling by fpRFDR is not strongly dependent on chemical shift differences or resonance offsets in contrast to previous recoupling methods under very fast MAS. To realize distance measurements without effects of spin relaxation, a constant-time version of fpRFDR (CT-fpRFDR) is introduced, in which the effective evolution period is varied by refocusing dipolar evolution with a rotor-synchronized solid echo while the total recoupling period is kept constant. From CT-fpRFDR experiments at a spinning speed of 30.3 kHz in a field of 17.6 T, the 13C-13C distance of [1-13C]Ala-[1-13C]Gly-Gly was determined to be 3.27 Å, which agrees well with the value of 3.20 Å obtained by x-ray diffraction. Also, two-dimensional (2D) 13C/13C chemical-shift correlation NMR spectrum in a field of 9.4 T was obtained with fpRFDR for fibrils of the segmentally 13C- and 15N-labeled Alzheimer's β-Amyloid fragments, Aβ16-22 (residues 16-22 taken from the 40-residue Aβ peptide) in which Leu-17 through Ala-21 are uniformly 13C- and 15N-labeled. Most 13C resonances for the main chain as well as for the side chains are assigned based on 2D 13C/13C chemical-shift correlation patterns specific to amino-acid types. Examination of the obtained 13C chemical shifts revealed the formation of β-strand across the entire molecule of Aβ16-22. Possibility of high throughput determination of global main-chain structures based on 13C shifts obtained from 2D 13C/13C chemical-shift correlation under very fast MAS is also discussed for uniformly/segmentally 13C-labeled protein/peptide samples.

Magnetic resonance metabolic profiling of estrogen receptor-positive breast cancer: correlation with currently used molecular markers

PubMed Central

Koo, Ja Seung; Kim, Siwon; Park, Vivian Youngjean; Kim, Eun-Kyung; Kim, Suhkmann; Kim, Min Jung

2017-01-01

Estrogen receptor (ER)-positive breast cancers overall have a good prognosis, however, some patients suffer relapses and do not respond to endocrine therapy. The purpose of this study was to determine whether there are any correlations between high-resolution magic angle spinning (HR-MAS) magnetic resonance spectroscopy (MRS) metabolic profiles of core needle biopsy (CNB) specimens and the molecular markers currently used in patients with ER-positive breast cancers. The metabolic profiling of CNB samples from 62 ER-positive cancers was performed by HR-MAS MRS. Metabolic profiles were compared according to human epidermal growth factor receptor 2 (HER2) and Ki-67 status, and luminal type, using the Mann-Whitney test. Multivariate analysis was performed with orthogonal projections to latent structure-discriminant analysis (OPLS-DA). In univariate analysis, the HER2-positive group was shown to have higher levels of glycine and glutamate, compared to the HER2-negative group (P<0.01, and P <0.01, respectively). The high Ki-67 group showed higher levels of glutamate than the low Ki-67 group without statistical significance. Luminal B cancers showed higher levels of glycine (P=0.01) than luminal A cancers. In multivariate analysis, the OPLS-DA models built with HR-MAS MR metabolic profiles showed visible discrimination between the subgroups according to HER2 and Ki-67 status, and luminal type. This study showed that the metabolic profiles of CNB samples assessed by HR-MAS MRS can be used to detect potential prognostic biomarkers as well as to understand the difference in metabolic mechanism among subtypes of ER-positive breast cancer. PMID:28969000

Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR.

PubMed

Jarlbring, Mathias; Sandström, Dan E; Antzutkin, Oleg N; Forsling, Willis

2006-05-09

The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.

Progress in proton-detected solid-state NMR (SSNMR): Super-fast 2D SSNMR collection for nano-mole-scale proteins

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka; Wickramasinghe, Ayesha; Matsuda, Isamu; Endo, Yuki; Ishii, Yuji; Nishiyama, Yusuke; Nemoto, Takahiro; Kamihara, Takayuki

2018-01-01

Proton-detected solid-state NMR (SSNMR) spectroscopy has attracted much attention due to its excellent sensitivity and effectiveness in the analysis of trace amounts of amyloid proteins and other important biological systems. In this perspective article, we present the recent sensitivity limit of 1H-detected SSNMR using "ultra-fast" magic-angle spinning (MAS) at a spinning rate (νR) of 80-100 kHz. It was demonstrated that the high sensitivity of 1H-detected SSNMR at νR of 100 kHz and fast recycling using the paramagnetic-assisted condensed data collection (PACC) approach permitted "super-fast" collection of 1H-detected 2D protein SSNMR. A 1H-detected 2D 1H-15N correlation SSNMR spectrum for ∼27 nmol of a uniformly 13C- and 15N-labeled GB1 protein sample in microcrystalline form was acquired in only 9 s with 50% non-uniform sampling and short recycle delays of 100 ms. Additional data suggests that it is now feasible to detect as little as 1 nmol of the protein in 5.9 h by 1H-detected 2D 1H-15N SSNMR at a nominal signal-to-noise ratio of five. The demonstrated sensitivity is comparable to that of modern solution protein NMR. Moreover, this article summarizes the influence of ultra-fast MAS and 1H-detection on the spectral resolution and sensitivity of protein SSNMR. Recent progress in signal assignment and structural elucidation by 1H-detected protein SSNMR is outlined with both theoretical and experimental aspects.

Measurements of relative chemical shift tensor orientations in solid-state NMR: new slow magic angle spinning dipolar recoupling experiments.

PubMed

Jurd, Andrew P S; Titman, Jeremy J

2009-08-28

Solid-state NMR experiments can be used to determine conformational parameters, such as interatomic distances and torsion angles. The latter can be obtained from measurements of the relative orientation of two chemical shift tensors, if the orientation of these with respect to the surrounding bonds is known. In this paper, a new rotor-synchronized magic angle spinning (MAS) dipolar correlation experiment is described which can be used in this way. Because the experiment requires slow MAS rates, a novel recoupling sequence, designed using symmetry principles, is incorporated into the mixing period. This recoupling sequence is based in turn on a new composite cyclic pulse referred to as COAST (for combined offset and anisotropy stabilization). The new COAST-C7(2)(1) sequence is shown to give good theoretical and experimental recoupling efficiency, even when the CSA far exceeds the MAS rate. In this regime, previous recoupling sequences, such as POST-C7(2)(1), exhibit poor recoupling performance. The effectiveness of the new method has been explored by a study of the dipeptide L-phenylalanyl-L-phenylalanine.

Spin-locking of half-integer quadrupolar nuclei in NMR of solids: The far off-resonance case.

PubMed

Odedra, Smita; Wimperis, Stephen

Spin-locking of spin I=3/2 and I=5/2 nuclei in the presence of large resonance offsets has been studied using both approximate and exact theoretical approaches and, in the case of I=3/2, experimentally. We show the variety of coherences and population states produced in a far off-resonance spin-locking NMR experiment (one consisting solely of a spin-locking pulse) and how these vary with the radiofrequency field strength and offset frequency. Under magic angle spinning (MAS) conditions and in the "adiabatic limit", these spin-locked states acquire a time dependence. We discuss the rotor-driven interconversion of the spin-locked states, using an exact density matrix approach to confirm the results of the approximate model. Using conventional and multiple-quantum filtered spin-locking 23 Na (I=3/2) NMR experiments under both static and MAS conditions, we confirm the results of the theoretical calculations, demonstrating the applicability of the approximate theoretical model to the far off-resonance case. This simplified model includes only the effects of the initial rapid dephasing of coherences that occurs at the start of the spin-locking period and its success in reproducing both experimental and exact simulation data indicates that it is this dephasing that is the dominant phenomenon in NMR spin-locking of quadrupolar nuclei, as we have previously found for the on-resonance and near-resonance cases. Potentially, far off-resonance spin-locking of quadrupolar nuclei could be of interest in experiments such as cross polarisation as a consequence of the spin-locking pulse being applied to a better defined initial state (the thermal equilibrium bulk magnetisation aligned along the z-axis) than can be created in a powdered solid with a selective radiofrequency pulse, where the effect of the pulse depends on the orientation of the individual crystallites. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Mao, J.-D.; Schimmelmann, A.; Mastalerz, Maria; Hatcher, P.G.; Li, Y.

2010-01-01

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.

Proton assisted recoupling and protein structure determination

NASA Astrophysics Data System (ADS)

de Paëpe, Gaël; Lewandowski, Józef R.; Loquet, Antoine; Böckmann, Anja; Griffin, Robert G.

2008-12-01

We introduce a homonuclear version of third spin assisted recoupling, a second-order mechanism that can be used for polarization transfer between 13C or 15N spins in magic angle spinning (MAS) NMR experiments, particularly at high spinning frequencies employed in contemporary high field MAS experiments. The resulting sequence, which we refer to as proton assisted recoupling (PAR), relies on a cross-term between 1H-13C (or 1H-15N) couplings to mediate zero quantum 13C-13C (or 15N-15N recoupling). In particular, using average Hamiltonian theory we derive an effective Hamiltonian for PAR and show that the transfer is mediated by trilinear terms of the form C1+/-C2-/+HZ for 13C-13C recoupling experiments (or N1+/-N2-/+HZ for 15N-15N). We use analytical and numerical simulations to explain the structure of the PAR optimization maps and to delineate the PAR matching conditions. We also detail the PAR polarization transfer dependence with respect to the local molecular geometry and explain the observed reduction in dipolar truncation. Finally, we demonstrate the utility of PAR in structural studies of proteins with 13C-13C spectra of uniformly 13C, 15N labeled microcrystalline Crh, a 85 amino acid model protein that forms a domain swapped dimer (MW=2×10.4 kDa). The spectra, which were acquired at high MAS frequencies (ωr2π>20 kHz) and magnetic fields (750-900 MHz 1H frequencies) using moderate rf fields, exhibit numerous cross peaks corresponding to long (up to 6-7 A˚) 13C-13C distances which are particularly useful in protein structure determination. Using results from PAR spectra we calculate the structure of the Crh protein.

Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment

NASA Astrophysics Data System (ADS)

Manu, V. S.; Veglia, Gianluigi

2016-12-01

Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

Recent Results from the MicroMAS Global Environmental MonitoringNanosatellite Mission

NASA Astrophysics Data System (ADS)

Blackwell, W. J.; Cahoy, K.

2014-12-01

The Micro-sized Microwave Atmospheric Satellite (MicroMAS) is a dual-spinning 3U CubeSat equipped with apassive microwave radiometer that observes in nine channels near the 118.75-GHz oxygen absorption line.MicroMAS is designed to observe convective thunderstorms, tropical cyclones, and hurricanes from a midinclinationorbit. The MicroMAS flight unit was developed by MIT Lincoln Laboratory and the MIT Space SystemsLaboratory and was launched to the International Space Station on July 13, 2014, and scheduled for an earlySeptember deployment for a ~90-day mission. The payload is housed in the "lower" 1U of the dual-spinning 3UCubeSat and mechanically rotated approximately once per second as the spacecraft orbits the Earth, resulting in across-track scanned beam with a full-width half-max (FWHM) beamwidth of 2.4 degrees and an approximately 17-km diameter footprint at nadir incidence from a nominal altitude of 400 km. The relatively low cost of MicroMASenables the deployment of a constellation of sensors, spaced equally around several orbit planes. A small fleet ofMicroMAS systems could yield high-resolution global temperature and water vapor profiles, as well as cloudmicrophysical and precipitation parameters.Significant advancements were made in the Assembly, Integration, and Test phase of the project developmentlifecycle. The flight software and communications architecture was refined and tested in relevant lab facilities. Thepower subsystem was modified to include additional required inhibits for the ISS launch. Hardware in the loop testsas well as simulations of the attitude determination and control system (ADCS) were performed to validate theunique dual-spinning, local vertical, local horizontal (LVLH) stabilized flight design. ADCS algorithms were testedon a 3-axis air bearing and custom rig inside a 3-axis programmable Helmholtz cage. Finally, the integratedspacecraft underwent a series of environmental tests in order to verify the results of thermal modeling analyses,prove the performance of critical design components in relevant environmental conditions, and validate the softwareand concept-of-operations developed for flight. We present these advancements, lessons-learned in developing ascience-oriented CubeSat system, and any available launch/on-orbit updates.

Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS 1H solid-state NMR spectroscopy and GIPAW calculations.

PubMed

Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

2017-10-01

Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional 1 H, 13 C and 15 N and two-dimensional 1 H- 13 C and 14 N- 1 H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the 1 H, 13 C and 14 N/ 15 N resonances. A two-dimensional 1 H- 1 H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

A quasi-optical and corrugated waveguide microwave transmission system for simultaneous dynamic nuclear polarization NMR on two separate 14.1 T spectrometers

PubMed Central

Dubroca, Thierry; Smith, Adam N.; Pike, Kevin J.; Froud, Stuart; Wylde, Richard; Trociewitz, Bianca; McKay, Johannes; Mentink-Vigier, Frederic; van Tol, Johan; Wi, Sungsool; Brey, William; Long, Joanna R.; Frydman, Lucio; Hill, Stephen

2018-01-01

Nuclear magnetic resonance (NMR) is an intrinsically insensitive technique, with Boltzmann distributions of nuclear spin states on the order of parts per million in conventional magnetic fields. To overcome this limitation, dynamic nuclear polarization (DNP) can be used to gain up to three orders of magnitude in signal enhancement, which can decrease experimental time by up to six orders of magnitude. In DNP experiments, nuclear spin polarization is enhanced by transferring the relatively larger electron polarization to NMR active nuclei via microwave irradiation. Here, we describe the design and performance of a quasi-optical system enabling the use of a single 395 GHz gyrotron microwave source to simultaneously perform DNP experiments on two different 14.1 T (1H 600 MHz) NMR spectrometers: one configured for magic angle spinning (MAS) solid state NMR; the other configured for solution state NMR experiments. In particular, we describe how the high power microwave beam is split, transmitted, and manipulated between the two spectrometers. A 13C enhancement of 128 is achieved via the cross effect for alanine, using the nitroxide biradical AMUPol, under MAS-DNP conditions at 110 K, while a 31P enhancement of 160 is achieved via the Overhauser effect for triphenylphosphine using the monoradical BDPA under solution NMR conditions at room temperature. The latter result is the first demonstration of Overhauser DNP in the solution state at a field of 14.1 T (1H 600 MHz). Moreover these results have been produced with large sample volumes (~100 μL, i.e. 3 mm diameter NMR tubes). PMID:29459343

A quasi-optical and corrugated waveguide microwave transmission system for simultaneous dynamic nuclear polarization NMR on two separate 14.1 T spectrometers

NASA Astrophysics Data System (ADS)

Dubroca, Thierry; Smith, Adam N.; Pike, Kevin J.; Froud, Stuart; Wylde, Richard; Trociewitz, Bianca; McKay, Johannes; Mentink-Vigier, Frederic; van Tol, Johan; Wi, Sungsool; Brey, William; Long, Joanna R.; Frydman, Lucio; Hill, Stephen

2018-04-01

Nuclear magnetic resonance (NMR) is an intrinsically insensitive technique, with Boltzmann distributions of nuclear spin states on the order of parts per million in conventional magnetic fields. To overcome this limitation, dynamic nuclear polarization (DNP) can be used to gain up to three orders of magnitude in signal enhancement, which can decrease experimental time by up to six orders of magnitude. In DNP experiments, nuclear spin polarization is enhanced by transferring the relatively larger electron polarization to NMR active nuclei via microwave irradiation. Here, we describe the design and performance of a quasi-optical system enabling the use of a single 395 GHz gyrotron microwave source to simultaneously perform DNP experiments on two different 14.1 T (1H 600 MHz) NMR spectrometers: one configured for magic angle spinning (MAS) solid state NMR; the other configured for solution state NMR experiments. In particular, we describe how the high power microwave beam is split, transmitted, and manipulated between the two spectrometers. A 13C enhancement of 128 is achieved via the cross effect for alanine, using the nitroxide biradical AMUPol, under MAS-DNP conditions at 110 K, while a 31P enhancement of 160 is achieved via the Overhauser effect for triphenylphosphine using the monoradical BDPA under solution NMR conditions at room temperature. The latter result is the first demonstration of Overhauser DNP in the solution state at a field of 14.1 T (1H 600 MHz). Moreover these results have been produced with large sample volumes (∼100 μL, i.e. 3 mm diameter NMR tubes).

A quasi-optical and corrugated waveguide microwave transmission system for simultaneous dynamic nuclear polarization NMR on two separate 14.1 T spectrometers.

PubMed

Dubroca, Thierry; Smith, Adam N; Pike, Kevin J; Froud, Stuart; Wylde, Richard; Trociewitz, Bianca; McKay, Johannes; Mentink-Vigier, Frederic; van Tol, Johan; Wi, Sungsool; Brey, William; Long, Joanna R; Frydman, Lucio; Hill, Stephen

2018-04-01

Nuclear magnetic resonance (NMR) is an intrinsically insensitive technique, with Boltzmann distributions of nuclear spin states on the order of parts per million in conventional magnetic fields. To overcome this limitation, dynamic nuclear polarization (DNP) can be used to gain up to three orders of magnitude in signal enhancement, which can decrease experimental time by up to six orders of magnitude. In DNP experiments, nuclear spin polarization is enhanced by transferring the relatively larger electron polarization to NMR active nuclei via microwave irradiation. Here, we describe the design and performance of a quasi-optical system enabling the use of a single 395 GHz gyrotron microwave source to simultaneously perform DNP experiments on two different 14.1 T ( 1 H 600 MHz) NMR spectrometers: one configured for magic angle spinning (MAS) solid state NMR; the other configured for solution state NMR experiments. In particular, we describe how the high power microwave beam is split, transmitted, and manipulated between the two spectrometers. A 13 C enhancement of 128 is achieved via the cross effect for alanine, using the nitroxide biradical AMUPol, under MAS-DNP conditions at 110 K, while a 31 P enhancement of 160 is achieved via the Overhauser effect for triphenylphosphine using the monoradical BDPA under solution NMR conditions at room temperature. The latter result is the first demonstration of Overhauser DNP in the solution state at a field of 14.1 T ( 1 H 600 MHz). Moreover these results have been produced with large sample volumes (∼100 µL, i.e. 3 mm diameter NMR tubes). Copyright © 2018 Elsevier Inc. All rights reserved.

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

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

Mao, Kanmi; Pruski, Marek

Two-dimensional through-bond {sup 1}H({sup 13}C) solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse {sup 1}H 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 {sup 1}H 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.

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

NASA Astrophysics Data System (ADS)

Mao, Kanmi; Pruski, Marek

2009-12-01

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.

Accurate determination of chemical shift tensor orientations of single-crystals by solid-state magic angle spinning NMR

NASA Astrophysics Data System (ADS)

Avadhut, Yamini S.; Weber, Johannes; Schmedt auf der Günne, Jörn

2017-09-01

An improved implementation of single-crystal magic-angle-spinning (MAS) NMR is presented which gives access to chemical shift tensors both in orientation (relative to the crystal axis system) and principal axis values. For mounting arbitrary crystals inside ordinary MAS rotors, a mounting tool is described which allows to relate the crystal orientation determined by diffraction techniques to the rotor coordinate system. The crystal is finally mounted into a MAS rotor equipped with a special insert which allows a defined reorientation of the single-crystal by 90°. The approach is based on the idea that the dispersive spectra, which are obtained when applying read-pulses at specific rotor-phases, not only yield the size of the eigenvalues but also encode the orientation of the different chemical shift (rank-2) tensors. For this purpose two 2D-data sets with orthogonal crystal orientation are fitted simultaneously. The presented analysis for chemical shift tensors is supported by an analytical formula which allows fast calculation of phase and amplitude of individual spinning side-bands and by a protocol which solves the problem of finding the correct reference phase of the spectrum. Different rotor-synchronized pulse-sequences are introduced for the same reason. Experiments are performed on L-alanine and O-phosphorylethanolamine and the observed errors are analyzed in detail. The experimental data are opposed to DFT-computed chemical shift tensors which have been obtained by the extended embedded ion method.

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide) based polyether-ester-sulfonate ionomers

NASA Astrophysics Data System (ADS)

Roach, David J.

Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. 1H and 7Li spin-lattice relaxation times (T1) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T1 values along with the presence of minima in T1 as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though lithium hopping is about ten times slower than the segmental motion. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments. Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (T g) have been investigated using solid-state nuclear magnetic resonance (NMR). Experiments detecting 13C with 1H decoupling under magic angle spinning (MAS) conditions identified the different components and relative mobilities of the polymer backbone of a suite of. lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) 1H-13C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content. Each of the main backbone components (PEO spacer and isophthalate groups) exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and 1H spin-lattice relaxation rate measurements. The temperature dependences of 13C linewidths were used to both qualitatively and quantitatively examine the effects of cation content on PEO mobility. Variable contact time 1H-13C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, determined from the rate of magnetization transfer from 1H to 13C nuclei, in all ionic samples becomes similar for T [special characters omitted] 1.1 Tg, indicating that the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results compliment previous findings and present an improved picture of the dependence of backbone dynamics on cation type and density in these amorphous PEO-based ionomer systems. 7Li PFG NMR experiments provided measurements of the self-diffusion coefficients for Li+ cations in the PEO600-y Li ionomer series over a range of temperatures. When the Tg values are taken into account, the self-diffusion coefficients of Li+ in each sample follow a similar trendline, indicating that lithium diffusion is independent of ion concentration at any given reduced inverse temperature, Tg/T. Ion aggregation increases Tg and slows both lithium cation diffusion and displacement, but there is no further slowing beyond the Tg effect in the PEO600-y Li ionomers samples. The differences in activation energies obtained from diffusion measurements and relaxation times suggest that at least one additional barrier must be overcome for cations emerge from local hopping motion to macroscopic cation transpfort. Using the Nernst- Einstein equation lithium diffusion coefficients were also calculated from conductivity measurements. The differences between the diffusion measured by the two separate techniques indicate the presence of ion pairs. The activation energy of lithium diffusion was found to be nearly identical between the PFG NMR and conductivity, suggesting that the conductivity and ionic diffusion are related to the same ionic dynamics. As the ion content within the PEO600-y Li samples increases the relative concentration of nonconducting ion pairs decrease. Also an increase in temperature causes a fraction of ion pairs to thermally dissociate into positive triple ions.

Crocus sativus Petals: Waste or Valuable Resource? The Answer of High-Resolution and High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance.

PubMed

Righi, Valeria; Parenti, Francesca; Tugnoli, Vitaliano; Schenetti, Luisa; Mucci, Adele

2015-09-30

Intact Crocus sativus petals were studied for the first time by high-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy, revealing the presence of kinsenoside (2) and goodyeroside A (3), together with 3-hydroxy-γ-butyrolactone (4). These findings were confirmed by HR-NMR analysis of the ethanol extract of fresh petals and showed that, even though carried out rapidly, partial hydrolysis of glucopyranosyloxybutanolides occurs during extraction. On the other hand, kaempferol 3-O-sophoroside (1), which is "NMR-silent" in intact petals, is present in extracts. These results suggest to evaluate the utilization of saffron petals for phytopharmaceutical and nutraceutical purposes to exploit a waste product of massive production of commercial saffron and point to the application of HR-MAS NMR for monitoring bioactive compounds directly on intact petals, avoiding the extraction procedure and the consequent hydrolysis reaction.

Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

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

Mao, Kanmi

The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., 13C and 15N) via the sensitive high-{gamma} nuclei (e.g., 1H and 19F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for 1H- 1H homonuclear decoupling. Also presented is a simple new strategy for optimization of 1H- 1H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in 1H detected 2D 1H{l_brace} 13C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional 13C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear 1H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5 m more » $$\\bar{x}$$, PMLG5 mm $$\\bar{x}$$x and SAM3) were analyzed to maximize the performance of through-bond transfer based on decoupling efficiency as well as scaling factors. Indirect detection with assistance of PMLG m $$\\bar{x}$$ during INEPTR transfer proved to offer the highest sensitivity gains of 3-10. In addition, the CRAMPS sequence was applied under fast MAS to increase the 1H resolution during t 1 evolution in the traditional, 13C detected HETCOR scheme. Two naturally abundant solids, tripeptide N-formyl-L-methionyl-L-leucyl-L-phenylalanine (f-MLF-OH) and brown coal, with well ordered and highly disordered structures, respectively, are studied to confirm the capabilities of these techniques. Concomitantly, a simple optimization of 1H homonuclear dipolar decoupling at MAS rates exceeding 10 kHz was developed (Chapter 4). The fine-tuned decoupling efficiency can be obtained by minimizing the signal loss due to transverse relaxation in a simple spin-echo experiment, using directly the sample of interest. The excellent agreement between observed decoupling pattern and earlier theoretical predictions confirmed the utility of this strategy. The properties of naturally abundant surface-bound fluorocarbon groups in mesoporous silica nanoparticles (MSNs) were investigated by the above-mentioned multidimensional solid-state NMR experiments and theoretical modeling (Chapter 5). Two conformations of (pentafluorophenyl)propyl groups (abbreviated as PFP) were determined as PFP-prone and PFP-upright, whose aromatic rings are located above the siloxane bridges and in roughly upright position, respectively. Several 1D and 2D NMR techniques were implemented in the characterizations, including indirectly detected 1H{l_brace} 13C{r_brace} and 19F{l_brace} 13C{r_brace} 2D HETCOR, Carr-Purcell-Meiboom-Gill (CPMG) assisted 29Si direct polarization and 29Si 19F 2D experiments, 2D double-quantum (DQ) 19F MAS NMR spectra and spin-echo measurements. Furthermore, conformational details of two types of PFP were confirmed by theoretical calculation, operated by Dr. Takeshi Kobayashi. Finally, the arrangement of two surfactants, cetyltrimetylammoium bromide (CTAB) and cetylpyridinium bromide (CPB), mixed inside the MSN pores, was studied by solid-state NMR (Chapter 6). By analyzing the 1H- 1H DQMAS and NOESY correlation spectra, the CTAB and CPB molecules were shown to co-exist inside the pores without forming significant monocomponent domains. A 'folded-over' conformation of CPB headgroups was proposed according to the results from 1H- 29Si 2D HETCOR.« less

Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Hou, Guangjin; Lu, Xingyu; Vega, Alexander J.; Polenova, Tatyana

2014-09-01

We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear 1H-X (X = 13C, 15N, 31P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the 1H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the 1H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from 1H chemical shift anisotropy, while keeping the 1H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [15N]-N-acetyl-valine and [U-13C,15N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate 1H-15N dipolar couplings in the context of 3D experiments is presented on U-13C,15N-enriched dynein light chain protein LC8.

Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot.

PubMed

Pecher, Oliver; Halat, David M; Lee, Jeongjae; Liu, Zigeng; Griffith, Kent J; Braun, Marco; Grey, Clare P

2017-02-01

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated "on-the-fly" re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g. 7 Li and 31 P at 117 and 122MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic 7 Li and 31 P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO 4 ; (2) paramagnetic 17 O VT-NMR of the solid oxide fuel cell cathode material La 2 NiO 4+δ ; (3) broadband 93 Nb static NMR of the Li-ion battery material BNb 2 O 5 ; and (4) broadband static 127 I NMR of a potential Li-air battery product LiIO 3 . In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1-25MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot

NASA Astrophysics Data System (ADS)

Pecher, Oliver; Halat, David M.; Lee, Jeongjae; Liu, Zigeng; Griffith, Kent J.; Braun, Marco; Grey, Clare P.

2017-02-01

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated "on-the-fly" re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g.7Li and 31P at 117 and 122 MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic 7Li and 31P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO4; (2) paramagnetic 17O VT-NMR of the solid oxide fuel cell cathode material La2NiO4+δ; (3) broadband 93Nb static NMR of the Li-ion battery material BNb2O5; and (4) broadband static 127I NMR of a potential Li-air battery product LiIO3. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1-25 MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems.

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

Pilgrim, C. D.; Callahan, J. R.; Colla, C. A.

Here, one-dimensional 27Al, 23Na Magic-Angle-Spinning (MAS) NMR and 27Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the δ-isomer of the Al 13 Keggin structure at high spinning speed and 14.1 T field. Values for the CQ and η parameters are on the same scale as those seen in other isomers of the Al 13 structure. Density functional theory (DFT) calculations are performed for comparison to the experimental fits using the B3PW91/6-31+G* and PBE0/6-31+G* levels of theory, with the Polarizable Continuum Model (PCM).

Efficient Time Propagation Technique for MAS NMR Simulation: Application to Quadrupolar Nuclei.

PubMed

Charpentier; Fermon; Virlet

1998-06-01

The quantum mechanical Floquet theory is investigated in order to derive an efficient way of performing numerical calculations of the dynamics of nuclear spin systems in MAS NMR experiments. Here, we take advantage of time domain integration of the quantum evolution over one period as proposed by Eden et al. (1). But a full investigation of the propagator U(t, t0), and especially its dependence with respect to t and t0 within a formalized approach, leads to further simplifications and to a substantial reduction in computation time when performing powder averaging for any complex sequence. Such an approximation is suitable for quadrupolar nuclei (I > 1/2) and can be applied to the simulation of the RIACT (rotational induced adiabatic coherence transfer) phenomenon that occurs under special experimental conditions in spin locking experiments (2-4). The present method is also compared to the usual infinite dimensional Floquet space approach (5, 6), which is shown to be rather inefficient. As far as we know, it has never been reported for quadrupolar nuclei with I >/= 3/2 in spin locking experiments. The method can also be easily extended to other areas of spectroscopy. Copyright 1998 Academic Press.

Spin-lattice relaxation of 13C in solid amino acids using the CP-MAS technique

NASA Astrophysics Data System (ADS)

Naito, A.; Ganapathy, S.; Akasaka, K.; McDowell, C. A.

It is shown by a simple application of relaxation theory that the 13C magnetization decays nonexponentially, in principle, in the CP-MAS experiment because of the distribution of the spin-lattice relaxation times; however, the deviation from the exponential decay is quite small. The transient Overhauser effect also contributes appreciably to the nonexponential decay of the 13C magnetization when the protons are not saturated during the 13C T1 measurements and the correlation time of the group rotational motion satisfies the condition, ω2τc2 ≦ 1. It is shown by both experiment and theory that the transient Overhauser effect in the solid state is much smaller than that expected for the liquid state. The 13C spin-lattice relaxation times of L-alanine, deutero- L-alanine, glycine, and L-serine were determined for the individual carbon atoms. The experimentally obtained 13C T1 values agree well with calculated ones, showing that the CH 3 group rotation provides the main source of the relaxation in alanine, while the NH 3+ group motion plays an important role for the relaxation in glycine and serene.

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy.

PubMed

Warner, Lisa; Gjersing, Erica; Follett, Shelby E; Elliott, K Wade; Dzyuba, Sergei V; Varga, Krisztina

2016-12-01

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentration of ionic liquids, has been challenging. In the present work the 13 C, 15 N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid - protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4 -mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6 to 3.5 M, which corresponds to 10%-60% v/v). Interactions between GB1 and [C 4 -mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15 N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4 -mim]Br were assigned using 3D methods under HR-MAS conditions. Thus, HR-MAS NMR is a viable tool that could aid in elucidation of the molecular mechanism of ionic liquid - protein interactions.

Comprehensive multiphase NMR spectroscopy: Basic experimental approaches to differentiate phases in heterogeneous samples

NASA Astrophysics Data System (ADS)

Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G.; Simpson, Myrna J.; Maas, Werner E.; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J.; Hume, Alan; Simpson, André J.

2012-04-01

Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate 1H and 13C spectra for the different phases. In addition, 19F performance is also addressed. To illustrate the capability of 19F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state.

Comprehensive multiphase NMR spectroscopy: basic experimental approaches to differentiate phases in heterogeneous samples.

PubMed

Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G; Simpson, Myrna J; Maas, Werner E; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Hume, Alan; Simpson, André J

2012-04-01

Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate (1)H and (13)C spectra for the different phases. In addition, (19)F performance is also addressed. To illustrate the capability of (19)F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state. Copyright © 2012 Elsevier Inc. All rights reserved.

Origin and Correction of Magnetic Field Inhomogeneity at the Interface in Biphasic NMR Samples

PubMed Central

Martin, Bryan T.; Chingas, G. C.

2012-01-01

The use of susceptibility matching to minimize spectral distortion of biphasic samples layered in a standard 5 mm NMR tube is described. The approach uses magic angle spinning (MAS) to first extract chemical shift differences by suppressing bulk magnetization. Then, using biphasic coaxial samples, magnetic susceptibilities are matched by titration with a paramagnetic salt. The matched phases are then layered in a standard NMR tube where they can be shimmed and examined. Line widths of two distinct spectral lines, selected to characterize homogeneity in each phase, are simultaneously optimized. Two-dimensional distortion-free, slice-resolved spectra of an octanol/water system illustrate the method. These data are obtained using a 2D stepped-gradient pulse sequence devised for this application. Advantages of this sequence over slice-selective methods are that acquisition efficiency is increased and processing requires only conventional software. PMID:22459062

Orbit of the mercury-manganese binary 41 Eridani

NASA Astrophysics Data System (ADS)

Hummel, C. A.; Schöller, M.; Duvert, G.; Hubrig, S.

2017-04-01

Context. Mercury-manganese (HgMn) stars are a class of slowly rotating chemically peculiar main-sequence late B-type stars. More than two-thirds of the HgMn stars are known to belong to spectroscopic binaries. Aims: By determining orbital solutions for binary HgMn stars, we will be able to obtain the masses for both components and the distance to the system. Consequently, we can establish the position of both components in the Hertzsprung-Russell diagram and confront the chemical peculiarities of the HgMn stars with their age and evolutionary history. Methods: We initiated a program to identify interferometric binaries in a sample of HgMn stars, using the PIONIER near-infrared interferometer at the VLTI on Cerro Paranal, Chile. For the detected systems, we intend to obtain full orbital solutions in conjunction with spectroscopic data. Results: The data obtained for the SB2 system 41 Eridani allowed the determination of the orbital elements with a period of just five days and a semi-major axis of under 2 mas. Including published radial velocity measurements, we derived almost identical masses of 3.17 ± 0.07 M⊙ for the primary and 3.07 ± 0.07 M⊙ for the secondary. The measured magnitude difference is less than 0.1 mag. The orbital parallax is 18.05 ± 0.17 mas, which is in good agreement with the Hipparcos trigonometric parallax of 18.33 ± 0.15 mas. The stellar diameters are resolved as well at 0.39 ± 0.03 mas. The spin rate is synchronized with the orbital rate. Based on observations made with ESO Telescopes at the La Silla Paranal Observatory under program IDs 088.C-0111, 189.C-0644, 090.D-0291, and 090.D-0917.

A cross-polarization based rotating-frame separated-local-field NMR experiment under ultrafast MAS conditions

NASA Astrophysics Data System (ADS)

Zhang, Rongchun; Damron, Joshua; Vosegaard, Thomas; Ramamoorthy, Ayyalusamy

2015-01-01

Rotating-frame separated-local-field solid-state NMR experiments measure highly resolved heteronuclear dipolar couplings which, in turn, provide valuable interatomic distances for structural and dynamic studies of molecules in the solid-state. Though many different rotating-frame SLF sequences have been put forth, recent advances in ultrafast MAS technology have considerably simplified pulse sequence requirements due to the suppression of proton-proton dipolar interactions. In this study we revisit a simple two-dimensional 1H-13C dipolar coupling/chemical shift correlation experiment using 13C detected cross-polarization with a variable contact time (CPVC) and systematically study the conditions for its optimal performance at 60 kHz MAS. In addition, we demonstrate the feasibility of a proton-detected version of the CPVC experiment. The theoretical analysis of the CPVC pulse sequence under different Hartmann-Hahn matching conditions confirms that it performs optimally under the ZQ (w1H - w1C = ±wr) condition for polarization transfer. The limits of the cross polarization process are explored and precisely defined as a function of offset and Hartmann-Hahn mismatch via spin dynamics simulation and experiments on a powder sample of uniformly 13C-labeled L-isoleucine. Our results show that the performance of the CPVC sequence and subsequent determination of 1H-13C dipolar couplings are insensitive to 1H/13C frequency offset frequency when high RF fields are used on both RF channels. Conversely, the CPVC sequence is quite sensitive to the Hartmann-Hahn mismatch, particularly for systems with weak heteronuclear dipolar couplings. We demonstrate the use of the CPVC based SLF experiment as a tool to identify different carbon groups, and hope to motivate the exploration of more sophisticated 1H detected avenues for ultrafast MAS.

Paramagnet induced signal quenching in MAS-DNP experiments in frozen homogeneous solutions

NASA Astrophysics Data System (ADS)

Corzilius, Björn; Andreas, Loren B.; Smith, Albert A.; Ni, Qing Zhe; Griffin, Robert G.

2014-03-01

The effects of nuclear signal quenching induced by the presence of a paramagnetic polarizing agent are documented for conditions used in magic angle spinning (MAS)-dynamic nuclear polarization (DNP) experiments on homogeneous solutions. In particular, we present a detailed analysis of three time constants: (1) the longitudinal build-up time constant TB for 1H; (2) the rotating frame relaxation time constant T1ρ for 1H and 13C and (3) T2 of 13C, the transverse relaxation time constant in the laboratory frame. These relaxation times were measured during microwave irradiation at a magnetic field of 5 T (140 GHz) as a function of the concentration of four polarizing agents: TOTAPOL, 4-amino-TEMPO, trityl (OX063), and Gd-DOTA and are compared to those obtained for a sample lacking paramagnetic doping. We also report the EPR relaxation time constants T1S and T2S, the DNP enhancements, ε, and the parameter E, defined below, which measures the sensitivity enhancement for the four polarizing agents as a function of the electron concentration. We observe substantial intensity losses (paramagnetic quenching) with all of the polarizing agents due to broadening mechanisms and cross relaxation during MAS. In particular, the monoradical trityl and biradical TOTAPOL induce ∼40% and 50% loss of signal intensity. In contrast there is little suppression of signal intensity in static samples containing these paramagnetic species. Despite the losses due to quenching, we find that all of the polarizing agents provide substantial gains in signal intensity with DNP, and in particular that the net enhancement is optimal for biradicals that operate with the cross effect. We discuss the possibility that much of this polarization loss can be regained with the development of instrumentation and methods to perform electron decoupling.

High resolution magic angle spinning NMR spectroscopy reveals that pectoralis muscle dystrophy in chicken is associated with reduced muscle content of anserine and carnosine.

PubMed

Sundekilde, Ulrik K; Rasmussen, Martin K; Young, Jette F; Bertram, Hanne Christine

2017-02-15

Increased incidences of pectoralis muscle dystrophy are observed in commercial chicken products, but the muscle physiological causes for the condition remain to be identified. In the present study a high-resolution magic angle spinning (HR-MAS) proton ((1)H) NMR spectroscopic examination of intact pectoralis muscle samples (n=77) were conducted to explore metabolite perturbations associated with the muscle dystrophy condition for the very first time. Both in chicken with an age of 21 and 31days, respectively, pectoralis muscle dystrophy was associated with a significantly lower content of anserine (p=0.034), carnosine (p=0.019) and creatine (p=0.049). These findings must be considered intriguing as they corroborate that characteristic muscle di-peptides composed of β-alanine and histidine derivatives such as anserine are extremely important in homeostasis of contractile muscles as a results of their role as buffering, anti-oxidative, and anti-glycation capacities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

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

Hou, Guangjin, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu; Lu, Xingyu, E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Vega, Alexander J., E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net

2014-09-14

We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {supmore » 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.« less

27Al MQMAS of the δ-Al 13-Keggin

DOE PAGES

Pilgrim, C. D.; Callahan, J. R.; Colla, C. A.; ...

2017-01-20

Here, one-dimensional 27Al, 23Na Magic-Angle-Spinning (MAS) NMR and 27Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the δ-isomer of the Al 13 Keggin structure at high spinning speed and 14.1 T field. Values for the CQ and η parameters are on the same scale as those seen in other isomers of the Al 13 structure. Density functional theory (DFT) calculations are performed for comparison to the experimental fits using the B3PW91/6-31+G* and PBE0/6-31+G* levels of theory, with the Polarizable Continuum Model (PCM).

Studies of phospholipid hydration by high-resolution magic-angle spinning nuclear magnetic resonance.

PubMed Central

Zhou, Z; Sayer, B G; Hughes, D W; Stark, R E; Epand, R M

1999-01-01

A sample preparation method using spherical glass ampoules has been used to achieve 1.5-Hz resolution in 1H magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of aqueous multilamellar dispersions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), serving to differentiate between slowly exchanging interlamellar and bulk water and to reveal new molecular-level information about hydration phenomena in these model biological membranes. The average numbers of interlamellar water molecules in multilamellar vesicles (MLVs) of DOPC and POPC were found to be 37.5 +/- 1 and 37.2 +/- 1, respectively, at a spinning speed of 3 kHz. Even at speeds as high as 9 kHz, the number of interlamellar waters remained as high as 31, arguing against dehydration effects for DOPC and POPC. Both homonuclear and heteronuclear nuclear Overhauser enhancement spectroscopy (NOESY and HOESY) were used to establish the location of water near the headgroup of a PC bilayer. 1H NMR comparisons of DOPC with a lipid that can hydrogen bond (monomethyldioleoylphosphatidylethanolamine, MeDOPE) showed the following trends: 1) the interlamellar water resonance was shifted to lower frequency for DOPC but to higher frequency for MeDOPE, 2) the chemical shift variation with temperature for interlamellar water was less than that of bulk water for MeDOPE MLVs, 3) water exchange between the two lipids was rapid on the NMR time scale if they were mixed in the same bilayer, 4) water exchange was slow if they were present in separate MLVs, and 5) exchange between bulk and interlamellar water was found by two-dimensional exchange experiments to be slow, and the exchange rate should be less than 157 Hz. These results illustrate the utility of ultra-high-resolution 1H MAS NMR for determining the nature and extent of lipid hydration as well as the arrangement of nuclei at the membrane/water interface. PMID:9876150

Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

PubMed Central

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2016-01-01

Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids. PMID:26801026

Strong-coupling induced damping of spin-echo modulations in magic-angle-spinning NMR: Implications for J coupling measurements in disordered solids

NASA Astrophysics Data System (ADS)

Guerry, Paul; Brown, Steven P.; Smith, Mark E.

2017-10-01

In the context of improving J coupling measurements in disordered solids, strong coupling effects have been investigated in the spin-echo and refocused INADEQUATE spin-echo (REINE) modulations of three- and four-spin systems under magic-angle-spinning (MAS), using density matrix simulations and solid-state NMR experiments on a cadmium phosphate glass. Analytical models are developed for the different modulation regimes, which are shown to be distinguishable in practice using Akaike's information criterion. REINE modulations are shown to be free of the damping that occurs for spin-echo modulations when the observed spin has the same isotropic chemical shift as its neighbour. Damping also occurs when the observed spin is bonded to a strongly-coupled pair. For mid-chain units, the presence of both direct and relayed damping makes both REINE and spin-echo modulations impossible to interpret quantitatively. We nonetheless outline how a qualitative comparison of the modulation curves can provide valuable information on disordered networks, possibly also pertaining to dynamic effects therein.

Solid State Nuclear Magnetic Resonance Studies of the Murchison Organic Macromolecule

NASA Technical Reports Server (NTRS)

Cody, G. D., III; Alexander, C. M. OD.; Tera, F.

2001-01-01

We have used high speed H-1 (DEPTH) and C-13 (VACP MAS-slow spinning) solid state NMR to determine the contributions of protonated vs non-protonated carbon in the Murchison Macromolecule. Additional information is contained in the original extended abstract.

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

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

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Dynamic Nuclear Polarization-Enhanced Biomolecular NMR Spectroscopy at High Magnetic Field with Fast Magic-Angle Spinning.

PubMed

Jaudzems, Kristaps; Bertarello, Andrea; Chaudhari, Sachin R; Pica, Andrea; Cala-De Paepe, Diane; Barbet-Massin, Emeline; Pell, Andrew J; Akopjana, Inara; Kotelovica, Svetlana; Gajan, David; Ouari, Olivier; Tars, Kaspars; Pintacuda, Guido; Lesage, Anne

2018-06-18

Dynamic nuclear polarization (DNP) is a powerful way to overcome the sensitivity limitation of magic-angle-spinning (MAS) NMR experiments. However, the resolution of the DNP NMR spectra of proteins is compromised by severe line broadening associated with the necessity to perform experiments at cryogenic temperatures and in the presence of paramagnetic radicals. High-quality DNP-enhanced NMR spectra of the Acinetobacter phage 205 (AP205) nucleocapsid can be obtained by combining high magnetic field (800 MHz) and fast MAS (40 kHz). These conditions yield enhanced resolution and long coherence lifetimes allowing the acquisition of resolved 2D correlation spectra and of previously unfeasible scalar-based experiments. This enables the assignment of aromatic resonances of the AP205 coat protein and its packaged RNA, as well as the detection of long-range contacts, which are not observed at room temperature, opening new possibilities for structure determination. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite-pulse and partially dipolar dephased multiCP for improved quantitative solid-state 13C NMR

NASA Astrophysics Data System (ADS)

Duan, Pu; Schmidt-Rohr, Klaus

2017-12-01

Improved multiple cross polarization (multiCP) pulse sequences for quickly acquiring quantitative 13C NMR spectra of organic solids are presented. Loss of 13C magnetization due to imperfect read-out and storage pulses in multiCP has been identified as a significant mechanism limiting polarization enhancement for 13C sites with weak couplings to 1H. This problem can be greatly reduced by composite 90° pulses with non-orthogonal phases that flip the magnetization onto the spin-lock field and back to the longitudinal direction for the 1H repolarization period; the observed loss is <3% for over ±10 kHz resonance offset and up to 20% flip-angle error. This composite-pulse multiCP (ComPmultiCP) sequence consistently provides performance superior to that of conventional multiCP, without any trade-off. The longer total CP time enabled by the composite pulses allows for a wider amplitude ramp during CP, which decreases the sensitivity to Hartmann-Hahn mismatch by a factor of two, with a <7% root-mean-square deviation within a 1-dB range for Boc-alanine. In samples with very short T1ρ, under-polarization of non-protonated carbons can be compensated by slight dipolar dephasing of CHn signals resulting from relatively weak decoupling during the Hahn spin echo period before detection. Quantitative spectra have been obtained by ComPmultiCP for low-crystallinity branched polyethylene at 4.5 kHz MAS, and in combination with partial dipolar dephasing for soil organic matter at 14 kHz MAS.

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

PubMed

Aimi, Keitaro; Ando, Shinji

2004-07-01

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. Copyright 2004 John Wiley & Sons, Ltd.

High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance of Intact Zebrafish Embryos Detects Metabolic Changes Following Exposure to Teratogenic Polymethoxyalkenes from Algae

PubMed Central

Roy, Upasana; Jaja-Chimedza, Asha; Sanchez, Kristel; Matysik, Joerg

2016-01-01

Abstract Techniques based on nuclear magnetic resonance (NMR) for imaging and chemical analyses of in vivo, or otherwise intact, biological systems are rapidly emerging and finding diverse applications within a wide range of fields. Very recently, several NMR-based techniques have been developed for the zebrafish as a model animal system. In the current study, the novel application of high-resolution magic angle spinning (HR-MAS) NMR is presented as a means of metabolic profiling of intact zebrafish embryos. Toward investigating the utility of HR-MAS NMR as a toxicological tool, these studies specifically examined metabolic changes of embryos exposed to polymethoxy-1-alkenes (PMAs)—a recently identified family of teratogenic compounds from freshwater algae—as emerging environmental contaminants. One-dimensional and two-dimensional HR-MAS NMR analyses were able to effectively identify and quantify diverse metabolites in early-stage (≤36 h postfertilization) embryos. Subsequent comparison of the metabolic profiles between PMA-exposed and control embryos identified several statistically significant metabolic changes associated with subacute exposure to the teratogen, including (1) elevated inositol as a recognized component of signaling pathways involved in embryo development; (2) increases in several metabolites, including inositol, phosphoryl choline, fatty acids, and cholesterol, which are associated with lipid composition of cell membranes; (3) concomitant increase in glucose and decrease in lactate; and (4) decreases in several biochemically related metabolites associated with central nervous system development and function, including γ-aminobutyric acid, glycine, glutamate, and glutamine. A potentially unifying model/hypothesis of PMA teratogenicity based on the data is presented. These findings, taken together, demonstrate that HR-MAS NMR is a promising tool for metabolic profiling in the zebrafish embryo, including toxicological applications. PMID:27348393

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

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

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

DOE PAGES

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.; ...

2016-08-11

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

Obtaining aluminas from the thermal decomposition of their different precursors: An {sup 27}Al MAS NMR and X-ray powder diffraction studies

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

Chagas, L.H.; De Carvalho, G.S.G.; San Gil, R.A.S.

2014-01-01

Graphical abstract: - Highlights: • We synthesized three precursors of alumina from different methods. • The calcination of the precursors generated several alumina polymorphs. • XRD and NMR were used for structural investigation of the polymorphs. • The synthesis route determines the structural and textural properties of the solids. - Abstract: A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. The characteristics of the four precursors were investigated by thermal, vibrationalmore » and X-ray powder diffraction (XRD) analysis. Additionally, the nuclear magnetic resonance, with magic angle spinning ({sup 27}Al MAS NMR), was used to verify the coordination of aluminum cations. Each precursor was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and {sup 27}Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al{sub 2}O{sub 3} phase, which in addition to structural investigation was subjected to textural analysis. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties, which in turn can significantly influence the performance of a supported catalyst.« less

Decomposition of adsorbed VX on activated carbons studied by {sup 31}P MAS NMR

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

Ishay Columbus; Daniel Waysbort; Liora Shmueli

2006-06-15

The fate of the persistent OP nerve agent O-ethyl S-(2-(diisopropylamino)ethyl) methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. Four types of activated carbon were used, including coal-based BPL. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) ((DES){sub 2}). Decomposition occurred irrespective of the phase from which VX was loaded,more » the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. 17 refs., 6 figs., 3 tabs.« less

The metabolic profile of lemon juice by proton HR-MAS NMR: the case of the PGI Interdonato Lemon of Messina.

PubMed

Cicero, Nicola; Corsaro, Carmelo; Salvo, Andrea; Vasi, Sebastiano; Giofré, Salvatore V; Ferrantelli, Vincenzo; Di Stefano, Vita; Mallamace, Domenico; Dugo, Giacomo

2015-01-01

We have studied by means of High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) the metabolic profile of the famous Sicilian lemon known as 'Interdonato Lemon of Messina PGI'. The PGI Interdonato Lemon of Messina possesses high organoleptic and healthy properties and is recognised as one of the most nutrient fruits. In particular, some of its constituents are actively studied for their chemo-preventive and therapeutic properties. In this paper, we have determined by means of HR-MAS NMR spectroscopy the molar concentration of the main metabolites constituent the juice of PGI Interdonato Lemon of Messina in comparison with that of the not-PGI Interdonato Lemon of Turkey. Our aim is to develop an analytical technique, in order to determine a metabolic fingerprint able to reveal commercial frauds in national and international markets.

Broadband MAS NMR spectroscopy in the low-power limit

NASA Astrophysics Data System (ADS)

Sanders, Kevin J.; Pell, Andrew J.; Wegner, Sebastian; Grey, Clare P.; Pintacuda, Guido

2018-04-01

We investigate the performance of broadband adiabatic inversion pulses in the high-power (short high-powered adiabatic pulse, SHAP) and low-power (single-sideband-selective adiabatic pulse, S3AP) RF regimes on a spin system subjected to large anisotropic interactions. We show by combined experimental results and spin dynamics simulations that when the magic-angle spinning rate exceeds 100 kHz S3APs begin outperforming SHAPs. This is especially true for low-gamma nuclei, such as 6 Li in paramagnetic Li-ion battery materials. Finally, we show how S3APs can be improved by combining multiple waveforms sweeping over multiple sidebands simultaneously, in order to produce inverted sideband profiles free from intensity biasing.

Structural characterisation of the Li argyrodites Li7PS6 and Li7PSe6 and their solid solutions: quantification of site preferences by MAS-NMR spectroscopy.

PubMed

Kong, Shiao Tong; Gün, Ozgül; Koch, Barbara; Deiseroth, Hans Jörg; Eckert, Hellmut; Reiner, Christof

2010-05-03

Li(7)PS(6) and Li(7)PSe(6) belong to a class of new solids that exhibit high Li(+) mobility. A series of quaternary solid solutions Li(7)PS(6-x)Se(x) (0 < or = x < or = 6) were characterised by X-ray crystallography and magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The high-temperature (HT) modifications were studied by single-crystal investigations (both F43m, Z=4, Li(7)PS(6): a=9.993(1) A, Li(7)PSe(6): a=10.475(1) A) and show the typical argyrodite structures with strongly disordered Li atoms. HT-Li(7)PS(6) and HT-Li(7)PSe(6) transform reversibly into low-temperature (LT) modifications with ordered Li atoms. X-ray powder diagrams show the structures of LT-Li(7)PS(6) and LT-Li(7)PSe(6) to be closely related to orthorhombic LT-alpha-Cu(7)PSe(6). Single crystals of the LT modifications are not available due to multiple twinning and formation of antiphase domains. The gradual substitution of S by Se shows characteristic site preferences closely connected to the functionalities of the different types of chalcogen atoms (S, Se). High-resolution solid-state (31)P NMR is a powerful method to differentiate quantitatively between the distinct (PS(4-n)Se(n))(3-) local environments. Their population distribution differs significantly from a statistical scenario, revealing a pronounced preference for P-S over P-Se bonding. This preference, shown for the series of LT samples, can be quantified in terms of an equilibrium constant specifying the melt reaction Se(P)+S(2-) <==>S(P)+Se(2-), prior to crystallisation. The (77)Se MAS-NMR spectra reveal that the chalcogen distributions in the second and third coordination sphere of the P atoms are essentially statistical. The number of crystallographically independent Li atoms in both LT modifications was analysed by means of (6)Li{(7)Li} cross polarisation magic angle spinning (CPMAS).

Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy

2015-10-01

Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110-120 kHz), 1H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong 1H-1H homonuclear dipolar couplings and narrow 1H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) 1H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about 1H-1H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical information for a variety of solid systems that possess high proton density.

Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

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

Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2015-10-14

Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which rendermore » it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) {sup 1}H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about {sup 1}H–{sup 1}H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical information for a variety of solid systems that possess high proton density.« less

Solid-state selective (13)C excitation and spin diffusion NMR to resolve spatial dimensions in plant cell walls.

PubMed

Foston, Marcus; Katahira, Rui; Gjersing, Erica; Davis, Mark F; Ragauskas, Arthur J

2012-02-15

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 (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. (13)C spin diffusion time constants (T(SD)) were extracted using a two-site spin diffusion theory developed for (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 (13)C enriched corn stover stem reveal that the lignin carbons are, on average, located at distances ∼0.7-2.0 nm from the carbons in hemicellulose and cellulose, whereas the pretreated material had larger separations.

Compensated second-order recoupling: application to third spin assisted recoupling†

PubMed Central

Giffard, Mathilde; Hediger, Sabine; Lewandowski, Józef R.; Bardet, Michel; Simorre, Jean-Pierre; Griffin, Robert G.; De Paëpe, Gaël

2015-01-01

We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-γ nuclei (13C–13C, 15N–15N, 15N–13C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U–[15N, 13C]-YajG) at high magnetic fields (up to 900 MHz 1H frequency) and fast sample spinning (up to 65 kHz MAS frequency). PMID:22513727

Determination of alcohol and extract concentration in beer samples using a combined method of near-infrared (NIR) spectroscopy and refractometry.

PubMed

Castritius, Stefan; Kron, Alexander; Schäfer, Thomas; Rädle, Matthias; Harms, Diedrich

2010-12-22

A new approach of combination of near-infrared (NIR) spectroscopy and refractometry was developed in this work to determine the concentration of alcohol and real extract in various beer samples. A partial least-squares (PLS) regression, as multivariate calibration method, was used to evaluate the correlation between the data of spectroscopy/refractometry and alcohol/extract concentration. This multivariate combination of spectroscopy and refractometry enhanced the precision in the determination of alcohol, compared to single spectroscopy measurements, due to the effect of high extract concentration on the spectral data, especially of nonalcoholic beer samples. For NIR calibration, two mathematical pretreatments (first-order derivation and linear baseline correction) were applied to eliminate light scattering effects. A sample grouping of the refractometry data was also applied to increase the accuracy of the determined concentration. The root mean squared errors of validation (RMSEV) of the validation process concerning alcohol and extract concentration were 0.23 Mas% (method A), 0.12 Mas% (method B), and 0.19 Mas% (method C) and 0.11 Mas% (method A), 0.11 Mas% (method B), and 0.11 Mas% (method C), respectively.

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

USGS Publications Warehouse

Ebert, L.B.; Robbins, E.I.; Rose, K.D.; Kastrup, R.V.; Scanlon, J.C.; Gebhard, L.A.; Garcia, A.R.

1990-01-01

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HClHF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C ratios, X-ray diffraction (XRD), 13C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp2-hybridized and 20% is sp3-hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300??C shows that the materials examined have not previously been subjected to temperatures as high as 300??C. ?? 1990.

Biopolymer nanocomposite films reinforced with nanocellulose whiskers

Treesearch

Amit Saxena; Marcus Foston; Mohamad Kassaee; Thomas J. Elder; Arthur J. Ragauskas

2011-01-01

A xylan nanocomposite film with improved strength and barrier properties was prepared by a solution casting using nanocellulose whiskers as a reinforcing agent. The 13C cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) analysis of the spectral data obtained for the NCW/xylan nanocomposite films indicated the signal intensity originating...

Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR

PubMed Central

2015-01-01

We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as 1H–13C and 1H–15N HETCOR or 13C–13C INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs. PMID:26393368

Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

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

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2016-01-21

Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and themore » use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t{sub 1} and t{sub 3} periods, respectively. In addition to through-space and through-bond {sup 13}C/{sup 1}H and {sup 13}C/{sup 13}C chemical shift correlations, the 3D {sup 1}H/{sup 13}C/{sup 1}H experiment also provides a COSY-type {sup 1}H/{sup 1}H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ({sup 1}H/{sup 1}H chemical shift correlation spectrum) at different {sup 13}C chemical shift frequencies from the 3D {sup 1}H/{sup 13}C/{sup 1}H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D {sup 1}H/{sup 13}C/{sup 1}H experiment would be useful to study the structure and dynamics of a variety of chemical and biological solids.« less

Insight into small molecule binding to the neonatal Fc receptor by X-ray crystallography and 100 kHz magic-angle-spinning NMR

PubMed Central

Macpherson, Alex; Smith-Penzel, Susanne; Basse, Nicolas; Lecomte, Fabien; Deboves, Hervé; Taylor, Richard D.; Norman, Tim; Porter, John; Waters, Lorna C.; Westwood, Marta; Cossins, Ben; Cain, Katharine; White, James; Griffin, Robert; Prosser, Christine; Kelm, Sebastian; Sullivan, Amy H.; Fox, David; Carr, Mark D.; Henry, Alistair; Taylor, Richard; Meier, Beat H.; Oschkinat, Hartmut; Lawson, Alastair D.

2018-01-01

Aiming at the design of an allosteric modulator of the neonatal Fc receptor (FcRn)–Immunoglobulin G (IgG) interaction, we developed a new methodology including NMR fragment screening, X-ray crystallography, and magic-angle-spinning (MAS) NMR at 100 kHz after sedimentation, exploiting very fast spinning of the nondeuterated soluble 42 kDa receptor construct to obtain resolved proton-detected 2D and 3D NMR spectra. FcRn plays a crucial role in regulation of IgG and serum albumin catabolism. It is a clinically validated drug target for the treatment of autoimmune diseases caused by pathogenic antibodies via the inhibition of its interaction with IgG. We herein present the discovery of a small molecule that binds into a conserved cavity of the heterodimeric, extracellular domain composed of an α-chain and β2-microglobulin (β2m) (FcRnECD, 373 residues). X-ray crystallography was used alongside NMR at 100 kHz MAS with sedimented soluble protein to explore possibilities for refining the compound as an allosteric modulator. Proton-detected MAS NMR experiments on fully protonated [13C,15N]-labeled FcRnECD yielded ligand-induced chemical-shift perturbations (CSPs) for residues in the binding pocket and allosteric changes close to the interface of the two receptor heterodimers present in the asymmetric unit as well as potentially in the albumin interaction site. X-ray structures with and without ligand suggest the need for an optimized ligand to displace the α-chain with respect to β2m, both of which participate in the FcRnECD–IgG interaction site. Our investigation establishes a method to characterize structurally small molecule binding to nondeuterated large proteins by NMR, even in their glycosylated form, which may prove highly valuable for structure-based drug discovery campaigns. PMID:29782488

Insight into small molecule binding to the neonatal Fc receptor by X-ray crystallography and 100 kHz magic-angle-spinning NMR.

PubMed

Stöppler, Daniel; Macpherson, Alex; Smith-Penzel, Susanne; Basse, Nicolas; Lecomte, Fabien; Deboves, Hervé; Taylor, Richard D; Norman, Tim; Porter, John; Waters, Lorna C; Westwood, Marta; Cossins, Ben; Cain, Katharine; White, James; Griffin, Robert; Prosser, Christine; Kelm, Sebastian; Sullivan, Amy H; Fox, David; Carr, Mark D; Henry, Alistair; Taylor, Richard; Meier, Beat H; Oschkinat, Hartmut; Lawson, Alastair D

2018-05-01

Aiming at the design of an allosteric modulator of the neonatal Fc receptor (FcRn)-Immunoglobulin G (IgG) interaction, we developed a new methodology including NMR fragment screening, X-ray crystallography, and magic-angle-spinning (MAS) NMR at 100 kHz after sedimentation, exploiting very fast spinning of the nondeuterated soluble 42 kDa receptor construct to obtain resolved proton-detected 2D and 3D NMR spectra. FcRn plays a crucial role in regulation of IgG and serum albumin catabolism. It is a clinically validated drug target for the treatment of autoimmune diseases caused by pathogenic antibodies via the inhibition of its interaction with IgG. We herein present the discovery of a small molecule that binds into a conserved cavity of the heterodimeric, extracellular domain composed of an α-chain and β2-microglobulin (β2m) (FcRnECD, 373 residues). X-ray crystallography was used alongside NMR at 100 kHz MAS with sedimented soluble protein to explore possibilities for refining the compound as an allosteric modulator. Proton-detected MAS NMR experiments on fully protonated [13C,15N]-labeled FcRnECD yielded ligand-induced chemical-shift perturbations (CSPs) for residues in the binding pocket and allosteric changes close to the interface of the two receptor heterodimers present in the asymmetric unit as well as potentially in the albumin interaction site. X-ray structures with and without ligand suggest the need for an optimized ligand to displace the α-chain with respect to β2m, both of which participate in the FcRnECD-IgG interaction site. Our investigation establishes a method to characterize structurally small molecule binding to nondeuterated large proteins by NMR, even in their glycosylated form, which may prove highly valuable for structure-based drug discovery campaigns.

The aluminum ordering in aluminosilicates: a dipolar 27Al NMR spectroscopy study.

PubMed

Gee, Becky A

2004-01-01

The spatial ordering of aluminum atoms in CsAl(SiO3)2 and 3Al2O3.2SiO2 was probed by 27Al dipolar solid-state NMR spectroscopy. The 27Al response to a Hahn spin-echo pulse sequence in a series of aluminum-containing model crystalline compounds demonstrates that quantitative 27Al homonuclear dipolar second moments can be obtained to within +/-20% of the theoretical values, if evaluation of the spin-echo response curve is limited to short evolution periods (2t1 < or = 0.10 ms). Additionally, selective excitation of the central transition m = 1/2 --> -1/2 is necessary in order to ensure quantitative results. Restriction of spin exchange affecting the dephasing of the magnetization may decelerate the spin-echo decay at longer evolution periods. Considering these restraints, the method was used to probe the spatial distribution of aluminum atoms among the tetrahedral sites in two aluminosilicate materials. Experimental 27Al spin-echo response data for the aluminosilicates CsAl(SiO3)2 (synthetic pollucite) and 3Al2O3.2SiO2 (mullite) are compared with theoretical data based on (I) various degrees of aluminum-oxygen-aluminum bond formation among tetrahedrally coordinated aluminum atoms (Al(T(d) )-O-Al(T(d) )) and (II) the maximum avoidance of Al(T(d) )-O-Al(T(d) ) bonding. Analysis of the second moment values and resulting echo decay responses suggests that partial suppression of spin exchange among aluminum atoms in crystallographically distinct sites may contribute to the 27Al spin echo decay in 3Al2O3.2SiO2, thus complicating quantitative analysis of the data. Silicon-29 and aluminum-27 magic angle spinning (MAS) NMR spectra of 3Al2O3.2SiO2 are consistent with those previously reported. The experimental 27Al spin-echo response behavior of CsAl(SiO3)2 differs from the theoretical response behavior based on the maximum avoidance of Al-O-Al bonding between tetrahedral aluminum sites in CsAl(SiO3)2. A single unresolved resonance is observed in both the silicon-29 and aluminum-27 MAS spectra of CsAl(SiO3)2. Copyright 2003 John Wiley & Sons, Ltd.

HR-MAS MR Spectroscopy of Breast Cancer Tissue Obtained with Core Needle Biopsy: Correlation with Prognostic Factors

PubMed Central

Choi, Ji Soo; Baek, Hyeon-Man; Kim, Suhkmann; Kim, Min Jung; Youk, Ji Hyun; Moon, Hee Jung; Kim, Eun-Kyung; Han, Kyung Hwa; Kim, Dong-hyun; Kim, Seung Il; Koo, Ja Seung

2012-01-01

The purpose of this study was to examine the correlation between high-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopy using core needle biopsy (CNB) specimens and histologic prognostic factors currently used in breast cancer patients. After institutional review board approval and informed consent were obtained for this study, CNB specimens were collected from 36 malignant lesions in 34 patients. Concentrations and metabolic ratios of various choline metabolites were estimated by HR-MAS MR spectroscopy using CNB specimens. HR-MAS spectroscopic values were compared according to histopathologic variables [tumor size, lymph node metastasis, histologic grade, status of estrogens receptor (ER), progesterone receptor (PR), HER2 (a receptor for human epidermal growth factor), and Ki-67, and triple negativity]. Multivariate analysis was performed with Orthogonal Projections to Latent Structure-Discriminant Analysis (OPLS-DA). HR-MAS MR spectroscopy quantified and discriminated choline metabolites in all CNB specimens of the 36 breast cancers. Several metabolite markers [free choline (Cho), phosphocholine (PC), creatine (Cr), taurine, myo-inositol, scyllo-inositol, total choline (tCho), glycine, Cho/Cr, tCho/Cr, PC/Cr] on HR-MAS MR spectroscopy were found to correlate with histologic prognostic factors [ER, PR, HER2, histologic grade, triple negativity, Ki-67, poor prognosis]. OPLS-DA multivariate models were generally able to discriminate the status of histologic prognostic factors (ER, PR, HER2, Ki-67) and prognosis groups. Our study suggests that HR-MAS MR spectroscopy using CNB specimens can predict tumor aggressiveness prior to surgery in breast cancer patients. In addition, it may be helpful in the detection of reliable markers for breast cancer characterization. PMID:23272149

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

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

2013-01-01

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

Transitions in Al Coordination during Gibbsite Crystallization Using High-Field 27 Al and 23 Na MAS NMR Spectroscopy

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

Hu, Jian Zhi; Zhang, Xin; Jaegers, Nicholas R.

Mechanisms of nucleation and growth of Al hydroxides such as gibbsite from aqueous solution, particularly in highly alkaline conditions, remain poorly understood. In this work, quantitative 27Al and 22Na MAS NMR experiments were conducted on solid samples extracted from the crystallization of gibbsite from an amorphous aluminum hydroxide gel precursor. The use of high magnetic field and fast sample spinning allowed transitional tetrahedral (AlT) and pentahedral (AlP) aluminum species to be observed along with the octahedral aluminum (AlO) that dominates the gibbsite product. Low-coordinated Al species could be detected at concentrations as low as 0.1% of the total Al sites.more » It is established that (a) AlT and AlP coexist on the surface of growing gibbsites even with a combined percentage over the total Al sites of less than 1%; (b) Different synthesis methods generate gibbsite with varying amounts of low-coordinated Al; (c) the amorphous gel precursor contains a significant amount of low-coordinated Al sites with AO: AlP: AlT ratios of approximately 4:2:1; (d) upon hydration, the external, low-coordinated Al sites become six-fold coordinated by interacting with the oxygen in H2O and the 27Al MAS NMR peak position shifts to that for the AlO sites; (e) gibbsite with increased long range order is synthesized over longer times by gradually incorporating residual AlP and AlT sites into octahedrally-coordinated AlO sites; (f) trace Na is predominantly a surface species on gibbsite particles. These findings provide a basis for understanding the gibbsite crystallization mechanism, along with a general means of characterizing gibbsite surface properties that are of equal importance for understanding related processes such as dissolution behavior.« less

The effect of single and repeated UVB radiation on rabbit cornea.

PubMed

Fris, Miroslav; Tessem, May-Britt; Cejková, Jitka; Midelfart, Anna

2006-12-01

Cumulative effect of ultraviolet radiation (UVR) is an important aspect of UV corneal damage. The purpose of this study was to apply high resolution magic angle spinning proton nuclear magnetic resonance (HR-MAS 1H NMR) spectroscopy to evaluate the effect of single and repeated UV radiation exposure of the same overall dose on the rabbit cornea. Corneal surfaces of 24 normal rabbit eyes were examined for the effects of UVB exposure (312 nm). In the first group (UVB1), animals were irradiated with a single dose (3.12 J/cm2; 21 min) of UVB radiation. The animals in the second group (UVB2) were irradiated three times for 7 min every other day (dose of 1.04 J/cm2; days 1, 3, 5) to give the same overall dose (3.12 J/cm2). The third group served as an untreated control group. One day after the last irradiation, the animals were sacrificed, and the corneas were removed and frozen. HR-MAS 1H NMR spectra from intact corneas were obtained. Special grouping patterns among the tissue samples and the relative percentage changes in particular metabolite concentrations were evaluated using modern statistical methods (multivariate analysis, one-way ANOVA). The metabolic profile of both groups of UVB-irradiated samples was significantly different from the control corneas. Substantial decreases in taurine, hypo-taurine and choline-derivatives concentrations and substantial elevation in glucose and betaine levels were observed following the UVR exposure. There was no significant difference between the effect of a single and repeated UVB irradiation of the same overall dose. For the first time, the effects of single and repeated UVR doses on the metabolic profile of the rabbit cornea were analysed and compared. The combination of HR-MAS 1H NMR spectroscopy and modern statistical methods (multivariate analysis, one-way ANOVA) proved suitable to assess the overall view of the metabolic alterations in the rabbit corneal tissue following UVB radiation exposure.

Metabolomics of Breast Cancer Using High-Resolution Magic Angle Spinning Magnetic Resonance Spectroscopy: Correlations with 18F-FDG Positron Emission Tomography-Computed Tomography, Dynamic Contrast-Enhanced and Diffusion-Weighted Imaging MRI.

PubMed

Yoon, Haesung; Yoon, Dahye; Yun, Mijin; Choi, Ji Soo; Park, Vivian Youngjean; Kim, Eun-Kyung; Jeong, Joon; Koo, Ja Seung; Yoon, Jung Hyun; Moon, Hee Jung; Kim, Suhkmann; Kim, Min Jung

2016-01-01

Our goal in this study was to find correlations between breast cancer metabolites and conventional quantitative imaging parameters using high-resolution magic angle spinning (HR-MAS) magnetic resonance spectroscopy (MRS) and to find breast cancer subgroups that show high correlations between metabolites and imaging parameters. Between August 2010 and December 2013, we included 53 female patients (mean age 49.6 years; age range 32-75 years) with a total of 53 breast lesions assessed by the Breast Imaging Reporting and Data System. They were enrolled under the following criteria: breast lesions larger than 1 cm in diameter which 1) were suspicious for malignancy on mammography or ultrasound (US), 2) were pathologically confirmed to be breast cancer with US-guided core-needle biopsy (CNB) 3) underwent 3 Tesla MRI with dynamic contrast-enhanced (DCE) and diffusion-weighted imaging (DWI) and positron emission tomography-computed tomography (PET-CT), and 4) had an attainable immunohistochemistry profile from CNB. We acquired spectral data by HR-MAS MRS with CNB specimens and expressed the data as relative metabolite concentrations. We compared the metabolites with the signal enhancement ratio (SER), maximum standardized FDG uptake value (SUV max), apparent diffusion coefficient (ADC), and histopathologic prognostic factors for correlation. We calculated Spearman correlations and performed a partial least squares-discriminant analysis (PLS-DA) to further classify patient groups into subgroups to find correlation differences between HR-MAS spectroscopic values and conventional imaging parameters. In a multivariate analysis, the PLS-DA models built with HR-MAS MRS metabolic profiles showed visible discrimination between high and low SER, SUV, and ADC. In luminal subtype breast cancer, compared to all cases, high SER, ADV, and SUV were more closely clustered by visual assessment. Multiple metabolites were correlated with SER and SUV in all cases. Multiple metabolites showed correlations with SER and SUV in the ER positive, HER2 negative, and Ki-67 negative groups. High levels of PC, choline, and glycine acquired from HR-MAS MRS using CNB specimens were noted in the high SER group via DCE MRI and the high SUV group via PET-CT, with significant correlations between choline and SER and between PC and SUV. Further studies should investigate whether HR-MAS MRS using CNB specimens can provide similar or more prognostic information than conventional quantitative imaging parameters.

Dynamic Nuclear Polarization Study of Inhibitor Binding to the M218–60 Proton Transporter from Influenza A

PubMed Central

Andreas, Loren B.; Barnes, Alexander B.; Corzilius, Björn; Chou, James J.; Miller, Eric A.; Caporini, Marc; Rosay, Melanie; Griffin, Robert G

2013-01-01

We demonstrate the use of dynamic nuclear polarization (DNP) to elucidate ligand binding to a membrane protein using dipolar recoupling magic angle spinning (MAS) NMR. In particular, we detect drug binding in the proton transporter M218–60 from influenza A using recoupling experiments at room temperature and with cryogenic DNP. The results indicate that the pore binding site of rimantadine is correlated with previously reported widespread chemical shift changes, suggesting functional binding in the pore. Futhermore, the 15N labeled ammonium of rimantadine was observed near A30 13Cβ and G34 13Cα suggesting a possible hydrogen bond to A30 Carbonyl. Cryogenic DNP was required to observe the weaker external binding site(s) in a ZF-TEDOR spectrum. This approach is generally applicable, particularly for weakly bound ligands, in which case the application of MAS NMR dipolar recoupling requires the low temperatures to quench dynamic exchange processes. For the fully protonated samples investigated, we observed DNP signal enhancements of ~10 at 400 MHz using only 4–6 mM of the polarizing agent TOTAPOL. At 600 MHz and with DNP, we measured a distance between the drug and the protein to a precision of 0.2 Å. PMID:23480101

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

PubMed

Brown, Steven P

2012-02-01

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-π 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. Copyright © 2011 Elsevier Inc. All rights reserved.

Methodological quality of meta-analyses on treatments for chronic obstructive pulmonary disease: a cross-sectional study using the AMSTAR (Assessing the Methodological Quality of Systematic Reviews) tool.

PubMed

Ho, Robin S T; Wu, Xinyin; Yuan, Jinqiu; Liu, Siya; Lai, Xin; Wong, Samuel Y S; Chung, Vincent C H

2015-01-08

Meta-analysis (MA) of randomised trials is considered to be one of the best approaches for summarising high-quality evidence on the efficacy and safety of treatments. However, methodological flaws in MAs can reduce the validity of conclusions, subsequently impairing the quality of decision making. To assess the methodological quality of MAs on COPD treatments. A cross-sectional study on MAs of COPD trials. MAs published during 2000-2013 were sampled from the Cochrane Database of Systematic Reviews and Database of Abstracts of Reviews of Effect. Methodological quality was assessed using the validated AMSTAR (Assessing the Methodological Quality of Systematic Reviews) tool. Seventy-nine MAs were sampled. Only 18% considered the scientific quality of primary studies when formulating conclusions and 49% used appropriate meta-analytic methods to combine findings. The problems were particularly acute among MAs on pharmacological treatments. In 48% of MAs the authors did not report conflict of interest. Fifty-eight percent reported harmful effects of treatment. Publication bias was not assessed in 65% of MAs, and only 10% had searched non-English databases. The methodological quality of the included MAs was disappointing. Consideration of scientific quality when formulating conclusions should be made explicit. Future MAs should improve on reporting conflict of interest and harm, assessment of publication bias, prevention of language bias and use of appropriate meta-analytic methods.

Methodological quality of meta-analyses on treatments for chronic obstructive pulmonary disease: a cross-sectional study using the AMSTAR (Assessing the Methodological Quality of Systematic Reviews) tool

PubMed Central

Ho, Robin ST; Wu, Xinyin; Yuan, Jinqiu; Liu, Siya; Lai, Xin; Wong, Samuel YS; Chung, Vincent CH

2015-01-01

Background: Meta-analysis (MA) of randomised trials is considered to be one of the best approaches for summarising high-quality evidence on the efficacy and safety of treatments. However, methodological flaws in MAs can reduce the validity of conclusions, subsequently impairing the quality of decision making. Aims: To assess the methodological quality of MAs on COPD treatments. Methods: A cross-sectional study on MAs of COPD trials. MAs published during 2000–2013 were sampled from the Cochrane Database of Systematic Reviews and Database of Abstracts of Reviews of Effect. Methodological quality was assessed using the validated AMSTAR (Assessing the Methodological Quality of Systematic Reviews) tool. Results: Seventy-nine MAs were sampled. Only 18% considered the scientific quality of primary studies when formulating conclusions and 49% used appropriate meta-analytic methods to combine findings. The problems were particularly acute among MAs on pharmacological treatments. In 48% of MAs the authors did not report conflict of interest. Fifty-eight percent reported harmful effects of treatment. Publication bias was not assessed in 65% of MAs, and only 10% had searched non-English databases. Conclusions: The methodological quality of the included MAs was disappointing. Consideration of scientific quality when formulating conclusions should be made explicit. Future MAs should improve on reporting conflict of interest and harm, assessment of publication bias, prevention of language bias and use of appropriate meta-analytic methods. PMID:25569783

Determination of the structural changes by Raman and {sup 13}C CP/MAS NMR spectroscopy on native corn starch with plasticizers

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

Cozar, O.; Filip, C.; Tripon, C.

The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and {sup 13}C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

On the crystal structure of the vaterite polymorph of CaCO3: a calcium-43 solid-state NMR and computational assessment.

PubMed

Burgess, Kevin M N; Bryce, David L

2015-02-01

The vaterite polymorph of CaCO3 has puzzled crystallographers for decades in part due to difficulties in obtaining single crystals. The multiple proposed structures for the vaterite polymorph of CaCO3 are assessed using a combined (43)Ca solid-state nuclear magnetic resonance (SSNMR) spectroscopic and computational approach. A combination of improved experimental and computational methods, along with a calibrated chemical shift scale and (43)Ca nuclear quadrupole moment, allow for improved insights relative to our earlier work (Bryce et al., J. Am. Chem. Soc. 2008, 130, 9282). Here, we synthesize a (43)Ca isotopically-enriched sample of vaterite and perform high-resolution quadrupolar SSNMR experiments including magic-angle spinning (MAS), double-rotation (DOR), and multiple-quantum (MQ) MAS experiments at magnetic field strengths of 9.4 and 21.1T. We identify one crystallographically unique Ca(2+) site in vaterite with a slight distribution in both chemical shifts and quadrupolar parameters. Both the experimental (43)Ca electric field gradient tensor and the isotropic chemical shift for vaterite are compared to those calculated with the gauge-including projector-augmented-wave (GIPAW) DFT method in an attempt to identify the model that best represents the crystal structure of vaterite. Simulations of (43)Ca DOR and MAS NMR spectra based on the NMR parameters computed for a total of 18 structural models for vaterite allow us to distinguish between these models. Among these 18, the P3221 and C2 structures provide simulated spectra and diffractograms in best agreement with all experimental data. Copyright © 2014 Elsevier Inc. All rights reserved.

Evaluation of efficiency of nested multiplex allele-specific PCR assay for detection of multidrug resistant tuberculosis directly from sputum samples.

PubMed

Mistri, S K; Sultana, M; Kamal, S M M; Alam, M M; Irin, F; Nessa, J; Ahsan, C R; Yasmin, M

2016-05-01

For an effective control of tuberculosis, rapid detection of multidrug resistant tuberculosis (MDR-TB) is necessary. Therefore, we developed a modified nested multiplex allele-specific polymerase chain reaction (MAS-PCR) method that enables rapid MDR-TB detection directly from sputum samples. The efficacy of this method was evaluated using 79 sputum samples collected from suspected tuberculosis patients. The performance of nested MAS-PCR method was compared with other MDR-TB detection methods like drug susceptibility testing (DST) and DNA sequencing. As rifampicin (RIF) resistance conforms to MDR-TB in greater than 90% cases, only the presence of RIF-associated mutations in rpoB gene was determined by DNA sequencing and nested MAS-PCR to detect MDR-TB. The concordance between nested MAS-PCR and DNA sequencing results was found to be 96·3%. When compared with DST, the sensitivity and specificity of nested MAS-PCR for RIF-resistance detection were determined to be 92·9 and 100% respectively. For developing- and high-TB burden countries, molecular-based tests have been recommended by the World Health Organization for rapid detection of MDR-TB. The results of this study indicate that, nested MAS-PCR assay might be a practical and relatively cost effective molecular method for rapid detection of MDR-TB from suspected sputum samples in developing countries with resource poor settings. © 2016 The Society for Applied Microbiology.

Quantitative analysis of backbone dynamics in a crystalline protein from nitrogen-15 spin-lattice relaxation.

PubMed

Giraud, Nicolas; Blackledge, Martin; Goldman, Maurice; Böckmann, Anja; Lesage, Anne; Penin, François; Emsley, Lyndon

2005-12-28

A detailed analysis of nitrogen-15 longitudinal relaxation times in microcrystalline proteins is presented. A theoretical model to quantitatively interpret relaxation times is developed in terms of motional amplitude and characteristic time scale. Different averaging schemes are examined in order to propose an analysis of relaxation curves that takes into account the specificity of MAS experiments. In particular, it is shown that magic angle spinning averages the relaxation rate experienced by a single spin over one rotor period, resulting in individual relaxation curves that are dependent on the orientation of their corresponding carousel with respect to the rotor axis. Powder averaging thus leads to a nonexponential behavior in the observed decay curves. We extract dynamic information from experimental decay curves, using a diffusion in a cone model. We apply this study to the analysis of spin-lattice relaxation rates of the microcrystalline protein Crh at two different fields and determine differential dynamic parameters for several residues in the protein.

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

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

Ok, Salim; Hoyt, David W.; Andersen, Amity

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

DOE PAGES

Ok, Salim; Hoyt, David W.; Andersen, Amity; ...

2017-01-18

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

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

Ok, Salim; Hoyt, David W.; Andersen, Amity

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nano-porous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed non-porous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2 bar, 32.6 bar, 56.4 bar, 65.1 bar, 112.7 bar, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Nano-Mole Scale Side-Chain Signal Assignment by 1H-Detected Protein Solid-State NMR by Ultra-Fast Magic-Angle Spinning and Stereo-Array Isotope Labeling

PubMed Central

Nishiyama, Yusuke; Endo, Yuki; Nemoto, Takahiro; Yamauchi, Kazuo; Asakura, Tetsuo; Takeda, Mitsuhiro; Terauchi, Tsutomu; Kainosho, Masatsune; Ishii, Yoshitaka

2015-01-01

We present a general approach in 1H-detected 13C solid-state NMR (SSNMR) for side-chain signal assignments of 10-50 nmol quantities of proteins using a combination of a high magnetic field, ultra-fast magic-angle spinning (MAS) at ~80 kHz, and stereo-array-isotope-labeled (SAIL) proteins [Kainosho M. et al., Nature 440, 52–57, 2006]. First, we demonstrate that 1H indirect detection improves the sensitivity and resolution of 13C SSNMR of SAIL proteins for side-chain assignments in the ultra-fast MAS condition. 1H-detected SSNMR was performed for micro-crystalline ubiquitin (~55 nmol or ~0.5mg) that was SAIL-labeled at seven isoleucine (Ile) residues. Sensitivity was dramatically improved by 1H-detected 2D 1H/13C SSNMR by factors of 5.4-9.7 and 2.1-5.0, respectively, over 13C-detected 2D 1H/13C SSNMR and 1D 13C CPMAS, demonstrating that 2D 1H-detected SSNMR offers not only additional resolution but also sensitivity advantage over 1D 13C detection for the first time. High 1H resolution for the SAIL-labeled side-chain residues offered reasonable resolution even in the 2D data. A 1H-detected 3D 13C/13C/1H experiment on SAIL-ubiquitin provided nearly complete 1H and 13C assignments for seven Ile residues only within ~2.5 h. The results demonstrate the feasibility of side-chain signal assignment in this approach for as little as 10 nmol of a protein sample within ~3 days. The approach is likely applicable to a variety of proteins of biological interest without any requirements of highly efficient protein expression systems. PMID:25856081

Dynamic Nuclear Polarization enhanced NMR at 187 GHz/284 MHz using an Extended Interaction Klystron amplifier.

PubMed

Kemp, Thomas F; Dannatt, Hugh R W; Barrow, Nathan S; Watts, Anthony; Brown, Steven P; Newton, Mark E; Dupree, Ray

2016-04-01

A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer which uses a 187 GHz (corresponding to (1)H NMR frequency of 284 MHz) Extended Interaction Klystron (EIK) amplifier as the microwave source is briefly described. Its performance is demonstrated for a biomolecule (bacteriorhodopsin), a pharmaceutical, and surface functionalised silica. The EIK is very compact and easily incorporated into an existing spectrometer. The bandwidth of the amplifier is sufficient that it obviates the need for a sweepable magnetic field, once set, for all commonly used radicals. The variable power (CW or pulsed) output from the EIK is transmitted to the DNP-NMR probe using a quasi-optic system with a high power isolator and a corrugated waveguide which feeds the microwaves into the DNP-NMR probe. Curved mirrors inside the probe project the microwaves down the axis of the MAS rotor, giving a very efficient system such that maximum DNP enhancement is achieved with less than 3 W output from the microwave source. The DNP-NMR probe operates with a sample temperature down to 90K whilst spinning at 8 kHz. Significant enhancements, in excess of 100 for bacteriorhodopsin in purple membrane (bR in PM), are shown along with spectra which are enhanced by ≈25 with respect to room temperature, for both the pharmaceutical furosemide and surface functionalised silica. These enhancements allow hitherto prohibitively time consuming experiments to be undertaken. The power at which the DNP enhancement in bR in PM saturates does not change significantly between 90K and 170 K even though the enhancement drops by a factor of ≈11. As the DNP build up time decreases by a factor 3 over this temperature range, the reduction in T1n is presumably a significant contribution to the drop in enhancement. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Theoretical description of RESPIRATION-CP

NASA Astrophysics Data System (ADS)

Nielsen, Anders B.; Tan, Kong Ooi; Shankar, Ravi; Penzel, Susanne; Cadalbert, Riccardo; Samoson, Ago; Meier, Beat H.; Ernst, Matthias

2016-02-01

We present a quintuple-mode operator-based Floquet approach to describe arbitrary amplitude modulated cross polarization experiments under magic-angle spinning (MAS). The description is used to analyze variants of the RESPIRATION approach (RESPIRATIONCP) where recoupling conditions and the corresponding first-order effective Hamiltonians are calculated, validated numerically and compared to experimental results for 15N-13C coherence transfer in uniformly 13C,15N-labeled alanine and in uniformly 2H,13C,15N-labeled (deuterated and 100% back-exchanged) ubiquitin at spinning frequencies of 16.7 and 90.9 kHz. Similarities and differences between different implementations of the RESPIRATIONCP sequence using either CW irradiation or small flip-angle pulses are discussed.

Automation of flow injection gas diffusion-ion chromatography for the nanomolar determination of methylamines and ammonia in seawater and atmospheric samples

PubMed Central

Gibb, Stuart W.; Wood, John W.; Fauzi, R.; Mantoura, C.

1995-01-01

The automation and improved design and performance of Flow Injection Gas Diffusion-Ion Chromatography (FIGD-IC), a novel technique for the simultaneous analysis of trace ammonia (NH3) and methylamines (MAs) in aqueous media, is presented. Automated Flow Injection Gas Diffusion (FIGD) promotes the selective transmembrane diffusion of MAs and NH3 from aqueous sample under strongly alkaline (pH > 12, NaOH), chelated (EDTA) conditions into a recycled acidic acceptor stream. The acceptor is then injected onto an ion chromatograph where NH3 and the MAs are fully resolved as their cations and detected conductimetrically. A versatile PC interfaced control unit and data capture unit (DCU) are employed in series to direct the selonoid valve switching sequence, IC operation and collection of data. Automation, together with other modifications improved both linearily (R2 > 0.99 MAs 0-100 nM, NH3 0-1000 nM) and precision (<8%) of FIGD-IC at nanomolar concentrations, compared with the manual procedure. The system was successfully applied to the determination of MAs and NH3 in seawater and in trapped particulate and gaseous atmospheric samples during an oceanographic research cruise. PMID:18925047

In-situ molecular-level elucidation of organofluorine binding sites in a whole peat soil.

PubMed

Longstaffe, James G; Courtier-Murias, Denis; Soong, Ronald; Simpson, Myrna J; Maas, Werner E; Fey, Michael; Hutchins, Howard; Krishnamurthy, Sridevi; Struppe, Jochem; Alaee, Mehran; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Simpson, André J

2012-10-02

The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)F→(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)F→(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

PubMed Central

Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

2014-01-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25–30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2–6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92–128 for cross-polarized 13C NMR signals from 15N,13C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6–3.8 s for 1H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute 13C NMR signal amplitudes and build-up times, are approximately 2–4 times lower than with the best triradicals. PMID:24887201

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

NASA Astrophysics Data System (ADS)

Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

2014-07-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized 13C NMR signals from 15N,13C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8 s for 1H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute 13C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals.

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR.

PubMed

Yau, Wai-Ming; Thurber, Kent R; Tycko, Robert

2014-07-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized (13)C NMR signals from (15)N,(13)C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8s for (1)H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute (13)C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals. Published by Elsevier Inc.

Cation Ordering in Li[NixMnxCo(1-2x)]O2-Layered Cathode Materials: A Nuclear Magnetic Resonance (NMR), Pair Distribution Function, X-ray Absorption Spectroscopy, and Electrochemical Study

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

Zeng,D.; Cabana, J.; Breger, J.

2007-01-01

Several members of the compositional series Li[NixMnxCo(1-2x)]O2 (0.01 = x = 1/3) were synthesized and characterized. X-ray diffraction results confirm the presence of the layered a-NaFeO2-type structure, while X-ray absorption near-edge spectroscopy experiments verify the presence of Ni2+, Mn4+, and Co3+. Their local environment and short-range ordering were investigated by using a combination of 6Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and neutron pair distribution function (PDF) analysis, associated with reverse Monte Carlo (RMC) calculations. The 6Li MAS NMR spectra of compounds with low Ni/Mn contents (x = 0.10) show several well-resolved resonances, which start to mergemore » when the amount of Ni and Mn increases, finally forming a broad resonance at high Ni/Mn contents. Analysis of the 6Li MAS NMR 6Li[Ni0.02Mn0.02Co0.96]O2 spectrum, is consistent with the formation of Ni2+ and Mn4+ clusters within the transition-metal layers, even at these low-doping levels. The oxidation state of Ni in this high Co content sample strongly depends upon the Li/transition metal ratio of the starting materials. Neutron PDF analysis of the highest Ni/Mn content sample Li[Ni1/3Mn1/3Co1/3]O2 shows a tendency for Ni cations to be close to Mn cations in the first coordination shell; however, the Co3+ ions are randomly distributed. Analysis of the intensity of the 'LiCoO2' resonance, arising from Li surrounded by Co3+ in its first two cation coordination shells, for the whole series provides further evidence for a nonrandom distribution of the transition-metal cations. The presence of the insulator-to-metal transition seen in the electrochemical profiles of these materials upon charging correlates strongly with the concentration of the 'LiCoO2' resonance.« less

Detection of cancer in cervical tissue biopsies using mobile lipid resonances measured with diffusion-weighted (1)H magnetic resonance spectroscopy.

PubMed

Zietkowski, D; Davidson, R L; Eykyn, T R; De Silva, S S; Desouza, N M; Payne, G S

2010-05-01

The purpose of this study was to implement a diffusion-weighted sequence for visualisation of mobile lipid resonances (MLR) using high resolution magic angle spinning (HR-MAS) (1)H MRS and to evaluate its use in establishing differences between tissues from patients with cervical carcinoma that contain cancer from those that do not. A stimulated echo sequence with bipolar gradients was modified to allow T(1) and T(2) measurements and optimised by recording signal loss in HR-MAS spectra as a function of gradient strength in model lipids and tissues. Diffusion coefficients, T(1) and apparent T(2) relaxation times were measured in model lipid systems. MLR profiles were characterised in relation to T(1) and apparent T(2) relaxation in human cervical cancer tissue samples. Diffusion-weighted (DW) spectra of cervical biopsies were quantified and peak areas analysed using linear discriminant analysis (LDA). The optimised sequence reduced spectral overlap by suppressing signals originating from low molecular weight metabolites and non-lipid contributions. Significantly improved MLR visualisation allowed visualisation of peaks at 0.9, 1.3, 1.6, 2.0, 2.3, 2.8, 4.3 and 5.3 ppm. MLR analysis of DW spectra showed at least six peaks arising from saturated and unsaturated lipids and those arising from triglycerides. Significant differences in samples containing histologically confirmed cancer were seen for peaks at 0.9 (p < 0.006), 1.3 (p < 0.04), 2.0 (p < 0.03), 2.8 (p < 0.003) and 4.3 ppm (p < 0.0002). LDA analysis of MLR peaks from DW spectra almost completely separated two clusters of cervical biopsies (cancer, 'no-cancer'), reflecting underlying differences in MLR composition. Generated Receiver Operating Characteristic (ROC) curves and calculated area under the curve (0.962) validated high sensitivity and specificity of the technique. Diffusion-weighting of HR-MAS spectroscopic sequences is a useful method for characterising MLR in cancer tissues and displays an accumulation of lipids arising during tumourigenesis and an increase in the unsaturated lipid and triglyceride peaks with respect to saturated MLR. Copyright © 2009 John Wiley & Sons, Ltd.

13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

USGS Publications Warehouse

Dennis, L.W.; Maciel, G.E.; Hatcher, P.G.; Simoneit, B.R.T.

1982-01-01

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500??C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of 13C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The 13C CP/MAS results appear to provide a good measure of thermal alteration. ?? 1982.

Multinuclear (27Al, 29Si, 47,49Ti) solid-state NMR of titanium substituted zeolite USY.

PubMed

Ganapathy, S; Gore, K U; Kumar, Rajiv; Amoureux, Jean-Paul

2003-01-01

Multinuclear solid-state NMR spectroscopy, employing 29Si MAS,27Al MAS/3Q-MAS and (47,49)Ti wide-line experiments, has been used for the structural characterization of titanium substituted ultra-stable zeolite Y (Ti-USY). 27Al MAS experiments show the presence of aluminum in four (Al(IV)), five (Al(V)), and six (Al(VI)) coordination, whereas the multiplicity within Al(IV) and Al(VI) is revealed by 27Al 3Q-MAS experiments. Two different tetrahedral and octahedral Al environments are resolved and their isotropic chemical shifts (delta(CS)) and second-order quadrupole interaction parameters (P(Q)) have been determined by a graphical analysis of the 3Q-MAS spectra. The emergence of signal with higher intensity at -101 ppm in the 29Si MAS spectrum of Ti-USY samples indicates the possible occurrence of Q4(3Si,1Ti) type silicon environments due to titanium substitution in the faujasite framework. High-field (11.74T) operation, using a probehead specially designed to handle a large sample volume, has enabled the acquisition of 47,49Ti static spectra and identification of the titanium environment in the zeolite. The chemical shielding and electric field gradient tensors for the titanium environment in the zeolite have been determined by a computer simulation of the quadrupolar broadened static 47,49Ti NMR spectra.

Angiotensin (1-7) and its receptor Mas are expressed in the human testis: implications for male infertility.

PubMed

Reis, Augusto B; Araújo, Fabiano C; Pereira, Virginia M; Dos Reis, Adelina M; Santos, Robson A; Reis, Fernando M

2010-02-01

The presence of classical components of the renin-angiotensin system has been demonstrated in the male reproductive tract, mainly in the testes and epididymis. The objective of this study was to verify the localization of angiotensin (Ang)-(1-7) and its receptor Mas in human testis. The study included 12 men with previously proven fertility submitted to orchiectomy for prostate cancer and 20 infertile men submitted to testicular biopsy for infertility work-up, comprising a subgroup with obstructive azoospermia/normal spermatogenesis (n = 8) and another with non-obstructive azoospermia and severely impaired spermatogenesis (n = 12). Testicular tissue samples were processed by immunohistochemistry and real time polymerase chain reaction. Ang-(1-7) was strongly expressed in the interstitial compartment, mainly in Leydig cells, with similar intensity in all groups evaluated. The peptide was also detected in the seminiferous tubules, but with much less intensity compared to interstitial cells. The receptor Mas was equally distributed between interstitial and tubular compartments and was found in all layers of the normal seminiferous epithelium. However, neither Ang-(1-7) nor Mas were detected in the seminiferous tubules of samples with impaired spermatogenesis. The testicular samples of infertile men with impaired spermatogenesis (non-obstructive azoospermia) expressed Mas and ACE2 mRNA at lower concentrations (fold change = 0.06 and 0.04, respectively, P < 0.05) than samples with full spermatogenesis (obstructive azoospermia). This shows, for the first time, the immunolocalization of Ang-(1-7) and its receptor Mas in testes of fertile and infertile men, and suggests that this system may be altered when spermatogenesis is severely impaired.

Metabolic profiling of ob/ob mouse fatty liver using HR-MAS 1H-NMR combined with gene expression analysis reveals alterations in betaine metabolism and the transsulfuration pathway.

PubMed

Gogiashvili, Mikheil; Edlund, Karolina; Gianmoena, Kathrin; Marchan, Rosemarie; Brik, Alexander; Andersson, Jan T; Lambert, Jörg; Madjar, Katrin; Hellwig, Birte; Rahnenführer, Jörg; Hengstler, Jan G; Hergenröder, Roland; Cadenas, Cristina

2017-02-01

Metabolic perturbations resulting from excessive hepatic fat accumulation are poorly understood. Thus, in this study, leptin-deficient ob/ob mice, a mouse model of fatty liver disease, were used to investigate metabolic alterations in more detail. Metabolites were quantified in intact liver tissues of ob/ob (n = 8) and control (n = 8) mice using high-resolution magic angle spinning (HR-MAS) 1 H-NMR. In addition, after demonstrating that HR-MAS 1 H-NMR does not affect RNA integrity, transcriptional changes were measured by quantitative real-time PCR on RNA extracted from the same specimens after HR-MAS 1 H-NMR measurements. Importantly, the gene expression changes obtained agreed with those observed by Affymetrix microarray analysis performed on RNA isolated directly from fresh-frozen tissue. In total, 40 metabolites could be assigned in the spectra and subsequently quantified. Quantification of lactate was also possible after applying a lactate-editing pulse sequence that suppresses the lipid signal, which superimposes the lactate methyl resonance at 1.3 ppm. Significant differences were detected for creatinine, glutamate, glycine, glycolate, trimethylamine-N-oxide, dimethylglycine, ADP, AMP, betaine, phenylalanine, and uridine. Furthermore, alterations in one-carbon metabolism, supported by both metabolic and transcriptional changes, were observed. These included reduced demethylation of betaine to dimethylglycine and the reduced expression of genes coding for transsulfuration pathway enzymes, which appears to preserve methionine levels, but may limit glutathione synthesis. Overall, the combined approach is advantageous as it identifies changes not only at the single gene or metabolite level but also deregulated pathways, thus providing critical insight into changes accompanying fatty liver disease. Graphical abstract A Evaluation of RNA integrity before and after HR-MAS 1 H-NMR of intact mouse liver tissue. B Metabolite concentrations and gene expression levels assessed in ob/ob (steatotic) and ob/+ (control) mice using HR-MAS 1 H-NMR and qRT-PCR, respectively.

¹H-MAS-NMR chemical shifts in hydrogen-bonded complexes of chlorophenols (pentachlorophenol, 2,4,6-trichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, and p-chlorophenol) and amine, and H/D isotope effects on ¹H-MAS-NMR spectra.

PubMed

Honda, Hisashi

2013-04-22

Chemical shifts (CS) of the ¹H nucleus in N···H···O type hydrogen bonds (H-bond) were observed in some complexes between chlorophenols [pentachlorophenol (PCP), 2,4,6-tricholorophenol (TCP), 2,6-dichlorophenol (26DCP), 3,5-dichlorophenol (35DCP), and p-chlorophenol (pCP)] and nitrogen-base (N-Base) by solid-state high-resolution ¹H-NMR with the magic-angle-spinning (MAS) method. Employing N-Bases with a wide range of pKa values (0.65-10.75), ¹H-MAS-NMR CS values of bridging H atoms in H-bonds were obtained as a function of the N-Base's pKa. The result showed that the CS values were increased with increasing pKa values in a range of DpKa < 0 [DpKa = pKa(N-Base)-pKa(chlorophenols)] and decreased when DpKa > 2: The maximum CS values was recorded in the PCP (pKa = 5.26)-4-methylpyridine (6.03), TCP (6.59)-imidazole (6.99), 26DCP (7.02)-2-amino-4-methylpyridine (7.38), 35DCP (8.04)-4-dimethylaminopyridine (9.61), and pCP (9.47)-4-dimethylaminopyridine (9.61) complexes. The largest CS value of 18.6 ppm was recorded in TCP-imidazole crystals. In addition, H/D isotope effects on ¹H-MAS-NMR spectra were observed in PCP-2-amino-3-methylpyridine. Based on the results of CS simulation using a B3LYP/6-311+G** function, it can be explained that a little changes of the N-H length in H-bond contribute to the H/D isotope shift of the ¹H-MAS-NMR peaks.

Multiple acquisitions via sequential transfer of orphan spin polarization (MAeSTOSO): How far can we push residual spin polarization in solid-state NMR?

NASA Astrophysics Data System (ADS)

Gopinath, T.; Veglia, Gianluigi

2016-06-01

Conventional multidimensional magic angle spinning (MAS) solid-state NMR (ssNMR) experiments detect the signal arising from the decay of a single coherence transfer pathway (FID), resulting in one spectrum per acquisition time. Recently, we introduced two new strategies, namely DUMAS (DUal acquisition Magic Angle Spinning) and MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), that enable the simultaneous acquisitions of multidimensional ssNMR experiments using multiple coherence transfer pathways. Here, we combined the main elements of DUMAS and MEIOSIS to harness both orphan spin operators and residual polarization and increase the number of simultaneous acquisitions. We show that it is possible to acquire up to eight two-dimensional experiments using four acquisition periods per each scan. This new suite of pulse sequences, called MAeSTOSO for Multiple Acquisitions via Sequential Transfer of Orphan Spin pOlarization, relies on residual polarization of both 13C and 15N pathways and combines low- and high-sensitivity experiments into a single pulse sequence using one receiver and commercial ssNMR probes. The acquisition of multiple experiments does not affect the sensitivity of the main experiment; rather it recovers the lost coherences that are discarded, resulting in a significant gain in experimental time. Both merits and limitations of this approach are discussed.

Design and Functional Validation of a Mechanism for Dual-Spinning CubeSats

NASA Technical Reports Server (NTRS)

Peters, Eric; Dave, Pratik; Kingsbury, Ryan; Marinan, Anne; Wise, Evan; Pong, Chris; Prinkey, Meghan; Cahoy, Kerri; Miller, David W.; Sklair, Devon

2014-01-01

The mission of the Micro-sized Microwave Atmospheric Satellite (MicroMAS) is to collect useful atmospheric images using a miniature passive microwave radiometer payload hosted on a low-cost CubeSat platform. In order to collect this data, the microwave radiometer payload must rotate to scan the ground-track perpendicular to the satellite's direction of travel. A custom motor assembly was developed to facilitate the rotation of the payload while allowing the spacecraft bus to remained fixed in the local-vertical, local-horizontal (LVLH) frame for increased pointing accuracy. This paper describes the mechanism used to enable this dual-spinning operation for CubeSats, and the lessons learned during the design, fabrication, integration, and testing phases of the mechanism's development lifecycle.

Solid-state NMR spin-echo investigation of the metalloproteins parvalbumin, concanavalin A, and pea and lentil lectins, substituted with cadmium-113

NASA Astrophysics Data System (ADS)

Marchetti, Paul S.; Bhattacharyya, Lokesh; Ellis, Paul D.; Brewer, C. Fred

Solid-state 113Cd NMR spectroscopy of static powder samples of 113Cd-substituted metalloproteins, parvalbumin, concanavalin A, and pea and lentil lectins, was carried out. Cross polarization followed by application of a train of uniformly spaced π pulses was employed to investigate the origin of residual cadmium NMR linewidths observed previously in these proteins. Fourier transformation of the resulting spin-echo train yielded spectra consisting of uniformly spaced lines having linewidths of the order of 1-2 ppm. The observed linewidths were not influenced by temperature as low as -50°C or by extent of protein hydration. Since the echo-train pulse sequence is able to eliminate inhomogeneous but not homogeneous contributions to the linewidths, there is a predominant inhomogeneous contribution to cadmium linewidths in the protein CP/MAS spectra. However, significant changes in spectral intensities were observed with change in temperature and extent of protein hydration. These intensity changes are attributed for parvalbumin and concanavalin A to changes in cross-polarization efficiency with temperature and hydration. For pea and lentil lectins, this effect is attributed to the elimination of static disorder at the pea and lentil S2 metal-ion sites due to sugar binding.

A novel microaneurysms detection approach based on convolutional neural networks with reinforcement sample learning algorithm.

PubMed

Budak, Umit; Şengür, Abdulkadir; Guo, Yanhui; Akbulut, Yaman

2017-12-01

Microaneurysms (MAs) are known as early signs of diabetic-retinopathy which are called red lesions in color fundus images. Detection of MAs in fundus images needs highly skilled physicians or eye angiography. Eye angiography is an invasive and expensive procedure. Therefore, an automatic detection system to identify the MAs locations in fundus images is in demand. In this paper, we proposed a system to detect the MAs in colored fundus images. The proposed method composed of three stages. In the first stage, a series of pre-processing steps are used to make the input images more convenient for MAs detection. To this end, green channel decomposition, Gaussian filtering, median filtering, back ground determination, and subtraction operations are applied to input colored fundus images. After pre-processing, a candidate MAs extraction procedure is applied to detect potential regions. A five-stepped procedure is adopted to get the potential MA locations. Finally, deep convolutional neural network (DCNN) with reinforcement sample learning strategy is used to train the proposed system. The DCNN is trained with color image patches which are collected from ground-truth MA locations and non-MA locations. We conducted extensive experiments on ROC dataset to evaluate of our proposal. The results are encouraging.

NMR crystallography of campho[2,3-c]pyrazole (Z' = 6): combining high-resolution 1H-13C solid-state MAS NMR spectroscopy and GIPAW chemical-shift calculations.

PubMed

Webber, Amy L; Emsley, Lyndon; Claramunt, Rosa M; Brown, Steven P

2010-09-30

(1)H-(13)C two-dimensional magic-angle spinning (MAS) solid-state NMR correlation spectra, recorded with the MAS-J-HMQC experiment, are presented for campho[2,3-c]pyrazole. For each (13)C moiety, there are six resonances associated with the six distinct molecules in the asymmetric unit cell (Z' = 6). The one-bond C-H correlations observed in the 2D (1)H-(13)C MAS-J-HMQC spectra allow the experimental determination of the (1)H and (13)C chemical shifts associated with the separate CH, CH(2), and CH(3) groups. (1)H and (13)C chemical shifts calculated by using the GIPAW (Gauge Including Projector Augmented Waves) plane-wave pseudopotential approach are presented. Calculations for the whole unit cell (12 × 29 = 348 atoms, with geometry optimization of all atoms) allow the assignment of the experimental (1)H and (13)C chemical shifts to the six distinct molecules. The calculated chemical shifts for the full crystal structure are compared with those for isolated molecules as extracted from the geometry-optimized crystal structure. In this way, the effect of intermolecular interactions on the observed chemical shifts is quantified. In particular, the calculations are sufficiently precise to differentiate the small (<1 ppm) differences between the (1)H chemical shifts of the six resonances associated with each distinct CH or CH(2) moiety.

Quantification In Situ of Crystalline Cholesterol and Calcium Phosphate Hydroxyapatite in Human Atherosclerotic Plaques by Solid-State Magic Angle Spinning NMR

PubMed Central

Guo, Wen; Morrisett, Joel D.; DeBakey, Michael E.; Lawrie, Gerald M.; Hamilton, James A.

2010-01-01

Because of renewed interest in the progression, stabilization, and regression of atherosclerotic plaques, it has become important to develop methods for characterizing structural features of plaques in situ and noninvasively. We present a nondestructive method for ex vivo quantification of 2 solid-phase components of plaques: crystalline cholesterol and calcium phosphate salts. Magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of human carotid endarterectomy plaques revealed 13C resonances of crystalline cholesterol monohydrate and a 31P resonance of calcium phosphate hydroxyapatite (CPH). The spectra were obtained under conditions in which there was little or no interference from other chemical components and were suitable for quantification in situ of the crystalline cholesterol and CPH. Carotid atherosclerotic plaques showed a wide variation in their crystalline cholesterol content. The calculated molar ratio of liquid-crystalline cholesterol to phospholipid ranged from 1.1 to 1.7, demonstrating different capabilities of the phospholipids to reduce crystallization of cholesterol. The spectral properties of the phosphate groups in CPH in carotid plaques were identical to those of CPH in bone. 31P MAS NMR is a simple, rapid method for quantification of calcium phosphate salts in tissue without extraction and time-consuming chemical analysis. Crystalline phases in intact atherosclerotic plaques (ex vivo) can be quantified accurately by solid-state 13C and 31PMAS NMR spectroscopy. PMID:10845882

13C CP/MAS NMR Studies of Hemoprotein Models with and without an Axial Hindered Base: (13)C Shielding Tensors and Comparison with Hemoproteins and X-ray Structural Data.

PubMed

Gerothanassis, I. P.; Momenteau, M.; Barrie, P. J.; Kalodimos, C. G.; Hawkes, G. E.

1996-04-24

13C cross-polarization magic-angle-spinning (CP/MAS) NMR spectra of several carbonmonoxide (93-99% (13)C enriched) hemoprotein models with 1,2-dimethylimidazole (1,2-diMeIm) and 1-methylimidazole (1-MeIm) as axial ligands are reported. This enables the (13)CO spinning sideband manifold to be measured and hence the principal components of the (13)CO chemical shift tensor to be obtained. Negative polar interactions in the binding pocket of the cap porphyrin model and inhibition of Fe-->CO back-donation result in a reduction in shielding anisotropy; on the contrary, positive distal polar interactions result in an increase in the shielding anisotropy and asymmetry parameter in some models. It appears that the axial hindered base 1,2-dimethylimidazole has little direct effect on the local geometry at the CO site, despite higher rates of CO desorption being observed for such complexes. This suggests that the mechanism by which steric interactions are released for the 1,2-diMeIm complexes compared to 1-MeIm complexes does not involve a significant increase in bending of the Fe-C-O unit. The asymmetry of the shielding tensor of all the heme model compounds studied is smaller than that found for horse myoglobin and rabbit hemoglobin.

Oral Appliance Treatment Response and Polysomnographic Phenotypes of Obstructive Sleep Apnea

PubMed Central

Sutherland, Kate; Takaya, Hisashi; Qian, Jin; Petocz, Peter; Ng, Andrew T.; Cistulli, Peter A.

2015-01-01

Study Objectives: Mandibular advancement splints (MAS) are an effective treatment for obstructive sleep apnea (OSA); however, therapeutic response is variable. Younger age, female gender, less obesity, and milder and supine-dependent OSA have variably been associated with treatment success in relatively small samples. Our objective was to utilize a large cohort of MAS treated patients (1) to compare efficacy across patients with different phenotypes of OSA and (2) to assess demographic, anthropometric, and polysomnography variables as treatment response predictors. Methods: Retrospective analysis of MAS-treated patients participating in clinical trials in sleep centers in Sydney, Australia between years 2000–2013. All studies used equivalent customized two-piece MAS devices and treatment protocols. Treatment response was defined as (1) apnea-hypopnea index (AHI) < 5/h, (2) AHI < 10/h and ≥ 50% reduction, and (3) ≥ 50% AHI reduction. Results: A total of 425 patients (109 female) were included (age 51.2 ± 10.9 years, BMI 29.2 ± 5.0 kg/m2). MAS reduced AHI by 50.3% ± 50.7% across the group. Supine-predominant OSA patients had lower treatment response rates than non-positional OSA (e.g., 36% vs. 59% for AHI < 10/h). REM-predominant OSA showed a lower response rate than either NREM or non-stage dependent OSA. In prediction modelling, age, baseline AHI, and anthropometric variables were predictive of MAS treatment outcome but not OSA phenotype. Gender was not associated with treatment outcome. Conclusions: Lower MAS treatment response rates were observed in supine and REM sleep. In a large sample, we confirm that demographic, anthropometric, and polysomnographic data only weakly inform about MAS efficacy, supporting the need for alternative objective prediction methods to reliably select patients for MAS treatment. Citation: Sutherland K, Takaya H, Qian J, Petocz P, Ng AT, Cistulli PA. Oral appliance treatment response and polysomnographic phenotypes of obstructive sleep apnea. J Clin Sleep Med 2015;11(8):861–868. PMID:25845897

MRS study of meningeal hemangiopericytoma and edema: a comparison with meningothelial meningioma.

PubMed

Righi, Valeria; Tugnoli, Vitaliano; Mucci, Adele; Bacci, Antonella; Bonora, Sergio; Schenetti, Luisa

2012-10-01

Intracranial hemangiopericytomas (HPCs) are rare tumors and their radiological appearance resembles that of meningiomas, especially meningothelial meningiomas. To increase the knowledge on the biochemical composition of this type of tumor for better diagnosis and prognosis, we performed a molecular study using ex vivo high resolution magic angle spinning (HR-MAS) magnetic resonance spectroscopy (MRS) perfomed on HPC and peritumoral edematous tissues. Moreover, to help in the discrimination between HPC and meningothelial meningioma we compared the ex vivo HR-MAS spectra of samples from one patient with HPC and 5 patients affected by meningothelial meningioma. Magnetic resonance imaging (MRI), in vivo localized single voxel 1H-MRS was also performed on the same patients prior to surgery and the in vivo and ex vivo MRS spectra were compared. We observed the presence of OH-butyrate, together with glucose in HPC and a low amount of N-acetylaspartate in the edema, that may reflect neuronal alteration responsible for associated epilepsy. Many differences between HPC and meningothelial meningioma were identified. The relative ratios of myo-inositol, glucose and gluthatione with respect to glutamate are higher in HPC compared to meningioma; whereas the relative ratios of creatine, glutamine, alanine, glycine and choline-containing compounds with respect to glutamate are lower in HPC compared to meningioma. These data will be useful to improve the interpretation of in vivo MRS spectra resulting in a more accurate diagnosis of these rare tumors.

Ex vivo metabolic fingerprinting identifies biomarkers predictive of prostate cancer recurrence following radical prostatectomy.

PubMed

Braadland, Peder R; Giskeødegård, Guro; Sandsmark, Elise; Bertilsson, Helena; Euceda, Leslie R; Hansen, Ailin F; Guldvik, Ingrid J; Selnæs, Kirsten M; Grytli, Helene H; Katz, Betina; Svindland, Aud; Bathen, Tone F; Eri, Lars M; Nygård, Ståle; Berge, Viktor; Taskén, Kristin A; Tessem, May-Britt

2017-11-21

Robust biomarkers that identify prostate cancer patients with high risk of recurrence will improve personalised cancer care. In this study, we investigated whether tissue metabolites detectable by high-resolution magic angle spinning magnetic resonance spectroscopy (HR-MAS MRS) were associated with recurrence following radical prostatectomy. We performed a retrospective ex vivo study using HR-MAS MRS on tissue samples from 110 radical prostatectomy specimens obtained from three different Norwegian cohorts collected between 2002 and 2010. At the time of analysis, 50 patients had experienced prostate cancer recurrence. Associations between metabolites, clinicopathological variables, and recurrence-free survival were evaluated using Cox proportional hazards regression modelling, Kaplan-Meier survival analyses and concordance index (C-index). High intratumoural spermine and citrate concentrations were associated with longer recurrence-free survival, whereas high (total-choline+creatine)/spermine (tChoCre/Spm) and higher (total-choline+creatine)/citrate (tChoCre/Cit) ratios were associated with shorter time to recurrence. Spermine concentration and tChoCre/Spm were independently associated with recurrence in multivariate Cox proportional hazards modelling after adjusting for clinically relevant risk factors (C-index: 0.769; HR: 0.72; P=0.016 and C-index: 0.765; HR: 1.43; P=0.014, respectively). Spermine concentration and tChoCre/Spm ratio in prostatectomy specimens were independent prognostic markers of recurrence. These metabolites can be noninvasively measured in vivo and may thus offer predictive value to establish preoperative risk assessment nomograms.

Ensemble based adaptive over-sampling method for imbalanced data learning in computer aided detection of microaneurysm.

PubMed

Ren, Fulong; Cao, Peng; Li, Wei; Zhao, Dazhe; Zaiane, Osmar

2017-01-01

Diabetic retinopathy (DR) is a progressive disease, and its detection at an early stage is crucial for saving a patient's vision. An automated screening system for DR can help in reduce the chances of complete blindness due to DR along with lowering the work load on ophthalmologists. Among the earliest signs of DR are microaneurysms (MAs). However, current schemes for MA detection appear to report many false positives because detection algorithms have high sensitivity. Inevitably some non-MAs structures are labeled as MAs in the initial MAs identification step. This is a typical "class imbalance problem". Class imbalanced data has detrimental effects on the performance of conventional classifiers. In this work, we propose an ensemble based adaptive over-sampling algorithm for overcoming the class imbalance problem in the false positive reduction, and we use Boosting, Bagging, Random subspace as the ensemble framework to improve microaneurysm detection. The ensemble based over-sampling methods we proposed combine the strength of adaptive over-sampling and ensemble. The objective of the amalgamation of ensemble and adaptive over-sampling is to reduce the induction biases introduced from imbalanced data and to enhance the generalization classification performance of extreme learning machines (ELM). Experimental results show that our ASOBoost method has higher area under the ROC curve (AUC) and G-mean values than many existing class imbalance learning methods. Copyright © 2016 Elsevier Ltd. All rights reserved.

DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline.

PubMed

Gowda, Vasantha; Laitinen, Risto S; Telkki, Ville-Veikko; Larsson, Anna-Carin; Antzutkin, Oleg N; Lantto, Perttu

2016-12-06

The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13 C and 15 N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13 C and 15 N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P2 1 /n. Both 13 C and 15 N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13 C and 15 N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.

Investigations of the structure and "interfacial" surface chemistry of Bioglass (RTM) materials by solid-state multinuclear NMR spectroscopy

NASA Astrophysics Data System (ADS)

Sarkar, Gautam

Bioactive materials such as BioglassRTM 45S5 (45% SiO 2, 24.5% CaO, 24.5% Na2O, and 6% P2O5 by weight) are sodium-phosphosilicate glasses containing independent three-dimensional silicate and phosphate networks and Na+ and Ca2+ ions as modifying cations. Due to their bioactivity, these materials are currently used as implants and for other surgical and clinical applications. The bioactivity of BioglassesRTM is due to their unique capability to form chemical bonds to tissues through an octacalciumphosphate (OCP)- and/or hydroxyapatite-like (HA) "interfacial" matrix. The formation of OCP and/or HA is preceded by the formation of a silica-rich surface layer and the subsequent growth of an amorphous calcium phosphate (a-CP) layer. Structural characterization of a series of commercial and synthesized Bioglass materials 45S5 52S, 55S, 60S, and synthesized 17O-labelled "Bioglass materials 45S, 52S, 55S and 60S" have been obtained using solid-state single-pulse magic-angle spinning (SP/MAS) 17O, 23Na, 29Si and 31P NMR. The 17O NMR isotropic chemical shifts and estimates of the quadrupole coupling constants (Cq) [at fixed asymmetry parameter ( hQ ) values of zero] have been obtained from solid-state spin-echo 17O SP/MAS NMR spectra of 17O-labelled "Bioglasses". The simulation results of these spectra reveal the presence of both bridging-oxygens (BO, i.e. ≡ Si-17OSi ≡ ) and non-bridging oxygens (NBO, i.e. ≡ Si-17O-Na+/Ca2+ ) in the silicate networks in these materials. 17O NMR spectra of these Bioglass materials do not show any direct evidence for the presence of BO and NBO atoms in the phosphate units; however, they are expected to be present in small amounts. In vitro reactions of BioglassRTM 45S5, 60S and 77S powders have been used to study the "interfacial" surface chemistry of these materials in simulated body-fluid (SBF, Kyoto or K9 solution) and/or 17O-enriched tris-buffer solution. 29Si and 31P SP/MAS NMR have been used to identify and quantify the extent of formation of surface silica species and follow the formation of phosphate species, respectively, while cross-polarization magic-angle spinning (CP/MAS) 29Si and 31P NMR have provided information about low intensity NMR peaks due to various silicon- and phosphorus-species present in the vicinity of associated protons on the surface of in vitro reacted BioglassRTM materials. The solid-state NMR investigations of the "interfacial" surface reactions of BioglassRTM materials are discussed in the context of the structure of these materials and the influence of this structure on the kinetics and the mechanism of their "interfacial" surface chemistry. (Abstract shortened by UMI.) BioglassRTM, trademark, University of Florida, Gainesville, FL, 32611.

1H-detected MAS solid-state NMR experiments enable the simultaneous mapping of rigid and dynamic domains of membrane proteins

NASA Astrophysics Data System (ADS)

Gopinath, T.; Nelson, Sarah E. D.; Veglia, Gianluigi

2017-12-01

Magic angle spinning (MAS) solid-state NMR (ssNMR) spectroscopy is emerging as a unique method for the atomic resolution structure determination of native membrane proteins in lipid bilayers. Although 13C-detected ssNMR experiments continue to play a major role, recent technological developments have made it possible to carry out 1H-detected experiments, boosting both sensitivity and resolution. Here, we describe a new set of 1H-detected hybrid pulse sequences that combine through-bond and through-space correlation elements into single experiments, enabling the simultaneous detection of rigid and dynamic domains of membrane proteins. As proof-of-principle, we applied these new pulse sequences to the membrane protein phospholamban (PLN) reconstituted in lipid bilayers under moderate MAS conditions. The cross-polarization (CP) based elements enabled the detection of the relatively immobile residues of PLN in the transmembrane domain using through-space correlations; whereas the most dynamic region, which is in equilibrium between folded and unfolded states, was mapped by through-bond INEPT-based elements. These new 1H-detected experiments will enable one to detect not only the most populated (ground) states of biomacromolecules, but also sparsely populated high-energy (excited) states for a complete characterization of protein free energy landscapes.

The effectiveness of 1H decoupling in the 13C MAS NMR of paramagnetic solids: An experimental case study incorporating copper(II) amino acid complexes

NASA Astrophysics Data System (ADS)

Willans, Mathew J.; Sears, Devin N.; Wasylishen, Roderick E.

2008-03-01

The use of continuous-wave (CW) 1H decoupling has generally provided little improvement in the 13C MAS NMR spectroscopy of paramagnetic organic solids. Recent solid-state 13C NMR studies have demonstrated that at rapid magic-angle spinning rates CW decoupling can result in reductions in signal-to-noise and that 1H decoupling should be omitted when acquiring 13C MAS NMR spectra of paramagnetic solids. However, studies of the effectiveness of modern 1H decoupling sequences are lacking, and the performance of such sequences over a variety of experimental conditions must be investigated before 1H decoupling is discounted altogether. We have studied the performance of several commonly used advanced decoupling pulse sequences, namely the TPPM, SPINAL-64, XiX, and eDROOPY sequences, in 13C MAS NMR experiments performed under four combinations of the magnetic field strength (7.05 or 11.75 T), rotor frequency (15 or 30 kHz), and 1H rf-field strength (71, 100, or 140 kHz). The effectiveness of these sequences has been evaluated by comparing the 13C signal intensity, linewidth at half-height, LWHH, and coherence lifetimes, T2', of the methine carbon of copper(II) bis( DL-alanine) monohydrate, Cu(ala) 2·H 2O, and methylene carbon of copper(II) bis( DL-2-aminobutyrate), Cu(ambut) 2, obtained with the advanced sequences to those obtained without 1H decoupling, with CW decoupling, and for fully deuterium labelled samples. The latter have been used as model compounds with perfect 1H decoupling and provide a measure of the efficiency of the 1H decoupling sequence. Overall, the effectiveness of 1H decoupling depends strongly on the decoupling sequence utilized, the experimental conditions and the sample studied. Of the decoupling sequences studied, the XiX sequence consistently yielded the best results, although any of the advanced decoupling sequences strongly outperformed the CW sequence and provided improvements over no 1H decoupling. Experiments performed at 7.05 T demonstrate that the XiX decoupling sequence is the least sensitive to changes in the 1H transmitter frequency and may explain the superior performance of this decoupling sequence. Overall, the most important factor in the effectiveness of 1H decoupling was the carbon type studied, with the methylene carbon of Cu(ambut) 2 being substantially more sensitive to 1H decoupling than the methine carbon of Cu(ala) 2·H 2O. An analysis of the various broadening mechanisms contributing to 13C linewidths has been performed in order to rationalize the different sensitivities of the two carbon sites under the four experimental conditions.

(1)H magnetic resonance spectroscopy of preinvasive and invasive cervical cancer: in vivo-ex vivo profiles and effect of tumor load.

PubMed

Mahon, Marrita M; Cox, I Jane; Dina, Roberto; Soutter, W Patrick; McIndoe, G Angus; Williams, Andreanna D; deSouza, Nandita M

2004-03-01

To compare in vivo (1)H magnetic resonance (MR) spectra of preinvasive and invasive cervical lesions with ex vivo magic angle spinning (MAS) spectra of intact biopsies from the same subjects and to establish the effects of tumor load in the tissue sampled on the findings. A total of 51 subjects (nine with normal cervix, 10 with cervical intraepithelial neoplasia [CIN], and 32 with cervical cancer) underwent endovaginal MR at 1.5 T. Single-voxel (3.4 cm(3)) (1)H MR spectra were acquired and voxel tumor load was calculated (tumor volume within voxel as a percentage of voxel volume). Resonances from triglycerides -CH(2) and -CH(3) and choline-containing compounds (Cho) were correlated with voxel tumor load. Biopsies analyzed by (1)H MAS-MR spectroscopy (MRS) had metabolite levels correlated with tumor load in the sample at histology. In vivo studies detected Cho in normal, CIN, and cancer patients with no significant differences in levels (P = 0.93); levels were independent of voxel tumor load. Triglyceride -CH(2) and -CH(3) signals in-phase with Cho were present in 77% and 29%, respectively, of cancer subjects (but not in normal women or those with CIN), but did not correlate with voxel tumor load. Ex vivo cancer biopsies showed levels of triglycerides -CH(2) and -CH(3) and of Cho that were significantly greater than in normal or CIN biopsies (P < 0.05); levels were independent of the tumor load in the sample. The presence of -CH(2) in vivo predicted the presence of cancer with a sensitivity and specificity of 77.4% and 93.8% respectively, positive (PPV) and negative (NPV) predictive values were 96% and 68.2%; for -CH(2) ex vivo, sensitivity was 100%; specificity, 69%; PPV, 82%; and NPV, 100%. Elevated lipid levels are detected by MRS in vivo and ex vivo in cervical cancer and are independent of tumor load in the volume of tissue sampled. Copyright 2004 Wiley-Liss, Inc.

Static (1)H dynamic nuclear polarization with the biradical TOTAPOL: a transition between the solid effect and the cross effect.

PubMed

Shimon, Daphna; Feintuch, Akiva; Goldfarb, Daniella; Vega, Shimon

2014-04-14

To study the solid state (1)H-DNP mechanism of the biradical TOTAPOL under static conditions the frequency swept DNP enhancement spectra of samples containing 20 mM and 5 mM TOTAPOL were measured as a function of MW irradiation time and temperature. We observed that under static DNP conditions the biradical TOTAPOL behaves similar to the monoradical TEMPOL, in contrast to MAS DNP where TOTAPOL is considerably more effective. As previously done for TEMPOL, the TOTAPOL DNP spectra were analyzed taking a superposition of a basic SE-DNP lineshape and a basic CE-DNP lineshape with different amplitudes. The analysis of the steady state DNP spectra showed that the SE was dominant in the 6-10 K range and the CE was dominant above 10 K. DNP spectra obtained as a function of MW irradiation time allowed resolving the individual SE and CE buildup times. At low temperatures the SE buildup time was faster than the CE buildup time and at all temperatures the CE buildup time was close to the nuclear spin-lattice relaxation time, T1n. Polarization calculations involving nuclear spin-diffusion for a model system of one electron and many nuclei suggested that the shortening of the T1n for increasing temperatures is the reason why the SE contribution to the overall enhancement was reduced.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

17O NMR Investigation of Water Structure and Dynamics

PubMed Central

Keeler, Eric G.; Michaelis, Vladimir K.; Griffin, Robert G.

2017-01-01

The structure and dynamics of the bound water in barium chlorate monohydrate were studied with 17O nuclear magnetic resonance (NMR) spectroscopy in samples that are stationary and spinning at the magic-angle in magnetic fields ranging from 14.1 to 21.1 T. 17O NMR parameters of the water were determined, and the effects of torsional oscillations of the water molecule on the 17O quadrupolar coupling constant (CQ) were delineated with variable temperature MAS NMR. With decreasing temperature and reduction of the librational motion, we observe an increase in the experimentally measured CQ explaining the discrepancy between experiments and predictions from density functional theory. In addition, at low temperatures and in the absence of 1H decoupling, we observe a well-resolved 1H–17O dipole splitting in the spectra, which provides information on the structure of the H2O molecule. The splitting arises because of the homogeneous nature of the coupling between the two 1H–17O dipoles and the 1H–1H dipole. PMID:27454747

Glycerin-Induced Conformational Changes in Bombyx mori Silk Fibroin Film Monitored by (13)C CP/MAS NMR and ¹H DQMAS NMR.

PubMed

Asakura, Tetsuo; Endo, Masanori; Hirayama, Misaki; Arai, Hiroki; Aoki, Akihiro; Tasei, Yugo

2016-09-09

In order to improve the stiff and brittle characteristics of pure Bombyx mori (B. mori) silk fibroin (SF) film in the dry state, glycerin (Glyc) has been used as a plasticizer. However, there have been very limited studies on the structural characterization of the Glyc-blended SF film. In this study, (13)C Cross Polarization/Magic Angle Spinning nuclear magnetic resonance (CP/MAS NMR) was used to monitor the conformational changes in the films by changing the Glyc concentration. The presence of only 5 wt % Glyc in the film induced a significant conformational change in SF where Silk I* (repeated type II β-turn and no α-helix) newly appeared. Upon further increase in Glyc concentration, the percentage of Silk I* increased linearly up to 9 wt % Glyc and then tended to be almost constant (30%). This value (30%) was the same as the fraction of Ala residue within the Silk I* form out of all Ala residues of SF present in B. mori mature silkworm. The ¹H DQMAS NMR spectra of Glyc-blended SF films confirmed the appearance of Silk I* in the Glyc-blended SF film. A structural model of Glyc-SF complex including the Silk I* form was proposed with the guidance of the Molecular Dynamics (MD) simulation using ¹H-¹H distance constraints obtained from the ¹H Double-Quantum Magic Angle Spinning (DQMAS) NMR spectra.

A robust heteronuclear dipolar recoupling method comparable to TEDOR for proteins in magic-angle spinning solid-state NMR

NASA Astrophysics Data System (ADS)

Zhang, Zhengfeng; Li, Jianping; Chen, Yanke; Xie, Huayong; Yang, Jun

2017-12-01

In this letter, we propose a robust heteronuclear dipolar recoupling method for proteins in magic-angle spinning (MAS) solid-state NMR. This method is as simple, robust and efficient as the well-known TEDOR in the aspect of magnetization transfer between 15N and 13C. Deriving from our recent band-selective dual back-to-back pulses (DBP) (Zhang et al., 2016), this method uses new phase-cycling schemes to realize broadband DBP (Bro-DBP). For broadband 15N-13C magnetization transfer (simultaneous 15N → 13C‧ and 15N → 13Cα), Bro-DBP has almost the same 15N → 13Cα efficiency while offers 30-40% enhancement on 15N → 13C‧ transfer, compared to TEDOR. Besides, Bro-DBP can also be used as a carbonyl (13C‧)-selected method, whose 15N → 13C‧ efficiency is up to 1.7 times that of TEDOR and is also higher than that of band-selective DBP. The performance of Bro-DBP is demonstrated on the N-formyl-[U-13C,15N]-Met-Leu-Phe-OH (fMLF) peptide and the U-13C, 15N labeled β1 immunoglobulin binding domain of protein G (GB1) microcrystalline protein. Since Bro-DBP is as robust, simple and efficient as TEDOR, we believe it is very useful for protein studies in MAS solid-state NMR.

Experimental Aspects of Polarization Optimized Experiments (POE) for Magic Angle Spinning Solid-State NMR of Microcrystalline and Membrane-Bound Proteins.

PubMed

Gopinath, T; Veglia, Gianluigi

2018-01-01

Conventional NMR pulse sequences record one spectrum per experiment, while spending most of the time waiting for the spin system to return to the equilibrium. As a result, a full set of multidimensional NMR experiments for biological macromolecules may take up to several months to complete. Here, we present a practical guide for setting up a new class of MAS solid-state NMR experiments (POE or polarization optimized experiments) that enable the simultaneous acquisition of multiple spectra of proteins, accelerating data acquisition. POE exploit the long-lived 15 N polarization of isotopically labeled proteins and enable one to obtain up to eight spectra, by concatenating classical NMR pulse sequences. This new strategy propels data throughput of solid-state NMR spectroscopy of fibers, microcrystalline preparations, as well as membrane proteins.

A Microbial Assessment Scheme to measure microbial performance of Food Safety Management Systems.

PubMed

Jacxsens, L; Kussaga, J; Luning, P A; Van der Spiegel, M; Devlieghere, F; Uyttendaele, M

2009-08-31

A Food Safety Management System (FSMS) implemented in a food processing industry is based on Good Hygienic Practices (GHP), Hazard Analysis Critical Control Point (HACCP) principles and should address both food safety control and assurance activities in order to guarantee food safety. One of the most emerging challenges is to assess the performance of a present FSMS. The objective of this work is to explain the development of a Microbial Assessment Scheme (MAS) as a tool for a systematic analysis of microbial counts in order to assess the current microbial performance of an implemented FSMS. It is assumed that low numbers of microorganisms and small variations in microbial counts indicate an effective FSMS. The MAS is a procedure that defines the identification of critical sampling locations, the selection of microbiological parameters, the assessment of sampling frequency, the selection of sampling method and method of analysis, and finally data processing and interpretation. Based on the MAS assessment, microbial safety level profiles can be derived, indicating which microorganisms and to what extent they contribute to food safety for a specific food processing company. The MAS concept is illustrated with a case study in the pork processing industry, where ready-to-eat meat products are produced (cured, cooked ham and cured, dried bacon).

Comparison of the Results of Studies of Air Pollution Fungi Using the SAS Super 100, MAS 100, and Air IDEAL.

PubMed

Łukaszuk, Cecylia; Krajewska-Kułak, Elżbieta; Guzowski, Andrzej; Kułak, Wojciech; Kraszyńska, Bogumiła

2017-07-20

Although several air sampling devices for identifying and enumerating airborne microorganisms are commercially available, each poses some limitations. The aim of this study was to evaluate air pollution fungi using three such samplers: SAS Super 100, Microbiological Air Sampler (MAS) 100, and Air IDEAL. Mycological air was taken from the cellars of a 17th-century church in Siemiatycze, Poland, and the nearby outdoor environment. With samplers placed 1.5 m above the floor, microbial flora in air samples collected inside and outside the cellar were detected. The number of colony-forming units (CFU) of fungi obtained with the three samplers from the cellars and outdoor environment differed; the most CFU were obtained with the Air IDEAL and the least with the SAS Super 100. Significant differences emerged in CFUs collected from air samples with the MAS 100 and SAS Super 100, on the one hand, and the SAS Super 100 and Air IDEAL, on the other. Otherwise, results among the samplers were different. More Cladosporium species were collected with the MAS 100 sampler, whereas more Fusarium and Aspergillus species were collected with the Air IDEAL sampler. Significant differences among CFU/m³ values among the tested sites depended on the sampler used.

Chitin and chitosan from the Norway lobster by-products: Antimicrobial and anti-proliferative activities.

PubMed

Sayari, Nadhem; Sila, Assaâd; Abdelmalek, Baha Eddine; Abdallah, Rihab Ben; Ellouz-Chaabouni, Semia; Bougatef, Ali; Balti, Rafik

2016-06-01

Chitin was recovered through enzymatic deproteinization of the Norway lobster (Nephrops norvegicus) processing by-products. The obtained chitin was characterized and converted into chitosan by N-deacetylation, the acid-soluble form of chitin. Chitosan samples were then characterized by Fourier transform infrared spectroscopy (FTIR) and 13 Cross polarization magic angle spinning nuclear magnetic resonance (CP/MAS)-NMR spectroscopy. The antimicrobial activity and anti-proliferative capacity of chitosan were evaluated. Antimicrobial activity assays indicated that prepared chitosan exhibited marked inhibitory activity against the bacterial and fungal strains tested. Further, cytotoxic effects of chitosan samples on human colon carcinoma cells HCT116 was evaluated using the MTT assay. Chitosan showed the antiproliferative capacity against the colon-cancer-cell HCT116 in a dose dependent manner with IC50 of 4.6mg/ml. Indeed, HCT116 cell proliferation was significantly inhibited (p<0.05) between 13.5 and 67.5% at 0.5-6mg/mL of chitosan after 24h of cell treatment. The chitosan showed high antitumor activity which seemed to be dependent on its characteristics such as acetylation degree. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of varying water adsorption on a Cu3(BTC)2 metal-organic framework (MOF) as studied by 1H and 13C solid-state NMR spectroscopy.

PubMed

Gul-E-Noor, Farhana; Jee, Bettina; Pöppl, Andreas; Hartmann, Martin; Himsl, Dieter; Bertmer, Marko

2011-05-07

The process of water adsorption on a dehydrated Cu(3)(BTC)(2) (copper (II) benzene 1,3,5-tricarboxylate) metal-organic framework (MOF) was studied with (1)H and (13)C solid-state NMR. Different relative amounts of water (0.5, 0.75, 1, 1.5, 2, and 5 mole equivalents with respect to copper) were adsorbed via the gas phase. (1)H and (13)C MAS NMR spectra of dehydrated and water-loaded Cu(3)(BTC)(2) samples gave evidence on the structural changes due to water adsorption within the MOF material as well as information on water dynamics. The analysis of (1)H spinning sideband intensities reveals differences in the (1)H-(63/65)Cu hyperfine coupling between dehydrated and water-loaded samples. The investigation was continued for 60 days to follow the stability of the Cu(3)(BTC)(2) network under humid conditions. NMR data reveal that Cu(3)(BTC)(2) decomposes quite fast with the decomposition being different for different water contents. This journal is © the Owner Societies 2011

NMR Studies of Cartilage Dynamics, Diffusion, Degradation

NASA Astrophysics Data System (ADS)

Huster, Daniel; Schiller, Jurgen; Naji, Lama; Kaufmann Jorn; Arnold, Klaus

An increasing number of people is suffering from rheumatic diseases, and, therefore, methods of early diagnosis of joint degeneration are urgently required. For their establishment, however, an improved knowledge about the molecular organisation of cartilage would be helpful. Cartilage consists of three main components: Water, collagen and chondroitin sulfate (CS) that is (together with further polysaccharides and proteins) a major constituent of the proteoglycans of cartilage. 1H and 13C MAS (magic-angle spinning) NMR (nuclear magnetic resonance) opened new perspectives for the study of the macromolecular components in cartilage. We have primarily studied the mobilities of CS and collagen in bovine nasal and pig articular cartilage (that differ significantly in their collagen/polysaccharide content) by measuring 13C NMR relaxation times as well as the corresponding 13C CP (cross polarisation) MAS NMR spectra. These data clearly indicate that the mobility of cartilage macromolecules is broadly distributed from almost completely rigid (collagen) to highly mobile (polysaccharides), which lends cartilage its mechanical strength and shock-absorbing properties.

Solid-State NMR Studies Reveal Native-like β-Sheet Structures in Transthyretin Amyloid

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

Lim, Kwang Hun; Dasari, Anvesh K. R.; Hung, Ivan

Structural characterization of amyloid rich in cross-β structures is crucial for unraveling the molecular basis of protein misfolding and amyloid formation associated with a wide range of human disorders. Elucidation of the β-sheet structure in noncrystalline amyloid has, however, remained an enormous challenge. Here we report structural analyses of the β-sheet structure in a full-length transthyretin amyloid using solid-state NMR spectroscopy. Magic-angle-spinning (MAS) solid-state NMR was employed to investigate native-like β-sheet structures in the amyloid state using selective labeling schemes for more efficient solid-state NMR studies. Analyses of extensive long-range 13 C- 13 C correlation MAS spectra obtained with selectivelymore » 13 CO- and 13 Cα-labeled TTR reveal that the two main β-structures in the native state, the CBEF and DAGH β-sheets, remain intact after amyloid formation. The tertiary structural information would be of great use for examining the quaternary structure of TTR amyloid.« less

Solid-State NMR Studies Reveal Native-like β-Sheet Structures in Transthyretin Amyloid

DOE PAGES

Lim, Kwang Hun; Dasari, Anvesh K. R.; Hung, Ivan; ...

2016-09-02

Structural characterization of amyloid rich in cross-β structures is crucial for unraveling the molecular basis of protein misfolding and amyloid formation associated with a wide range of human disorders. Elucidation of the β-sheet structure in noncrystalline amyloid has, however, remained an enormous challenge. Here we report structural analyses of the β-sheet structure in a full-length transthyretin amyloid using solid-state NMR spectroscopy. Magic-angle-spinning (MAS) solid-state NMR was employed to investigate native-like β-sheet structures in the amyloid state using selective labeling schemes for more efficient solid-state NMR studies. Analyses of extensive long-range 13 C- 13 C correlation MAS spectra obtained with selectivelymore » 13 CO- and 13 Cα-labeled TTR reveal that the two main β-structures in the native state, the CBEF and DAGH β-sheets, remain intact after amyloid formation. The tertiary structural information would be of great use for examining the quaternary structure of TTR amyloid.« less

NMR characterization and sorption behavior of agricultural and forest soil humic substances

NASA Astrophysics Data System (ADS)

Li, Chengliang; Berns, Anne E.; Séquaris, Jean-Marie; Klumpp, Erwin

2010-05-01

Humic substances are the predominant components of the organic matter in the terrestrial system, which are not only important for the physicochemical properties of soil but are also dominant factors for controlling the environmental behaviors and fates of some organic contaminants, such as hydrophobic compounds. Nonylphenol [4-(1-ethyl-1, 3 dimethylpentyl) phenol] (NP), a ubiquitous hydrophobic pollutant, has recently focused the attention owing to its endocrine disruptors property. Sorption behavior of NP on humic substances, which were isolated from agricultural and forest soils, was investigated by using the dialysis technique at room temperature. 14C-labeled NP was used to quantify the partitioning behavior. Humic substances were characterized by 13C Cross-Polarization/Magic-Angle-Spinning Nuclear Magnetic Resonance (CP/MAS NMR). The results showed that the partition parameters of NP on various humic acids were slightly different. Relationships between partition coefficients and the functional groups of humic substances identified by CP/MAS NMR were analyzed.

The Multidimensional Attitudes Scale toward Persons with Disabilities (MAS): Construction and Validation

ERIC Educational Resources Information Center

Findler, Liora; Vilchinsky, Noa; Werner, Shirli

2007-01-01

This study presents the development of a new instrument, the "Multidimensional Attitudes Scale Toward Persons With Disabilities" (MAS). Based on the multidimensional approach, it posits that attitudes are composed of three dimensions: affect, cognition, and behavior. The scale was distributed to a sample of 132 people along with a…

Electrochemical and solid-state NMR studies on LiCoO 2 coated with Al 2O 3 derived from carboxylate-alumoxane

NASA Astrophysics Data System (ADS)

Fey, George T. K.; Kao, H. M.; Muralidharan, P.; Kumar, T. P.; Cho, Y. D.

The surface of LiCoO 2 cathodes was coated with various wt.% of Al 2O 3 derived from methoxyethoxy acetate-alumoxane (MEA-alumoxane) by a mechano-thermal coating procedure, followed by calcination at 723 K in air for 10 h. The structure and morphology of the surface modified LiCoO 2 samples have been characterized with XRD, SEM, EDS, TEM, BET, XPS/ESCA and solid-state 27Al magic angle spinning (MAS) NMR techniques. The Al 2O 3 coating forms a thin layer on the surface of the core material with an average thickness of 20 nm. The corresponding 27Al MAS NMR spectrum basically exhibited the same characteristics as the spectrum for pristine Al 2O 3 derived from MEA-alumoxane, indicating that the local environment of aluminum atoms was not significantly changed at coating levels below 1 wt.%. This provides direct evidence that Al 2O 3 was on the surface of the core materials. The LiCoO 2 coated with 1 wt.% Al 2O 3 sustained continuous cycle stability 13 times longer than pristine LiCoO 2. A comparison of the electrochemical impedance behavior of the pristine and coated materials revealed that the failure of pristine cathode performance is associated with an increase in the particle-particle resistance upon continuous cycling. Coating improved the cathode performance by suppressing the characteristic structural phase transitions (hexagonal to monoclinic to hexagonal) that occur in pristine LiCoO 2 during the charge-discharge processes.

In Situ Flow MAS NMR Spectroscopy and Synchrotron PDF Analyses of the Local Response of the Brønsted Acidic Site in SAPO-34 during Hydration at Elevated Temperatures.

PubMed

Kalantzopoulos, Georgios N; Lundvall, Fredrik; Checchia, Stefano; Lind, Anna; Wragg, David S; Fjellvåg, Helmer; Arstad, Bjørnar

2018-02-19

In situ flow magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and synchrotron-based pair distribution function (PDF) analyses were applied to study water's interactions with the Brønsted acidic site and the surrounding framework in the SAPO-34 catalyst at temperatures up to 300 °C for NMR spectroscopy and 700 °C for PDF. 29 Si enrichment of the sample enabled detailed NMR spectroscopy investigations of the T-atom generating the Brønsted site. By NMR spectroscopy, we observed dehydration above 100 °C and a coalescence of Si peaks due to local framework adjustments. Towards 300 °C, the NMR spectroscopy data indicated highly mobile acidic protons. In situ total X-ray scattering measurements analyzed by PDF showed clear changes in the Al local environment in the 250-300 °C region, as the Al-O bond lengths showed a sudden change. This fell within the same temperature range as the increased Brønsted proton mobility. We suggest that the active site in this catalyst under industrial conditions comprises not only the Brønsted proton but also SiO 4 . To the best of our knowledge, this is the first work proposing a structural model of a SAPO catalyst by atomic PDF analysis. The combination of synchrotron PDF analysis with in situ NMR spectroscopy is promising in revealing the dynamic features of a working catalyst. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of mesoporous zeolite single crystals with cheap porogens

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

Tao Haixiang; Li Changlin; Ren Jiawen

2011-07-15

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystalmore » pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.« less

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

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

Gill, Lance; Beste, Ariana; Chen, Banghao

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE PAGES

Gill, Lance; Beste, Ariana; Chen, Banghao; ...

2017-03-22

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less

Revisiting HgCl 2: A solution- and solid-state 199Hg NMR and ZORA-DFT computational study

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Carver, Colin T.; Larsen, Ross E.; Dmitrenko, Olga; Bai, Shi; Dybowski, C.

2009-07-01

The 199Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric ( η = 0) within experimental error. The 199Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemical-shift results (solution and solid state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects. 199Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

Inverse Magnus force in free molecular flow

NASA Astrophysics Data System (ADS)

Herczynski, A.; Weidman, P.

2003-11-01

The sidewise force on a spinning sphere translating in a rarified gas is calculated assuming that the flow can be treated as a stream of free molecules. This approach was first introduced by Newton in his investigation of the drag force. While it is not fruitful at subsonic flows in normal conditions, it gives remarkably accurate results at hypersonic speeds. Here it is applied to the high Knudsen number flow over spinning spheres, cylinders, cubes and more generally any spinning parallelepiped. In all cases, the force is in the opposite direction to that of the classical Magnus effect in continuum flow. The simple calculation for a sphere reproduces the isothermal result obtained recently by Borg, et al. (Phys. Fluids, 15, 2003) using Maxwellian distribution functions. For any parallelepiped, including the cube, just like for the sphere and the cylinder, the force is shown to be steady. In each of these, the magnitude of the inverse Magnus force is proprtional to the product of the angular speed, translational speed, and the mas of the gas displaced by the object.

13C CP MAS NMR and GIAO-CHF calculations of coumarins.

PubMed

Zolek, Teresa; Paradowska, Katarzyna; Wawer, Iwona

2003-01-01

13C cross-polarization magic-angle spinning NMR spectra were recorded for a series of solid coumarins. Ab initio calculations of shielding constants were performed with the use of GIAO-CHF method. The combined CPMAS NMR and theoretical approach was successful in characterizing solid-state conformations of coumarins; a relationship sigma (ppm) = -1.032 xdelta + 205.28 (R(2) = 0.9845) can be used to obtain structural information for coumarins, for which solid-state NMR or crystal structure data are not available. Copyright 2002 Elsevier Science (USA)

Reactions of CW Agents HD And GD with the Polymer Fabrics PVAM and CHEMCAT 41

DTIC Science & Technology

2015-09-01

analyses of the rates of G agent decomposition were followed by the methods of solids NMR (high resolution magic angle spinning, HR-MAS). A P-31...molecular weight copolymer of 30-35 kDa. The Erkol copolymer forms a pH 12 solution in water and functions as Lewis base when hydrated .6 GD and DFP...Reactions The hydrated PVAm film, containing 20% glycerol, was found to completely deplete and decompose a two-fold excess of DFP vapor (peaks -8 and

Impact of chemotherapy on metabolic reprogramming: Characterization of the metabolic profile of breast cancer MDA-MB-231 cells using 1H HR-MAS NMR spectroscopy.

PubMed

Maria, Roberta M; Altei, Wanessa F; Selistre-de-Araujo, Heloisa S; Colnago, Luiz A

2017-11-30

Doxorubicin, cisplatin, and tamoxifen are part of many chemotherapeutic regimens. However, studies investigating the effect of chemotherapy on the metabolism of breast cancer cells are still limited. We used 1 H high-resolution magic angle spinning (HR-MAS) NMR spectroscopy to study the metabolic profile of human breast cancer MDA-MB-231 cells either untreated (control) or treated with tamoxifen, cisplatin, and doxorubicin. 1 H HR-MAS NMR single pulse spectra evidenced signals from all mobile cell compounds, including fatty acids (membranes), water-soluble proteins, and metabolites. NMR spectra showed that phosphocholine (i.e., a biomarker of breast cancer malignant transformation) signals were stronger in control than in treated cells, but significantly decreased upon treatment with tamoxifen/cisplatin. NMR spectra acquired with Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence were interpreted only qualitatively because signal areas were attenuated according to their transverse relaxation times (T 2 ). The CPMG method was used to identify soluble metabolites such as organic acids, amino acids, choline and derivatives, taurine, guanidine acetate, tyrosine, and phenylalanine. The fatty acid variations observed by single pulse as well as the lactate, acetate, glycine, and phosphocholine variations observed through CPMG 1 H HR-MAS NMR have potential to characterize both responder and non-responder tumors in a molecular level. Additionally, we emphasized that comparable tumors (i.e., with the same origin, in this case breast cancer) may respond totally differently to chemotherapy. Our observations reinforce the theory that alterations in cellular metabolism may contribute to the development of a malignant phenotype and cell resistance. Copyright © 2017 Elsevier B.V. All rights reserved.

Periodic organosilica hollow nanospheres as anode materials for lithium ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Sasidharan, Manickam; Nakashima, Kenichi; Gunawardhana, Nanda; Yokoi, Toshiyuki; Ito, Masanori; Inoue, Masamichi; Yusa, Shin-Ichi; Yoshio, Masaki; Tatsumi, Takashi

2011-11-01

Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance (29Si MAS NMR and 13CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles.Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance (29Si MAS NMR and 13CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles. Electronic supplementary information (ESI) available: FTIR, Raman spectral data, additional TEM pictures, N2 adsorption and physical characteristics of hollow particles data, and cycling performance of dense silica particles. See DOI: 10.1039/c1nr10804b

Chicken parvovirus and its associations with malabsorption syndrome.

PubMed

Finkler, F; Lima, D A; Cerva, C; Moraes, L B; Cibulski, S P; Teixeira, T F; Santos, H F; Almeida, L L; Roehe, P M; Franco, A C

2016-08-01

Malabsorption syndrome (MAS) is a multifactorial syndrome which is characterized by enteric disorders and reduced growth rates of broilers. Such condition is responsible for significant economic losses to the poultry industry. A possible association between chicken parvovirus (ChPV) infections and the occurrence of MAS has been proposed. However, such association has not to date been elucidated in view that ChPV has been detected in healthy as well as in MAS-affected chickens. This study aimed to detect and quantify ChPV loads in sera and tissues of MAS-affected, as well as in healthy broilers. Fifty nine, 39-day-old broilers (50 diseased, 9 healthy birds), obtained from the same flocks, were examined. The highest ChPV DNA loads were detected in MAS-affected broilers, particularly in fecal samples and intestinal tissues (~5500 genomic copies/300ng of total DNA). The average viral genome load in serum in MAS-affected birds was 1134copies/mL, whereas no viral DNA was found in sera and thymus tissues from healthy animals. These findings reveal that MAS-affected broilers consistently carry ChPV DNA is serum, whereas healthy animals do not. In addition, viral loads in tissues (bursa of Fabricius, spleen, intestine and liver) of MAS-affected birds were significantly higher in comparison to the same tissues from healthy broilers. Although preliminary, the results obtained here indicate an association between the detection of ChPV DNA in serum, in addition to high ChPV viral loads in tissues, and the occurrence of MAS in broilers. Further experiments should be performed to confirm such results. Copyright © 2016. Published by Elsevier Ltd.

FTIR and 1H MAS NMR investigations on the correlation between the frequency of stretching vibration and the chemical shift of surface OH groups of solids

NASA Astrophysics Data System (ADS)

Brunner, Eike; Karge, H. G.; Pfeifer, H.

1992-03-01

The study of surface hydroxyl groups of solids, especially of zeolites, belongs to the 'classical' topics of IR spectroscopy since physico-chemical information may be derived from the wavenumber (nu) OH of the stretching vibration of the different hydroxyls. On the other hand, the last decade has seen the development of high resolution solid-state NMR spectroscopy and through the use of the so-called magic-angle-spinning technique (MAS) the signals of different hydroxyl species can be resolved in the 1H NMR spectra of solids. The chemical shift (delta) H describing the position of these lines may be used as well as (nu) OH to characterize quantitatively the strength of acidity of surface OH groups of solids. In a first comparison of (nu) OH with (delta) H for several types of surface OH groups, a linear correlation between them could be found. The aim of this paper was to prove the validity of this correlation for a wide variety of hydroxyls. The IR measurements were carried out on a Perkin-Elmer FTIR spectrometer 1800 at the Fritz Haber Institute of the Max Planck Society, Berlin, and the 1H MAS NMR spectra were recorded on a Bruker MSL- 300 at the University of Leipzig.

Advanced slow-magic angle spinning probe for magnetic resonance imaging and spectroscopy

DOEpatents

Wind, Robert A.; Hu, Jian Zhi; Minard, Kevin R.; Rommereim, Donald N.

2006-01-24

The present invention relates to a probe and processes useful for magnetic resonance imaging and spectroscopy instruments. More particularly, the invention relates to a MR probe and processes for obtaining resolution enhancements of fluid objects, including live specimens, using an ultra-slow (magic angle) spinning (MAS) of the specimen combined with a modified phase-corrected magic angle turning (PHORMAT) pulse sequence. Proton NMR spectra were measured of the torso and the top part of the belly of a female BALBc mouse in a 2T field, while spinning the animal at a speed of 1.5 Hz. Results show that even in this relatively low field with PHORMAT, an isotropic spectrum is obtained with line widths that are a factor 4.6 smaller than those obtained in a stationary mouse. Resolution of ¹H NMR metabolite spectra are thus significantly enhanced. Results indicate that PHORMAT has the potential to significantly increase the utility of ¹H NMR spectroscopy for in vivo biochemical, biomedical and/or medical applications involving large-sized biological objects such as mice, rats and even humans within a hospital setting. For small-sized objects, including biological objects, such as excised tissues, organs, live bacterial cells, and biofilms, use of PASS at a spinning rate of 30 Hz and above is preferred.

Physical characterization of functionalized spider silk: electronic and sensing properties

PubMed Central

Steven, Eden; Park, Jin Gyu; Paravastu, Anant; Lopes, Elsa Branco; Brooks, James S; Englander, Ongi; Siegrist, Theo; Kaner, Papatya; Alamo, Rufina G

2011-01-01

This work explores functional, fundamental and applied aspects of naturally harvested spider silk fibers. Natural silk is a protein polymer where different amino acids control the physical properties of fibroin bundles, producing, for example, combinations of β-sheet (crystalline) and amorphous (helical) structural regions. This complexity presents opportunities for functional modification to obtain new types of material properties. Electrical conductivity is the starting point of this investigation, where the insulating nature of neat silk under ambient conditions is described first. Modification of the conductivity by humidity, exposure to polar solvents, iodine doping, pyrolization and deposition of a thin metallic film are explored next. The conductivity increases exponentially with relative humidity and/or solvent, whereas only an incremental increase occurs after iodine doping. In contrast, iodine doping, optimal at 70 °C, has a strong effect on the morphology of silk bundles (increasing their size), on the process of pyrolization (suppressing mass loss rates) and on the resulting carbonized fiber structure (that becomes more robust against bending and strain). The effects of iodine doping and other functional parameters (vacuum and thin film coating) motivated an investigation with magic angle spinning nuclear magnetic resonance (MAS-NMR) to monitor doping-induced changes in the amino acid-protein backbone signature. MAS-NMR revealed a moderate effect of iodine on the helical and β-sheet structures, and a lesser effect of gold sputtering. The effects of iodine doping were further probed by Fourier transform infrared (FTIR) spectroscopy, revealing a partial transformation of β-sheet-to-amorphous constituency. A model is proposed, based on the findings from the MAS-NMR and FTIR, which involves iodine-induced changes in the silk fibroin bundle environment that can account for the altered physical properties. Finally, proof-of-concept applications of functionalized spider silk are presented for thermoelectric (Seebeck) effects and incandescence in iodine-doped pyrolized silk fibers, and metallic conductivity and flexibility of micron-sized gold-sputtered silk fibers. In the latter case, we demonstrate the application of gold-sputtered neat spider silk to make four-terminal, flexible, ohmic contacts to organic superconductor samples. PMID:27877440

Spatially offset AGN candidates in the CLASS survey

NASA Astrophysics Data System (ADS)

Skipper, Chris J.; Browne, Ian W. A.

2018-04-01

Prompted by a recent claim by Barrows et al. that X-ray active galactic nuclei (AGNs) are often found significantly offset from the centres of their host galaxies, we have looked for examples of compact radio sources that are offset from the optical centroids of nearby (z < 0.2) galaxies. We have selected a sample of 345 galaxies from the Sloan Digital Sky Survey (SDSS) galaxy catalogue, which have nearby compact radio sources listed in the Cosmic-Lens All Sky Survey (CLASS) catalogue. We find only three matches (˜0.87 per cent of the sample) with offsets greater than 600 milliarcsec (mas), which is considerably fewer than we would have expected from the Barrows et al. X-ray survey. We fit our histogram of offsets with a Rayleigh distribution with σ = 60.5 mas, but find that there is an excess of objects with separations greater than ˜150 mas. Assuming that this excess represents AGNs with real offsets, we place an upper limit of ˜17 per cent on the fraction of offset AGNs in our radio-selected sample. We select 38 objects with offsets greater than 150 mas, and find they have some diverse properties: Some are well known, such as Mrk 273 and Arp 220, some have dust lanes, which may have affected the optical astrometry, and a few are strong new candidates for offset AGNs.

Development and Initial Validation of the Macrophage Activation Syndrome/Primary Hemophagocytic Lymphohistiocytosis Score, a Diagnostic Tool that Differentiates Primary Hemophagocytic Lymphohistiocytosis from Macrophage Activation Syndrome.

PubMed

Minoia, Francesca; Bovis, Francesca; Davì, Sergio; Insalaco, Antonella; Lehmberg, Kai; Shenoi, Susan; Weitzman, Sheila; Espada, Graciela; Gao, Yi-Jin; Anton, Jordi; Kitoh, Toshiyuki; Kasapcopur, Ozgur; Sanner, Helga; Merino, Rosa; Astigarraga, Itziar; Alessio, Maria; Jeng, Michael; Chasnyk, Vyacheslav; Nichols, Kim E; Huasong, Zeng; Li, Caifeng; Micalizzi, Concetta; Ruperto, Nicolino; Martini, Alberto; Cron, Randy Q; Ravelli, Angelo; Horne, AnnaCarin

2017-10-01

To develop and validate a diagnostic score that assists in discriminating primary hemophagocytic lymphohistiocytosis (pHLH) from macrophage activation syndrome (MAS) related to systemic juvenile idiopathic arthritis. The clinical, laboratory, and histopathologic features of 362 patients with MAS and 258 patients with pHLH were collected in a multinational collaborative study. Eighty percent of the population was assessed to develop the score and the remaining 20% constituted the validation sample. Variables that entered the best fitted model of logistic regression were assigned a score, based on their statistical weight. The MAS/HLH (MH) score was made up with the individual scores of selected variables. The cutoff in the MH score that discriminated pHLH from MAS best was calculated by means of receiver operating characteristic curve analysis. Score performance was examined in both developmental and validation samples. Six variables composed the MH score: age at onset, neutrophil count, fibrinogen, splenomegaly, platelet count, and hemoglobin. The MH score ranged from 0 to 123, and its median value was 97 (1st-3rd quartile 75-123) and 12 (1st-3rd quartile 11-34) in pHLH and MAS, respectively. The probability of a diagnosis of pHLH ranged from <1% for a score of <11 to >99% for a score of  ≥123. A cutoff value of ≥60 revealed the best performance in discriminating pHLH from MAS. The MH score is a powerful tool that may aid practitioners to identify patients who are more likely to have pHLH and, thus, could be prioritized for functional and genetic testing. Copyright © 2017 Elsevier Inc. All rights reserved.

Application of High-Resolution Magic-Angle Spinning NMR Spectroscopy to Define the Cell Uptake of MRI Contrast Agents

NASA Astrophysics Data System (ADS)

Calabi, Luisella; Alfieri, Goffredo; Biondi, Luca; De Miranda, Mario; Paleari, Lino; Ghelli, Stefano

2002-06-01

A new method, based on proton high-resolution magic-angle spinning ( 1H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible.

Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

PubMed

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2015-07-21

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

Effects of Cornus mas L. and Morus rubra L. extracts on penicillin-induced epileptiform activity: an electrophysiological and biochemical study.

PubMed

Tubaş, Filiz; Per, Sedat; Taşdemir, Abdulkadir; Bayram, Ayşe Kaçar; Yıldırım, Mehmet; Uzun, Aydın; Saraymen, Recep; Gümüş, Hakan; Elmalı, Ferhan; Per, Hüseyin

2017-01-01

Traditionally, Morus rubra L. (Moraceae) (red mulberry) and Cornus mas L. (Cornacea) (cornelian cherry) fruits are eaten fresh and are also used in marmalades, juices, jam, natural dyes in Turkey and are believed to have beneficial effects in case of multiple health issues such as antipyretic, diarrhea and intestinal parasites. However, the effects of M. rubra and C. mas on epilepsy has not been known. This study evaluates the effects of M. rubra and C. mas extracts on penicillin-induced epileptiform activity. Sixty Wistar rats randomly divided into ten groups (n=6): control, sham, penicillin, penicillin+M. rubra extract (2.5, 5, 10, 20 mg/kg) and penicillin+C. mas extract (2.5, 5, 10 mg/kg). Epileptiform activity was induced by using penicillin (500 IU, i.c.) and electrocorticogram records (150 min) were obtained. Also, biochemical analysis in blood samples were evaluated. According to the electrocorticogram analysis, the effective dose was detected as 10 mg/kg for both C. mas and M. rubra. This dose decreased the spike frequencies of convulsions while amplitude wasn't changed by both substances. In erythrocyte studies, there were significant differences regarding nitric oxide in the control, sham and penicillin groups. There were significant differences regarding malondialdehyde in all groups. In the plasma, there were significant differences among groups regarding xanthine oxidase in the penicillin‑C. mas and penicillin‑M. rubra groups. There were differences regarding malondialdehyde in the penicillin-C. mas and M. rubra-C. mas groups. Both extracts reduced the frequency of epileptiform activity. After administration of the extracts malondialdehyde levels decreased also in both erythrocytes and plasma.

Chemical characterization of fractions of dissolved humic substances from a marginal sea—a case from the Southern Yellow Sea

NASA Astrophysics Data System (ADS)

Zhang, Yaoling; Yang, Keli; Du, Jinzhou; Zhang, Fenfen; Dong, Yaping; Li, Wu

2018-03-01

Marine dissolved organic matter (DOM) is one of the largest dynamic pools of organic carbon in the global carbon cycle, yet DOM is still chemically poorly characterized. To better understand the origin, composition, and cycling of DOM in the China marginal sea, dissolved humic substances (DHS) were isolated from seawaters in two locations in the Southern Yellow Sea. The DHS were subdivided into fulvic acids (FAs), humic acids (HAs) and the XAD-4 fractions. Complementary analytical approaches were used to characterize the isolated DHS samples including stable carbon isotopic composition, Fourier transform infrared spectroscopy (FTIR), 13C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR), and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). The results demonstrated that both DHS samples encountered the influences from marine source, indicating that algal and microbial-derived materials are the predominant precursors for the studied samples. The three fractions of DHS showed different properties. FAs presented more aromatic features, whereas HAs contained more aliphatic lipids and proteinaceous materials. The XAD-4 fractions were enriched in 13C and contained more carbohydrates but less aromatic compounds. The lower molecular weight and higher heteroatom content and number of carboxyl groups for the XAD-4 fractions may give them considerable geochemical significance for aspects of trace metal species, bioavailability of pollutants, mineral weathering and water acidification in marine environments.

Chicken parvovirus viral loads in cloacal swabs from malabsorption syndrome-affected and healthy broilers.

PubMed

Finkler, Fabrine; de Lima, Diane Alves; Cerva, Cristine; Cibulski, Samuel Paulo; Teixeira, Thais Fumaco; Dos Santos, Helton Fernandes; de Almeida, Laura Lopes; Roehe, Paulo Michel; Franco, Ana Cláudia

2016-12-01

Chicken parvovirus (ChPV) has been associated with malabsorption syndrome (MAS) in broilers. However, the participation of this virus in such syndrome is unclear, since it may be detected in diseased and healthy chickens. In the course of these studies, it was argued whether ChPV genome loads might be correlated to the occurrence of MAS. To check such a hypothesis, a SYBR green-based quantitative polymerase chain reaction was developed to detect and quantify ChPV genomes. Cloacal swabs from 68 broilers with MAS and 59 from healthy animals were collected from different poultry farms. Genomes of ChPV were detected in all samples, regardless of their health status. However, viral genome loads in MAS-affected broilers were significantly higher (1 × 10 5 genome copies per 100 ng DNA) than in healthy animals (1.3 × 10 3 GC/100 ng DNA). These findings indicate that there is an association between high ChPV genome loads and the occurrence of MAS in broilers.

Cross-validating a bidimensional mathematics anxiety scale.

PubMed

Haiyan Bai

2011-03-01

The psychometric properties of a 14-item bidimensional Mathematics Anxiety Scale-Revised (MAS-R) were empirically cross-validated with two independent samples consisting of 647 secondary school students. An exploratory factor analysis on the scale yielded strong construct validity with a clear two-factor structure. The results from a confirmatory factor analysis indicated an excellent model-fit (χ(2) = 98.32, df = 62; normed fit index = .92, comparative fit index = .97; root mean square error of approximation = .04). The internal consistency (.85), test-retest reliability (.71), interfactor correlation (.26, p < .001), and positive discrimination power indicated that MAS-R is a psychometrically reliable and valid instrument for measuring mathematics anxiety. Math anxiety, as measured by MAS-R, correlated negatively with student achievement scores (r = -.38), suggesting that MAS-R may be a useful tool for classroom teachers and other educational personnel tasked with identifying students at risk of reduced math achievement because of anxiety.

Clay Minerals

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

Mueller, Karl T.; Sanders, Rebecca L.; Washton, Nancy M.

2014-03-14

Clay minerals are important components of the environment and are involved or implicated in processes such as the uptake of pollutants and the release of nutrients and as potential platforms for a number of chemical reactions. Owing to their small particle sizes (typically, on the order of microns or smaller) and mixing with a variety of other minerals and soil components, advanced characterization methods are needed to study their structures, dynamics, and reactivities. In this article, we describe the use of solid-state NMR methods to characterize the structures and chemistries of clay minerals. Early one-pulse magic-angle spinning (MAS) NMR studiesmore » of 27Al and 29Si have now been enhanced and extended with new studies utilizing advanced methodologies (such as Multiple Quantum MAS) as well as studies of less-sensitive nuclei. In additional work, the issue of reactivity of clay minerals has been addressed, including studies of reactive surface area in the environment. Utilizations of NMR-sensitive nuclides within the clay minerals themselves, and in molecules that react with specific sites on the clay mineral surfaces, have aided in understanding the reactivity of these complex aluminosilicate systems.« less

A (1)H HR-MAS NMR-Based Metabolomic Study for Metabolic Characterization of Rice Grain from Various Oryza sativa L. Cultivars.

PubMed

Song, Eun-Hye; Kim, Hyun-Ju; Jeong, Jaesik; Chung, Hyun-Jung; Kim, Han-Yong; Bang, Eunjung; Hong, Young-Shick

2016-04-20

Rice grain metabolites are important for better understanding of the plant physiology of various rice cultivars and thus for developing rice cultivars aimed at providing diverse processed products. However, the variation of global metabolites in rice grains has rarely been explored. Here, we report the identification of intra- or intercellular metabolites in rice (Oryza sativa L.) grain powder using a (1)H high-resolution magic angle spinning (HR-MAS) NMR-based metabolomic approach. Compared with nonwaxy rice cultivars, marked accumulation of lipid metabolites such as fatty acids, phospholipids, and glycerophosphocholine in the grains of waxy rice cultivars demonstrated the distinct metabolic regulation and adaptation of each cultivar for effective growth during future germination, which may be reflected by high levels of glutamate, aspartate, asparagine, alanine, and sucrose. Therefore, this study provides important insights into the metabolic variations of diverse rice cultivars and their associations with environmental conditions and genetic backgrounds, with the aim of facilitating efficient development and the improvement of rice grain quality through inbreeding with genetic or chemical modification and mutation.

15N photo-CIDNP MAS NMR analysis of reaction centers of Chloracidobacterium thermophilum.

PubMed

Zill, Jeremias C; He, Zhihui; Tank, Marcus; Ferlez, Bryan H; Canniffe, Daniel P; Lahav, Yigal; Bellstedt, Peter; Alia, A; Schapiro, Igor; Golbeck, John H; Bryant, Donald A; Matysik, Jörg

2018-03-30

Photochemically induced dynamic nuclear polarization (photo-CIDNP) has been observed in the homodimeric, type-1 photochemical reaction centers (RCs) of the acidobacterium, Chloracidobacterium (Cab.) thermophilum, by 15 N magic-angle spinning (MAS) solid-state NMR under continuous white-light illumination. Three light-induced emissive (negative) signals are detected. In the RCs of Cab. thermophilum, three types of (bacterio)chlorophylls have previously been identified: bacteriochlorophyll a (BChl a), chlorophyll a (Chl a), and Zn-bacteriochlorophyll a' (Zn-BChl a') (Tsukatani et al. in J Biol Chem 287:5720-5732, 2012). Based upon experimental and quantum chemical 15 N NMR data, we assign the observed signals to a Chl a cofactor. We exclude Zn-BChl because of its measured spectroscopic properties. We conclude that Chl a is the primary electron acceptor, which implies that the primary donor is most likely Zn-BChl a'. Chl a and 8 1 -OH Chl a have been shown to be the primary electron acceptors in green sulfur bacteria and heliobacteria, respectively, and thus a Chl a molecule serves this role in all known homodimeric type-1 RCs.

Synthesis of kalsilite from microcline powder by an alkali-hydrothermal process

NASA Astrophysics Data System (ADS)

Su, Shuang-qing; Ma, Hong-wen; Yang, Jing; Zhang, Pan; Luo, Zheng

2014-08-01

The properties of aluminosilicate kalsilite have attracted the interest of researchers in chemical synthesis, ceramic industry, biofuels, etc. In this study, kalsilite was hydrothermally synthesized from microcline powder in a KOH solution. The microcline powder, rich in potassium, aluminum, and silicon, was collected from Mountain Changling in Northwestern China. The effects of temperature, time, and KOH concentration on the decomposition of microcline were investigated. The kalsilite and intermediate products were characterized by means of wet chemistry analysis, X-ray Diffraction (XRD), infrared spectrometry (IR), 29Si magic angle spinning nuclear magnetic resonance (29Si MAS NMR), 27Al MAS NMR, and scanning electron microscope (SEM). With increasing temperature, the microcline powder transforms into a metastable KAlSiO4 polymorph before transforming further into pure kalsilite. A mixture of both kalsilite and metastable KAlSiO4 polymorph is obtained when the hydrothermal reaction is carried out within 2 h; but after 2 h, kalsilite is the predominant product. The concentration of KOH, which needs to be larger than 4.3 M, is an important parameter influencing the synthesis of kalsilite.

High-field 95 Mo and 183 W static and MAS NMR study of polyoxometalates.

PubMed

Haouas, Mohamed; Trébosc, Julien; Roch-Marchal, Catherine; Cadot, Emmanuel; Taulelle, Francis; Martineau-Corcos, Charlotte

2017-10-01

The potential of high-field NMR to measure solid-state 95 Mo and 183 W NMR in polyoxometalates (POMs) is explored using some archetypical structures like Lindqvist, Keggin and Dawson as model compounds that are well characterized in solution. NMR spectra in static and under magic angle spinning (MAS) were obtained, and their analysis allowed extraction of the NMR parameters, including chemical shift anisotropy and quadrupolar coupling parameters. Despite the inherent difficulties of measurement in solid state of these low-gamma NMR nuclei, due mainly to the low spectral resolution and poor signal-to-noise ratio, the observed global trends compare well with the solution-state NMR data. This would open an avenue for application of solid-state NMR to POMs, especially when liquid-state NMR is not possible, e.g., for poorly soluble or unstable compounds in solution, and for giant molecules with slow tumbling motion. This is the case of Keplerate where we provide here the first NMR characterization of this class of POMs in the solid state. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Fast REDOR with CPMG multiple-echo acquisition

NASA Astrophysics Data System (ADS)

Hung, Ivan; Gan, Zhehong

2014-01-01

Rotational-Echo Double Resonance (REDOR) is a widely used experiment for distance measurements in solids. The conventional REDOR experiment measures the signal dephasing from hetero-nuclear recoupling under magic-angle spinning (MAS) in a point by point manner. A modified Carr-Purcell Meiboom-Gill (CPMG) multiple-echo scheme is introduced for fast REDOR measurement. REDOR curves are measured from the CPMG echo amplitude modulation under dipolar recoupling. The real time CPMG-REDOR experiment can speed up the measurement by an order of magnitude. The effects from hetero-nuclear recoupling, the Bloch-Siegert shift and echo truncation to the signal acquisition are discussed and demonstrated.

A comparison of laser ablation-inductively coupled plasma-mass spectrometry and high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers

NASA Astrophysics Data System (ADS)

de Gois, Jefferson S.; Van Malderen, Stijn J. M.; Cadorim, Heloisa R.; Welz, Bernhard; Vanhaecke, Frank

2017-06-01

This work describes the development and comparison of two methods for the direct determination of Br in polymer samples via solid sampling, one using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and the other using high-resolution continuum source graphite furnace molecular absorption spectrometry with direct solid sample analysis (HR-CS SS-GF MAS). The methods were optimized and their accuracy was evaluated by comparing the results obtained for 6 polymeric certified reference materials (CRMs) with the corresponding certified values. For Br determination with LA-ICP-MS, the 79Br+ signal could be monitored interference-free. For Br determination via HR-CS SS-GF MAS, the CaBr molecule was monitored at 625.315 nm with integration of the central pixel ± 1. Bromine quantification by LA-ICP-MS was performed via external calibration against a single CRM while using the 12C+ signal as an internal standard. With HR-CS SS-GF MAS, Br quantification could be accomplished using external calibration against aqueous standard solutions. Except for one LA-ICP-MS result, the concentrations obtained with both techniques were in agreement with the certified values within the experimental uncertainty as evidenced using a t-test (95% confidence level). The limit of quantification was determined to be 100 μg g- 1 Br for LA-ICP-MS and 10 μg g- 1 Br for HR-CS SS-GF MAS.

Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs).

PubMed

Yuan, Jia; Hapis, Stefania; Breitzke, Hergen; Xu, Yeping; Fasel, Claudia; Kleebe, Hans-Joachim; Buntkowsky, Gerd; Riedel, Ralf; Ionescu, Emanuel

2014-10-06

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

A "special perspectives" issue: Recent achievements and new directions in biomolecular solid state NMR

NASA Astrophysics Data System (ADS)

Tycko, Robert

2015-04-01

Twenty years ago, applications of solid state nuclear magnetic resonance (NMR) methods to real problems involving biological systems or biological materials were few and far between. Starting in the 1980s, a small number of research groups had begun to explore the possibility of obtaining structural and dynamical information about peptides, proteins, and other biopolymers from solid state NMR spectra. Progress was initially slow due to the relatively primitive state of solid state NMR probes, spectrometers, sample preparation methods, and pulse sequence techniques, coupled with the small number of people contributing to this research area. By the early 1990s, with the advent of new ideas about pulse sequence techniques such as dipolar recoupling, improvements in techniques for orienting membrane proteins and in technology for magic-angle spinning (MAS), improvements in the capabilities of commercial NMR spectrometers, and general developments in multidimensional spectroscopy, it began to appear that biomolecular solid state NMR might have a viable future. It was not until 1993 that the annual number of publications in this area crept above twenty.

Determination of NH proton chemical shift anisotropy with 14N-1H heteronuclear decoupling using ultrafast magic angle spinning solid-state NMR

NASA Astrophysics Data System (ADS)

Pandey, Manoj Kumar; Nishiyama, Yusuke

2015-12-01

The extraction of chemical shift anisotropy (CSA) tensors of protons either directly bonded to 14N nuclei (I = 1) or lying in their vicinity using rotor-synchronous recoupling pulse sequence is always fraught with difficulty due to simultaneous recoupling of 14N-1H heteronuclear dipolar couplings and the lack of methods to efficiently decouple these interactions. This difficulty mainly arises from the presence of large 14N quadrupolar interactions in comparison to the rf field that can practically be achieved. In the present work it is demonstrated that the application of on-resonance 14N-1H decoupling with rf field strength ∼30 times weaker than the 14N quadrupolar coupling during 1H CSA recoupling under ultrafast MAS (90 kHz) results in CSA lineshapes that are free from any distortions from recoupled 14N-1H interactions. With the use of extensive numerical simulations we have shown the applicability of our proposed method on a naturally abundant L-Histidine HCl·H2O sample.

Self-immobilization and/or thermal treatment for preparing silica-poly(methyloctylsiloxane) stationary phases.

PubMed

Bottoli, Carla B G; Vigna, Camila R M; Fischer, Gerd; Albert, Klaus; Collins, Kenneth E; Collins, Carol H

2004-03-19

Batches of poly(methyloctylsiloxane) (PMOS)-loaded silica were prepared by the deposition of PMOS, into the pores of HPLC silica. Portions of PMOS-loaded silica were allowed to remain at ambient temperature, without further treatment for 2, 9, 20, 31, 51, 105 and 184 days after preparation to undergo self-immobilization (irreversible adsorption of a layer of polymer on silica at ambient temperature in the absence of initiators). Other portions were subjected to a thermal treatment (100 degrees C for 4h) after 1, 2, 5, 7, 9, 15, 20, 25, 70, 111 and 184 days. Self-immobilized and thermally treated samples were characterized by % C, 29Si cross-polarization magic angle spinning (CP/MAS) NMR spectroscopy and reversed-phase column performance. The results show that thermal immobilization accelerates the distribution and rearrangement of the polymer on the silica surface. However, from the time that a monolayer has been formed by self-immobilization (approximately 100 days for PMOS on Kromasil silica), the thermal treatment does not alter this configuration and, thus, does not change the resulting chromatographic parameters.

Fabrication of Cellulose Film with Enhanced Mechanical Properties in Ionic Liquid 1-Allyl-3-methylimidaxolium Chloride (AmimCl)

PubMed Central

Pang, Jinhui; Liu, Xin; Zhang, Xueming; Wu, Yuying; Sun, Runcang

2013-01-01

More and more attention has been paid to environmentally friendly bio-based renewable materials as the substitution of fossil-based materials, due to the increasing environmental concerns. In this study, regenerated cellulose films with enhanced mechanical property were prepared via incorporating different plasticizers using ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as the solvent. The characteristics of the cellulose films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis (TG), X-ray diffraction (XRD), 13C Solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) and tensile testing. The results showed that the cellulose films exhibited a homogeneous and smooth surface structure. It was noted that the thermal stability of the regenerated cellulose film plasticized with glycerol was increased compared with other regenerated cellulose films. Furthermore, the incorporation of plasticizers dramatically strengthened the tensile strength and improved the hydrophobicity of cellulose films, as compared to the control sample. Therefore, these notable results exhibited the potential utilization in producing environmentally friendly cellulose films with high performance properties. PMID:28809209

Recoupling of Heteronuclear Dipolar Interactions with Rotational-Echo Double-Resonance at High Magic-Angle Spinning Frequencies

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Tounge, Brett A.; Rienstra, Chad M.; Herzfeld, Judith; Griffin, Robert G.

2000-09-01

Heteronuclear dipolar recoupling with rotational-echo double-resonance (REDOR) is investigated in the rapid magic-angle spinning regime, where radiofrequency irradiation occupies a significant fraction of the rotor period (10-60%). We demonstrate, in two model 13C-15N spin systems, [1-13C, 15N] and [2-13C, 15N]glycine, that REDOR ΔS/S0 curves acquired at high MAS rates and relatively low recoupling fields are nearly identical to the ΔS/S0 curve expected for REDOR with ideal δ-function pulses. The only noticeable effect of the finite π pulse length on the recoupling is a minor scaling of the dipolar oscillation frequency. Experimental results are explained using both numerical calculations and average Hamiltonian theory, which is used to derive analytical expressions for evolution under REDOR recoupling sequences with different π pulse phasing schemes. For xy-4 and extensions thereof, finite pulses scale only the dipolar oscillation frequency by a well-defined factor. For other phasing schemes (e.g., xx-4 and xx¯-4) both the frequency and amplitude of the oscillation are expected to change.

Technology Development for a Hyperspectral Microwave Atmospheric Sounder (HyMAS)

NASA Technical Reports Server (NTRS)

Blackwell, W.; Galbraith, C.; Hilliard, L.; Racette, P.; Thompson, E.

2014-01-01

The Hyperspectral Microwave Atmospheric Sounder (HyMAS) is being developed at Lincoln Laboratories and accommodated by the Goddard Space Flight Center for a flight opportunity on a NASA research aircraft. The term hyperspectral microwave is used to indicate an all-weather sounding instrument that performs equivalent to hyperspectral infrared sounders in clear air with vertical resolution of approximately 1 km. Deploying the HyMAS equipped scanhead with the existing Conical Scanning Microwave Imaging Radiometer (CoSMIR) shortens the path to a flight demonstration. Hyperspectral microwave is achieved through the use of independent RF antennas that sample the volume of the Earths atmosphere through various levels of frequencies, thereby producing a set of dense, spaced vertical weighting functions.

Mercury's spin-orbit model and signature of C/MR2

NASA Astrophysics Data System (ADS)

Rambaux, N.; Bois, E.

2003-04-01

The upcoming missions, MESSENGER (Solomon etal 2001, Planet. Space Sci 49) and Bepi Colombo (Milani etal 2001, Planet. Space Sci 49) with onboard instrumentation capable of measuring the rotational parameters stimulate the objective to reach an accurate theory of the rotational motion of Mercury. Our work deals with the physical and dynamical causes that induce librations around an equilibrium state defined by the 3:2 spin-orbit resonance of Mercury. In order to integrate the spin-orbit motion of Mercury, we have used our gravitational model of the solar System including the Moon's spin-orbit motion. This model, called SONYR (acronym of Spin-Orbit N-bodY Relativistic model), was previously built by Bois, Journet and Vokrouhlicky in accordance with the requirements of the Lunar Laser Ranging observational accuracy (see for instance a review by Bois 2000, C. R. Acad. Sci. Série IV, or Bois and Vokrouhlický 1995). Using the model, the present study is devoted to the main perturbations acting on the spin-orbit motion of Mercury such as the planetary interactions (and their hierarchy) and the dynamical figure of the planet. The effect of the torque of Venus is 105 times smaller in magnitude than the one due to the Sun. Moreover, the complete rotation of Mercury exhibits two proper frequencies, namely 15.825 and 1089 years, and one secular variation of 271043 years which is due to the nodal precession between the equatorial plane of Mercury and its orbital plane. It is the second synchronism of Mercury mentioned by Beletski in 1986. We have made into evidence that the 3:2 resonance of Mercury is preserved by this second synchronism, which can be understood as a spin-orbit secular resonance. We have shown that the secular resonance variable ψ - Ω librates with a frequency of 1089 years. Our model integration starts with an initial obliquity of 1.65 arcminute (re-evaluate from the Cassini state) and gives an amplitude of libration in longitude of the order of 20 arcseconds, which is in agreement with Balogh and Giamperi (2002, Rep. Prog. Phys. 65). Besides, we have computed in the Hermean librations the impact of the variation of the greatest principal moment of inertia, cm2. The maximal signature on the obliquity is then 1.4 mas (milliarsecond) on the 176 day period, and the one on the libration in longitude is 0.4 mas on the 87.9 day period, resulting from an increase of the cm2 value of 1%. These values have to be understood as upper bounds of such signatures. These two effects permit to contribute to precise the relationship between the cm2 coefficient and the internal structure of Mercury. References : Balog, A., and Giamperi, G., 2002, Rep. Prog. Phys. 65, 529-560. Beletski, V, 1986, "Essais sur le Mouvement des Corps Cosmiques", Mir (ed), Moscou. Bois, E., 2000, C. R. Acad. Sci. Paris, t. 1, Série IV, 809-823. Bois, E., and Vokrouhlický, D., 1995, Astronomy and Astrophysics 300, 559-567. Milani, A., Vokrouhlicky, D., and Bonanno, C., 2001, Planet. Space Sci 49, 1579. Solomon, etal, 2001, Planet. Space Sci 49, 1445.

Characterization of the relation between CT technical parameters and accuracy of quantification of lung attenuation on quantitative chest CT.

PubMed

Trotta, Brian M; Stolin, Alexander V; Williams, Mark B; Gay, Spencer B; Brody, Alan S; Altes, Talissa A

2007-06-01

The purpose of this study was to assess the compromise between CT technical parameters and the accuracy of CT quantification of lung attenuation. Materials that simulate water (0 H), healthy lung (-650 H), borderline emphysematous lung (-820 H), and severely emphysematous lung (-1,000 H) were placed at both the base and the apex of the lung of an anthropomorphic phantom and outside the phantom. Transaxial CT images through the samples were obtained while the effective tube current was varied from 440 to 10 mAs, kilovoltage from 140 to 80 kVp, and slice thickness from 0.625 to 10 mm. Mean +/- SD attenuation within the samples and the standard quantitative chest CT measurements, the percentage of pixels with attenuation less than -910 H and 15th percentile of attenuation, were computed. Outside the phantom, variations in CT parameters produced less than 2.0% error in all measurements. Within the anthropomorphic phantom at 30 mAs, error in measurements was much larger, ranging from zero to 200%. Below approximately 80 mAs, mean attenuation became increasingly biased. The effects were most pronounced at the apex of the lungs. Mean attenuation of the borderline emphysematous sample of apex decreased 55 H as the tube current was decreased from 300 to 30 mAs. Both the 15th percentile of attenuation and percentage of pixels with less than -910 H attenuation were more sensitive to variations in effective tube current than was mean attenuation. For example, the -820 H sample should have 0% of pixels less than -910 H, which was true at 400 mA. At 30 mA in the lung apex, however, the measurement was highly inaccurate, 51% of pixels being below this value. Decreased kilovoltage and slice thickness had analogous, but lesser, effects. The accuracy of quantitative chest CT is determined by the CT acquisition parameters. There can be significant decreases in accuracy at less than 80 mAs for thin slices in an anthropomorphic phantom, the most pronounced effects occurring in the lung apex.

Fabrication of Nanocomposites of SnO2 and MgAl2O4 for Gas Sensing Applications

NASA Astrophysics Data System (ADS)

Nithyavathy, N.; Arunmetha, S.; Vinoth, M.; Sriram, G.; Rajendran, V.

2016-04-01

Simple solid-state and sol-gel routes have been used to synthesize nanocomposites of tin oxide and magnesium aluminate at calcination temperature of 900 K for gas sensing applications. The effects of the surface structure of magnesium aluminate on the gas response for different concentrations of tin oxide addition were investigated for potential use in gas sensors. (SnO2) x doped in small amounts x into magnesium aluminate resulted in three nanocomposite samples MAS0.25, MAS0.50, and MAS0.75 for x = 0.25, 0.50, and 0.75, respectively, plus MgAl2O4 (MA) for x = 0. The response to different pressures of gases such as oxygen (O2), carbon monoxide (CO), and ethanol (C2H5OH) was quantitatively analyzed for all samples at different operating temperatures. The temperature was varied linearly by increasing the supply to a heating pad mounted below the sensor sample, regardless of the gas pressure inside the chamber. All the sample materials showed good response at different gas pressures (1 bar to 2 bar) and operating temperatures (300 K to 600 K). It was noted that the composite samples showed enhanced and fast response to gases, at both lower and higher operating temperatures, with detection of even the smallest change in gas pressure.

Redundant systematic reviews on the same topic in surgery: a study protocol for a meta-epidemiological investigation.

PubMed

Katsura, Morihiro; Kuriyama, Akira; Tada, Masafumi; Yamamoto, Kazumichi; Furukawa, Toshi A

2017-08-21

We are witnessing an explosive increase in redundant and overlapping publications of systematic reviews and meta-analyses (SRs/MAs) on the same topic, which often present conflicting results and interpretations, in the current medical literature. They represent wasted efforts on the part of investigators and peer reviewers and may confuse and possibly mislead clinicians and policymakers. Here, we present a protocol for a meta-epidemiological investigation to describe how often there are overlapping SRs/MAs on the same topic, to assess the quality of these multiple publications, and to investigate the causes of discrepant results between multiple SRs/MAs in the field of major surgery. We will use MEDLINE/PubMed to identify all SRs/MAs of randomised controlled trials (RCTs) published in 2015 regarding major surgical interventions. After identifying the 'benchmark' SRs/MAs published in 2015, a process of screening in MEDLINE will be carried out to identify the previous SRs/MAs of RCTs on the same topic that were published within 5 years of the 'benchmark' SRs/MAs. We will tabulate the number of previous SRs/MAs on the same topic of RCTs, and then describe their variations in numbers of RCTs included, sample sizes, effect size estimates and other characteristics. We will also assess the differences in quality of each SR/MA using A Measurement Tool to Assess Systematic Reviews (AMSTAR) score. Finally, we will investigate the potential reasons to explain the discrepant results between multiple SRs/MAs. No formal ethical approval and informed consent are required because this study will not collect primary individual data. The intended audiences of the findings include clinicians, healthcare researchers and policymakers. We will publish our findings as a scientific report in a peer-reviewed journal. In PROSPERO CRD42017059077, March 2017. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Characterization of lithium coordination sites with magic-angle spinning NMR

NASA Astrophysics Data System (ADS)

Haimovich, A.; Goldbourt, A.

2015-05-01

Lithium, in the form of lithium carbonate, is one of the most common drugs for bipolar disorder. Lithium is also considered to have an effect on many other cellular processes hence it possesses additional therapeutic as well as side effects. In order to quantitatively characterize the binding mode of lithium, it is required to identify the interacting species and measure their distances from the metal center. Here we use magic-angle spinning (MAS) solid-state NMR to study the binding site of lithium in complex with glycine and water (LiGlyW). Such a compound is a good enzyme mimetic since lithium is four-coordinated to one water molecule and three carboxylic groups. Distance measurements to carbons are performed using a 2D transferred echo double resonance (TEDOR) MAS solid-state NMR experiment, and water binding is probed by heteronuclear high-resolution proton-lithium and proton-carbon correlation (wPMLG-HETCOR) experiments. Both HETCOR experiments separate the main complex from impurities and non-specifically bound lithium species, demonstrating the sensitivity of the method to probe the species in the binding site. Optimizations of the TEDOR pulse scheme in the case of a quadrupolar nucleus with a small quadrupole coupling constant show that it is most efficient when pulses are positioned on the spin-1/2 (carbon-13) nucleus. Since the intensity of the TEDOR signal is not normalized, careful data analysis that considers both intensity and dipolar oscillations has to be performed. Nevertheless we show that accurate distances can be extracted for both carbons of the bound glycine and that these distances are consistent with the X-ray data and with lithium in a tetrahedral environment. The lithium environment in the complex is very similar to the binding site in inositol monophosphatase, an enzyme associated with bipolar disorder and the putative target for lithium therapy. A 2D TEDOR experiment applied to the bacterial SuhB gene product of this enzyme was designed to probe direct correlations between lithium, the enzyme inhibitor, and the closest carboxyl carbons of the binding site. At this point, the chemical shift of the bound carboxyl groups in this 29 kDa enzyme could be determined.

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

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

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2015-07-21

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

An ensemble of paired spin(-1/2) nuclei in a rotating solid: Polarization evolution and NMR spectrum in a wobbling frame.

PubMed

Kundla, Enn

2007-04-01

The evolution of the magnetic polarization of an ensemble of paired spin(-1/2) nuclei in an MAS NMR (nuclear magnetic resonance) experiment and the induced spectrum are described theoretically by means of a Liouville-von Neumann equation representation in a wobbling rotating frame in combination with the averaged Hamiltonian theory. In this method, the effect of a high-intensity external static magnetic field and the effects of the leftover interaction components of the Hamiltonian that commute with the approximate Hamiltonian are taken into account simultaneously and equivalently. This method reproduces details that really exist in the recorded spectra, caused by secular terms in the Hamiltonian, which might otherwise be smoothed out owing to the approximate treatment of the effects of the secular terms. Complete analytical expressions, which describe the whole NMR spectrum including the rotational sideband sets, and which consider all the relevant intermolecular interactions, are obtained.

15x optical zoom and extreme optical image stabilisation: diffraction limited integral field spectroscopy with the Oxford SWIFT spectrograph

NASA Astrophysics Data System (ADS)

Tecza, Matthias; Thatte, Niranjan; Clarke, Fraser; Lynn, James; Freeman, David; Roberts, Jennifer; Dekany, Richard

2012-09-01

When commissioned in November 2008 at the Palomar 200 inch Hale Telescope, the Oxford SWIFT I and z band integral field spectrograph, fed by the adaptive optics system PALAO, provided a wide (3×) range of spatial resolutions: three plate scales of 235 mas, 160 mas, and 80 mas per spaxel over a contiguous field-of-view of 89×44 pixels. Depending on observing conditions and guide star brightness we can choose a seeing limited scale of 235 mas per spaxel, or 160 mas and 80 mas per spaxel for very bright guide star AO with substantial increase of enclosed energy. Over the last two years PALAO was upgraded to PALM-3000: an extreme, high-order adaptive optics system with two deformable mirrors with more than 3000 actuators, promising diffraction limited performance in SWIFT's wavelength range. In order to take advantage of this increased spatial resolution we upgraded SWIFT with new pre-optics allowing us to spatially Nyquist sample the diffraction limited PALM-3000 point spread function with 16 mas resolution, reducing the spaxel scale by another factor of 5×. We designed, manufactured, integrated and tested the new pre-optics in the first half of 2011 and commissioned it in December 2011. Here we present the opto-mechanical design and assembly of the new scale changing optics, as well as laboratory and on-sky commissioning results. In optimal observing conditions we achieve substantial Strehl ratios, delivering the near diffraction limited spatial resolution in the I and z bands.

Thermal maturity of type II kerogen from the New Albany Shale assessed by13C CP/MAS NMR

USGS Publications Warehouse

Werner-Zwanziger, U.; Lis, G.; Mastalerz, Maria; Schimmelmann, A.

2005-01-01

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance. ?? 2004 Elsevier Inc. All rights reserved.

Combining Nuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations to Characterize Carvedilol Polymorphs.

PubMed

Rezende, Carlos A; San Gil, Rosane A S; Borré, Leandro B; Pires, José Ricardo; Vaiss, Viviane S; Resende, Jackson A L C; Leitão, Alexandre A; De Alencastro, Ricardo B; Leal, Katia Z

2016-09-01

The experiments of carvedilol form II, form III, and hydrate by (13)C and (15)N cross-polarization magic-angle spinning (CP MAS) are reported. The GIPAW (gauge-including projector-augmented wave) method from DFT (density functional theory) calculations was used to simulate (13)C and (15)N chemical shifts. A very good agreement was found for the comparison between the global results of experimental and calculated nuclear magnetic resonance (NMR) chemical shifts for carvedilol polymorphs. This work aims a comprehensive understanding of carvedilol crystalline forms employing solution and solid-state NMR as well as DFT calculations. Copyright © 2016. Published by Elsevier Inc.

The investigation of the effect of thermal treatment on bentonites from Turkey with Fourier transform infrared and solid state nuclear magnetic resonance spectroscopic methods.

PubMed

Erdoğan Alver, Burcu; Alver, Ozgür

2012-08-01

There is a great deal of interest in the building industry in burned clays for production of building materials. Therefore, the effect of heat treatment on natural bentonite from Turkey was investigated by Fourier transform infrared (FT-IR) between the region of 4000-400cm(-1) and (29)Si, (27)Al magic angle spinning nuclear magnetic resonance (MAS NMR) measurement techniques at various temperatures between 200 and 700°C for 2h. The structural changes were also investigated upon heat treatment. Copyright © 2012 Elsevier B.V. All rights reserved.

Near-Infrared (NIR) Spectroscopy of Synthetic Hydroxyapatites and Human Dental Tissues.

PubMed

Kolmas, Joanna; Marek, Dariusz; Kolodziejski, Waclaw

2015-08-01

Near-infrared spectroscopy (NIR) was used to analyze synthetic hydroxyapatite calcined at various temperatures, synthetic carbonated hydroxyapatite, and human hard dental tissues (enamel and dentin). The NIR bands of those materials in the combination, first-overtone, and second-overtone spectral regions were assigned and evaluated for structural characterization. They were attributed to adsorbed and structural water, structural hydroxyl (OH) groups and surface P-OH groups. The NIR spectral features were quantitatively discussed in view of proton solid-state magic-angle spinning nuclear magnetic resonance ((1)H MAS NMR) results. We conclude that the NIR spectra of apatites are useful in the structural characterization of synthetic and biogenic apatites.

Meconium Aspiration Syndrome: A Role for Fetal Systemic Inflammation

PubMed Central

LEE, JoonHo; ROMERO, Roberto; LEE, Kyung A; KIM, Eun Na; KORZENIEWSKI, Steven J; CHAEMSAITHONG, Piya; YOON, Bo Hyun

2017-01-01

Background Meconium aspiration syndrome (MAS) is a leading cause of morbidity and mortality in term infants. Meconium-stained amniotic fluid (MSAF) occurs in approximately one of every seven pregnancies, but only 5% of neonates exposed to MSAF develop MAS. Why some infants exposed to meconium develop MAS while others do not is a fundamental question. Patients with MSAF have a higher frequency of intra-amniotic infection/inflammation than those with clear fluid. We propose that fetal systemic inflammation is a risk factor for the development of MAS in patients with MSAF. Objective To investigate whether intra-amniotic inflammation and funisitis, the histopathologic landmark of a fetal inflammatory response, predispose to MAS. Study Design A prospective cohort study was conducted from 1995 through 2009. Amniotic fluid (AF) samples (n=1,281) were collected at the time of cesarean delivery from women who delivered singleton newborns at term (gestational age ≥38 weeks). Intra-amniotic inflammation was diagnosed if the AF concentration of matrix metalloproteinase-8 (MMP-8) was >23 ng/ml. Funisitis was diagnosed by histologic examination if inflammation was present in the umbilical cord. Results The prevalence of MSAF was 9.2% (118/1,281), and 10.2% (12/118) of neonates exposed to MSAF developed MAS. There were no significant differences in the median gestational age or umbilical cord arterial pH at birth between neonates who developed MAS and those who did not (each p > 0.1). Mothers whose newborns developed MAS had a higher median AF MMP-8 (456.8 ng/ml vs.157.2 ng/ml; p < 0.05). Newborns exposed to intra-amniotic inflammation had a higher rate of MAS than those who were not exposed to intra-amniotic inflammation [13.0% (10/77) vs. 0% (0/32), p = 0.03], as did those exposed to funisitis [31.3% (5/16) vs. 7.3% (6/82), relative risk, 4.3; 95% confidence interval, 1.5–12.3]. Among the 89 newborns for whom both AF and placental histology were available, MAS was more common in patients with both intra-amniotic inflammation and funisitis than in those without intra-amniotic inflammation and funisitis [28.6% (4/14) vs. 0% (0/28), p = 0.009], while the rate of MAS did not show a significant difference between patients with intra-amniotic inflammation alone (without funisitis) and those without intra-amniotic inflammation and funisitis [10.9% (5/46) vs. 0% (0/28)]. Conclusion The combination of intra-amniotic inflammation with fetal systemic inflammation is an important antecedent of MAS. This concept has implications for the understanding of the mechanisms of disease responsible for MAS and for the development of prognostic models and therapeutic interventions for this disorder. PMID:26484777

Periodic organosilica hollow nanospheres as anode materials for lithium ion rechargeable batteries.

PubMed

Sasidharan, Manickam; Nakashima, Kenichi; Gunawardhana, Nanda; Yokoi, Toshiyuki; Ito, Masanori; Inoue, Masamichi; Yusa, Shin-ichi; Yoshio, Masaki; Tatsumi, Takashi

2011-11-01

Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance ((29)Si MAS NMR and (13)CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles.

Evidence for cross-linking in tomato cutin using HR-MAS NMR spectroscopy.

PubMed

Deshmukh, Ashish P; Simpson, André J; Hatcher, Patrick G

2003-11-01

Cutin is a polyester biopolymer component of plant leaf and fruit cuticles, most often associated with waxes and cuticular polysaccharides, and sometimes with another aliphatic biopolymer called cutan. Insolubility of these cuticular biopolymers has made it difficult to apply traditional analytical techniques for structure determination, because most techniques providing molecular level details require solubility. By using the relatively new technique of one and two-dimensional high-resolution magic angle spinning (HR-MAS) NMR spectroscopy, with added information from solid-state 13C NMR spectroscopy, detailed through-bond connectivities and assignments are made for cutin from Lycopersicon esculentum (tomato) fruit. Based on the data obtained, tomato cutin is found to be predominantly an aliphatic polyester with some olefinic and aromatic moieties, consistent with previous studies that employed various degradative approaches. Aside from esters, there are free primary and secondary alcohol groups, as well as free fatty acids. A significant finding is the presence of alpha-branched fatty acids/esters. Mid-chain hydroxyls appear to be generally unesterified, but esters of mid-chain hydroxyls have been identified. The alpha-branched fatty acids/esters and esters of mid-chain hydroxyls could point towards cross-linking.

Further refinement of 17O TRAPDOR NMR methods for determining oxygen speciation in multi-component oxide glasses

NASA Astrophysics Data System (ADS)

LaComb, M.; Stebbins, J. F.

2017-12-01

Solid state nuclear magnetic resonance (NMR) spectroscopy has often been utilized to determine network speciation in oxide glasses, typically using NMR-active nuclides such as 11B, 27Al and 17O. High field strength magnets allow for visible separation between bridging (BO) and non-bridging oxygens (NBO) in 17O magic-angle spinning (MAS) NMR spectra, but many questions remain due to limited ability to directly observe NBO associated with silicon, boron or aluminum in ternary glass systems with MAS NMR techniques. Recent studies have utilized the combination of 17O{27Al} and 17O{11B} TRAnsfer of Population in DOuble-Resonance (TRAPDOR) NMR to attempt to separate out resonances for these different bridging and non-bridging oxygen species in multicomponent calcium aluminosilicate and aluminoborosilicate glasses and rare-earth aluminoborosilicates. With improved technology and better resolution of spectral components we were able to expand this study to a wider range of calcium aluminosilicate, aluminoborate and aluminoborosilicate glasses and further separate out resonances for both bridging and non-bridging oxygens coordinated with aluminum, boron and/or silicon cations in these glasses.

Microwave assisted saponification (MAS) followed by on-line liquid chromatography (LC)-gas chromatography (GC) for high-throughput and high-sensitivity determination of mineral oil in different cereal-based foodstuffs.

PubMed

Moret, Sabrina; Scolaro, Marianna; Barp, Laura; Purcaro, Giorgia; Conte, Lanfranco S

2016-04-01

A high throughput, high-sensitivity procedure, involving simultaneous microwave-assisted extraction (MAS) and unsaponifiable extraction, followed by on-line liquid chromatography (LC)-gas chromatography (GC), has been optimised for rapid and efficient extraction and analytical determination of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in cereal-based products of different composition. MAS has the advantage of eliminating fat before LC-GC analysis, allowing an increase in the amount of sample extract injected, and hence in sensitivity. The proposed method gave practically quantitative recoveries and good repeatability. Among the different cereal-based products analysed (dry semolina and egg pasta, bread, biscuits, and cakes), egg pasta packed in direct contact with recycled paperboard had on average the highest total MOSH level (15.9 mg kg(-1)), followed by cakes (10.4 mg kg(-1)) and bread (7.5 mg kg(-1)). About 50% of the pasta and bread samples and 20% of the biscuits and cake samples had detectable MOAH amounts. The highest concentrations were found in an egg pasta in direct contact with recycled paperboard (3.6 mg kg(-1)) and in a milk bread (3.6 mg kg(-1)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range.

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

Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C,15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity andmore » line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high quality artifact-free datasets.« less

Sensitivity gains, linearity, and spectral reproducibility in nonuniformly sampled multidimensional MAS NMR spectra of high dynamic range

PubMed Central

Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin; Sun, Shangjin; Rice, David; Hoch, Jeffrey C.; Rovnyak, David

2014-01-01

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C, 15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high-quality artifact-free datasets. PMID:24752819

In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

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

Perras, Frédéric A.; Sadow, Aaron; Pruski, Marek

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radicalmore » distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.« less

In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

DOE PAGES

Perras, Frédéric A.; Sadow, Aaron; Pruski, Marek

2017-06-09

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radicalmore » distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.« less

Spin Vector Distribution in the Koronis Family for a Sample Complete to IAU H=10.88

NASA Astrophysics Data System (ADS)

Slivan, Stephen M.; Hosek, Matt; Sokol, Alyssa; Maynard, Sarah; Payne, Anna; Radford, Arden; Springmann, Alessondra; Mailhot, Emily; Midkiff, Alan; Russell, April; Stephens, Robert D.

2016-10-01

Because they share the same formation age, asteroid family members have experienced similar evolution for similar lengths of time, offering valuable information to help understand spin evolution processes. Clustered distributions of spin vectors determined from observations of ten of the largest Koronis family members (Slivan 2002) revealed evidence of spin modification by YORP thermal radiation torques (Vokrouhlický et al. 2003). The currently known spin vector sample in the Koronis family (Slivan et al., 2003; Slivan et al., 2009, Hanuš et al., 2011; Hanuš et al., 2013; Durech et al., 2016) clearly shows the two spin groupings observed among the large members: (1) the larger group with low-obliquity retrograde spin and periods between about 3 h and 30 h, and (2) a smaller group with prograde spin obliquity near 45° and periods near 8 h, characteristic of trapping in the s6 spin-orbit resonance (Vokrouhlický et al. 2003). There's also one "stray" longer-period prograde object with smaller obliquity, perhaps trapped in some other resonance.A limitation of the existing spin vector sample, which (using IAU H as a proxy for size) includes 16 of the brightest 27 members of the family, is that selection biases render it complete only to the brightest 12 members. Slivan et al. (2008) began a lightcurve observing program to increase the sample of Koronis family spin vectors down to about 20 km diameter.We report pole solutions that were determined for fourteen survey objects using lightcurves recorded from 2005-2016, which complete the Koronis spin vector sample to the brightest 22 members, now including 24 of the brightest 27 members. The larger sample adds several objects to the existing group of low-obliquity retrograde rotators, increasing the period range upward to almost 60 h, and also identifies two companions for the stray longer-period prograde spin object, strengthening the case for the presence of a second cluster of objects trapped in a spin-orbit resonance. The more complete distribution also reveals two new "strays" of its own - one lone fast prograde rotator, and one spin vector of atypical high obliquity, close to the ecliptic plane.

VizieR Online Data Catalog: 1876 open clusters multimembership catalog (Sampedro+, 2017)

NASA Astrophysics Data System (ADS)

Sampedro, L.; Dias, W. S.; Alfaro, E. J.; Monteiro, H.; Molino, A.

2017-10-01

We use version 3.5 of the New Optically Visible Open Clusters and Candidates catalogue (hereafter DAML02; Dias et al., 2002, Cat. B/ocl), to select a sample of 2167 open clusters to be analysed. The stellar positions and the proper motions are taken from the UCAC4 (Zacharias et al., 2013, Cat. I/322). The catalogue contains data for over 113 million stars (105 million of them with proper-motion data), and is complete down to magnitude R=16. The positional accuracy of the listed objects is about 15-100mas per coordinate, depending on the magnitude. Formal errors in proper motions range from about 1 to 10mas/yr, depending on the magnitude and the observational history. Systematic errors in the proper motions are estimated to be about 1-4mas/yr. (2 data files).

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

PubMed

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

2014-11-01

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

Current-induced spin polarization in InGaAs and GaAs epilayers with varying doping densities

NASA Astrophysics Data System (ADS)

Luengo-Kovac, M.; Huang, S.; Del Gaudio, D.; Occena, J.; Goldman, R. S.; Raimondi, R.; Sih, V.

2017-11-01

The current-induced spin polarization and momentum-dependent spin-orbit field were measured in InxGa1 -xAs epilayers with varying indium concentrations and silicon doping densities. Samples with higher indium concentrations and carrier concentrations and lower mobilities were found to have larger electrical spin generation efficiencies. Furthermore, current-induced spin polarization was detected in GaAs epilayers despite the absence of measurable spin-orbit fields, indicating that the extrinsic contributions to the spin-polarization mechanism must be considered. Theoretical calculations based on a model that includes extrinsic contributions to the spin dephasing and the spin Hall effect, in addition to the intrinsic Rashba and Dresselhaus spin-orbit coupling, are found to reproduce the experimental finding that the crystal direction with the smaller net spin-orbit field has larger electrical spin generation efficiency and are used to predict how sample parameters affect the magnitude of the current-induced spin polarization.

Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

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

Feng, Ju; Isern, Nancy G.; Burton, Sarah D.

2013-10-31

NMR metabolomics, consisting of solid state high resolution (hr) magic angle spinning (MAS) 1H NMR (1H hr-MAS), liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver . The melanoma group can be differentiated from its control group by PCA analysis of the absolute concentrations or by the absolute peak intensities of metabolites from either 1H hr-MAS NMR data on intact liver tissues or liquid state 1H-NMR spectra on liver tissue extracts. In particular, we found that the absolute concentrations of alanine, glutamate, creatine, creatinine, fumarate andmore » cholesterol are elevated in the melanoma group as compared to controls, while the absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acylglycerol are decreased. The ratio of glycerophosphocholine to phosphocholine is increased by about 1.5 fold in the melanoma group, while the absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma.« less

Single-crystal X-ray diffraction and NMR crystallography of a 1:1 cocrystal of dithianon and pyrimethanil.

PubMed

Pöppler, Ann Christin; Corlett, Emily K; Pearce, Harriet; Seymour, Mark P; Reid, Matthew; Montgomery, Mark G; Brown, Steven P

2017-03-01

A single-crystal X-ray diffraction structure of a 1:1 cocrystal of two fungicides, namely dithianon (DI) and pyrimethanil (PM), is reported [systematic name: 5,10-dioxo-5H,10H-naphtho[2,3-b][1,4]dithiine-2,3-dicarbonitrile-4,6-dimethyl-N-phenylpyrimidin-2-amine (1/1), C 14 H 4 N 2 O 2 S 2 ·C 12 H 13 N 2 ]. Following an NMR crystallography approach, experimental solid-state magic angle spinning (MAS) NMR spectra are presented together with GIPAW (gauge-including projector augmented wave) calculations of NMR chemical shieldings. Specifically, experimental 1 H and 13 C chemical shifts are determined from two-dimensional 1 H- 13 C MAS NMR correlation spectra recorded with short and longer contact times so as to probe one-bond C-H connectivities and longer-range C...H proximities, whereas H...H proximities are identified in a 1 H double-quantum (DQ) MAS NMR spectrum. The performing of separate GIPAW calculations for the full periodic crystal structure and for isolated molecules allows the determination of the change in chemical shift upon going from an isolated molecule to the full crystal structure. For the 1 H NMR chemical shifts, changes of 3.6 and 2.0 ppm correspond to intermolecular N-H...O and C-H...O hydrogen bonding, while changes of -2.7 and -1.5 ppm are due to ring current effects associated with C-H...π interactions. Even though there is a close intermolecular S...O distance of 3.10 Å, it is of note that the molecule-to-crystal chemical shifts for the involved sulfur or oxygen nuclei are small.

Molecular insight into the electrostatic membrane surface potential by 14n/31p MAS NMR spectroscopy: nociceptin-lipid association.

PubMed

Lindström, Fredrick; Williamson, Philip T F; Gröbner, Gerhard

2005-05-11

Exploiting naturally abundant (14)N and (31)P nuclei by high-resolution MAS NMR (magic angle spinning nuclear magnetic resonance) provides a molecular view of the electrostatic potential present at the surface of biological model membranes, the electrostatic charge distribution across the membrane interface, and changes that occur upon peptide association. The spectral resolution in (31)P and (14)N MAS NMR spectra is sufficient to probe directly the negatively charged phosphate and positively charged choline segment of the electrostatic P(-)-O-CH(2)-CH(2)-N(+)(CH(3))(3) headgroup dipole of zwitterionic DMPC (dimyristoylphosphatidylcholine) in mixed-lipid systems. The isotropic shifts report on the size of the potential existing at the phosphate and ammonium group within the lipid headgroup while the chemical shielding anisotropy ((31)P) and anisotropic quadrupolar interaction ((14)N) characterize changes in headgroup orientation in response to surface potential. The (31)P/(14)N isotropic chemical shifts for DMPC show opposing systematic changes in response to changing membrane potential, reflecting the size of the electrostatic potential at opposing ends of the P(-)-N(+) dipole. The orientational response of the DMPC lipid headgroup to electrostatic surface variations is visible in the anisotropic features of (14)N and (31)P NMR spectra. These features are analyzed in terms of a modified "molecular voltmeter" model, with changes in dynamic averaging reflecting the tilt of the C(beta)-N(+)(CH)(3) choline and PO(4)(-) segment. These properties have been exploited to characterize the changes in surface potential upon the binding of nociceptin to negatively charged membranes, a process assumed to proceed its agonistic binding to its opoid G-protein coupled receptor.

Switching-angle sample spinning NMR probe with a commercially available 20 kHz spinning system

NASA Astrophysics Data System (ADS)

Mizuno, Takashi; Takegoshi, K.; Terao, Takehiko

2004-11-01

A switching-angle sample spinning (SASS) probe workable at high spinning speeds was developed using a commercially available rotor/housing system. Details of the construction are described. As application examples of the SASS probe, we report experiments of powder pattern separation at the spinning speed of 20 kHz and broadband 13C- 13C polarization transfer at 16 kHz.

Fast Magic-Angle Spinning Three-Dimensional NMR Experiment for Simultaneously Probing H-H and N-H Proximities in Solids.

PubMed

Reddy, G N Manjunatha; Malon, Michal; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

2016-12-06

A fast magic-angle spinning (MAS, 70 kHz) solid-state NMR experiment is presented that combines 1 H Double-Quantum (DQ) and 14 N- 1 H HMQC (Heteronuclear Multiple-Quantum Coherence) pulse-sequence elements, so as to simultaneously probe H-H and N-H proximities in molecular solids. The proposed experiment can be employed in both two-dimensional (2D) and three-dimensional (3D) versions: first, a 2D 14 N HMQC-filtered 1 H-DQ experiment provides specific DQ-SQ correlation peaks for proton pairs that are in close proximities to the nitrogen sites, thereby achieving spectral filtration. Second, a proton-detected three-dimensional (3D) 1 H(DQ)- 14 N(SQ)- 1 H(SQ) experiment correlates 1 H(DQ)- 1 H(SQ) chemical shifts with 14 N shifts such that longer range N···H-H correlations are observed between protons and nitrogen atoms with internuclear NH distances exceeding 3 Å. Both 2D and 3D versions of the proposed experiment are demonstrated for an amino acid hydrochloride salt, l-histidine·HCl·H 2 O, and a DNA nucleoside, guanosine·2H 2 O. In the latter case, the achieved spectral filtration ensures that DQ cross peaks are only observed for guanine NH and CH8 1 H resonances and not ribose and water 1 H resonances, thus providing insight into the changes in the solid-state structure of this hydrate that occur over time; significant changes are observed in the NH and NH 2 1 H chemical shifts as compared to the freshly recrystallized sample previously studied by Reddy et al., Cryst. Growth Des. 2015, 15, 5945.

Multiple acquisition of magic angle spinning solid-state NMR experiments using one receiver: Application to microcrystalline and membrane protein preparations

NASA Astrophysics Data System (ADS)

Gopinath, T.; Veglia, Gianluigi

2015-04-01

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

Multiple acquisition of magic angle spinning solid-state NMR experiments using one receiver: application to microcrystalline and membrane protein preparations.

PubMed

Gopinath, T; Veglia, Gianluigi

2015-04-01

Solid-state NMR spectroscopy of proteins is a notoriously low-throughput technique. Relatively low-sensitivity and poor resolution of protein samples require long acquisition times for multidimensional NMR experiments. To speed up data acquisition, we developed a family of experiments called Polarization Optimized Experiments (POE), in which we utilized the orphan spin operators that are discarded in classical multidimensional NMR experiments, recovering them to allow simultaneous acquisition of multiple 2D and 3D experiments, all while using conventional probes with spectrometers equipped with one receiver. POE allow the concatenation of multiple 2D or 3D pulse sequences into a single experiment, thus potentially combining all of the aforementioned advances, boosting the capability of ssNMR spectrometers at least two-fold without the addition of any hardware. In this perspective, we describe the first generation of POE, such as dual acquisition MAS (or DUMAS) methods, and then illustrate the evolution of these experiments into MEIOSIS, a method that enables the simultaneous acquisition of multiple 2D and 3D spectra. Using these new pulse schemes for the solid-state NMR investigation of biopolymers makes it possible to obtain sequential resonance assignments, as well as distance restraints, in about half the experimental time. While designed for acquisition of heteronuclei, these new experiments can be easily implemented for proton detection and coupled with other recent advancements, such as dynamic nuclear polarization (DNP), to improve signal to noise. Finally, we illustrate the application of these methods to microcrystalline protein preparations as well as single and multi-span membrane proteins reconstituted in lipid membranes. Copyright © 2015 Elsevier Inc. All rights reserved.

Multiple Acquisition of Magic Angle Spinning Solid-State NMR Experiments Using One Receiver: Application to Microcrystalline and Membrane Protein Preparations

PubMed Central

Gopinath, T.; Veglia, Gianluigi

2015-01-01

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

Correlation between electron spin resonance spectra and oil yield in eastern oil shales

USGS Publications Warehouse

Choudhury, M.; Rheams, K.F.; Harrell, J.W.

1986-01-01

Organic free radical spin concentrations were measured in 60 raw oil shale samples from north Alabama and south Tennessee and compared with Fischer assays and uranium concentrations. No correlation was found between spin concentration and oil yield for the complete set of samples. However, for a 13 sample set taken from a single core hole, a linear correlation was obtained. No correlation between spin concentration and uranium concentration was found. ?? 1986.

X-ray diffraction and spectroscopic study of wiluite: implications for the vesuvianite-group nomenclature

NASA Astrophysics Data System (ADS)

Panikorovskii, Taras L.; Mazur, Anton S.; Bazai, Ayya V.; Shilovskikh, Vladimir V.; Galuskin, Evgeny V.; Chukanov, Nikita V.; Rusakov, Vyacheslav S.; Zhukov, Yurii M.; Avdontseva, Evgenia Yu.; Aksenov, Sergey M.; Krivovichev, Sergey V.

2017-09-01

Two wiluite samples from the Wiluy River, Yakutia, Russia have been investigated by means of single-crystal and powder X-ray diffraction, electron microprobe analysis, 1H, 27Al, 11B, and 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR), thermogravimetric analysis (DSC/TGA), X-ray photoelectron spectroscopy (XPS) at the Si2p, Ca2p, Al2p, Mg1s, B1s and Fe2p core levels, 57Fe Mössbauer spectroscopy, infrared (IR) spectroscopy and optical measurements. The crystal structures have been refined in the P4/ nnc space group [ a = 15.7027(3), c = 11.7008(3) Å, V = 2885.1(1) Å3 for 1 and a = 15.6950(2), c = 11.6787(4) Å, V = 2876.9(1) Å3 for 2] to R 1 = 0.022 and R 1 = 0.021, respectively. In the crystal structure of wiluite, five-coordinated Y1 site is predominantly occupied by Mg. IR spectra of wiluite substantially different from those of vesuvianite, in particular, by the presence of additional bands in the range 1080‒1415 cm-1, which correspond to symmetric B‒O stretching vibrations of the BO 3 3- and BO 4 5- groups. According to the MAS NMR data, tetrahedrally coordinated T1 site is occupied by B3+ with minor amounts of Al3+. The general formula of wiluite can be written as follows ( Z = 2): Ca19Mg(Al,Mg,Fe,Ti,Mn)12(B,Al,◻)5(Si2O7)4(SiO4)10(O,OH)9O2-3. The diversity of vesuvianite-group minerals is largely determined by the population of the Y1 sites. However, wiluite is characterized by the presence of additional T1 and T2 sites and should be considered as special among other vesuvianite-group minerals. The reasonability of subdivision of the wiluite subgroup within the vesuvianite group is discussed.

Application of 1H and 23Na magic angle spinning NMR spectroscopy to define the HRBC up-taking of MRI contrast agents

NASA Astrophysics Data System (ADS)

Calabi, Luisella; Paleari, Lino; Biondi, Luca; Linati, Laura; De Miranda, Mario; Ghelli, Stefano

2003-09-01

The up-take of Gd(III) complexes of BOPTA, DTPA, DOTA, EDTP, HPDO3A, and DOTP in HRBC has been evaluated by measuring the lanthanide induced shift (LIS) produced by the corresponding dysprosium complexes (DC) on the MAS-NMR resonances of water protons and free sodium ions. These complexes are important in their use as MRI contrast agents (MRI-CA) in diagnostics. 1H and 23Na MAS-NMR spectra of HRBC suspension, collected at 9.395 T, show only one signal due to extra- and intra-cellular water (or sodium). In MAS spectra, the presence of DC in a cellular compartment produces the LIS of only the nuclei (water proton or sodium) in that cellular compartment and this LIS can be related to the DC concentrations (by the experimental curves of LIS vs. DC concentrations) collected in the physiological solution. To obtain correct results about LIS, the use of MAS technique is mandatory, because it guarantees the only the nuclei staying in the same cellular compartment where the LC is present show the LIS. In all the cases considered, the addition of the DC to HRBC (100% hematocrit) produced a shift of only the extra-cellular water (or sodium) signal and the gradient of concentration ( GC) between extra- and intra-cellular compartments resulted greater than 100:1, when calculated by means of sodium signals. These high values of GC are direct proofs that none of the tested dysprosium complexes crosses the HRBC membrane. Since the DC are iso-structural to the gadolinium complexes the corresponding gadolinium ones (MRI-CA) do not cross the HRBC membrane and, consequently, they are not up-taken in HRBC. The GC values calculated by means of water proton signals resulted much lower than those obtained by sodium signals. This proves that the choice of the isotope is a crucial step in order to use this method in the best way. In fact, GC value depends on the lowest detectable LIS which, in turn, depends on the nature of the LC (lanthanide complex) and the observed isotopes.

Parallax Results from URAT Epoch Data

NASA Astrophysics Data System (ADS)

Finch, Charlie T.; Zacharias, Norbert

2016-06-01

We present 1103 trigonometric parallaxes and proper motions from the United States Naval Observatory Robotic Astrometric Telescope (URAT) observations taken at the Naval Observatory Flagstaff Station (NOFS) over a three-year period from 2012 April to 2015 June covering the entire sky north of about -10^\\circ decl. We selected two samples: previously suspected nearby stars from known photometric distances and stars showing a large, significant parallax signature in URAT epoch data without any prior selection criteria. All systems presented in this paper have an observed parallax ≥40 mas with no previous published trigonometric parallax. The formal errors on these weighted parallax solutions are mostly between 4 and 10 mas. This sample gives a significant (of the order of 50%) increase to the number of known systems having a trigonometric parallax to be within 25 pc of the Sun (without applying Lutz-Kelker bias corrections). A few of these are found to be within 10 pc. Many of these new nearby stars display a total proper motion of less than 200 mas yr-1. URAT parallax results have been verified against Hipparcos and Yale data for stars in common. The publication of all signifigant parallax observations from URAT data is in preparation for CDS.

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)

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

2014-01-01

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.

CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING DERMAL WIPE AND SURFACE WIPE SAMPLES FOR ANALYSIS OF POLAR ORGANIC POLLUTANTS (SOP-5.27)

EPA Science Inventory

The method for extracting and preparing a dermal or surface wipe sample for analysis of acidic persistent organic pollutants is summarized in this standard operating procedure. It covers the extraction and concentration of samples that are to be analyzed by gas chromatography/mas...

MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-06-01

Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

Urinary Trivalent Methylated Arsenic Species in a Population Chronically Exposed to Inorganic Arsenic

PubMed Central

Valenzuela, Olga L.; Borja-Aburto, Victor H.; Garcia-Vargas, Gonzalo G.; Cruz-Gonzalez, Martha B.; Garcia-Montalvo, Eliud A.; Calderon-Aranda, Emma S.; Del Razo, Luz M.

2005-01-01

Chronic exposure to inorganic arsenic (iAs) has been associated with increased risk of various forms of cancer and of noncancerous diseases. Metabolic conversions of iAs that yield highly toxic and genotoxic methylarsonite (MAsIII) and dimethylarsinite (DMAsIII) may play a significant role in determining the extent and character of toxic and cancer-promoting effects of iAs exposure. In this study we examined the relationship between urinary profiles of MAsIII and DMAsIII and skin lesion markers of iAs toxicity in individuals exposed to iAs in drinking water. The study subjects were recruited among the residents of an endemic region of central Mexico. Drinking-water reservoirs in this region are heavily contaminated with iAs. Previous studies carried out in the local populations have found an increased incidence of pathologies, primarily skin lesions, that are characteristic of arseniasis. The goal of this study was to investigate the urinary profiles for the trivalent and pentavalent As metabolites in both high- and low-iAs–exposed subjects. Notably, methylated trivalent arsenicals were detected in 98% of analyzed urine samples. On average, the major metabolite, DMAsIII, represented 49% of total urinary As, followed by DMAsV (23.7%), iAsV (8.6%), iAsIII (8.5%), MAsIII (7.4%), and MAsV (2.8%). More important, the average MAsIII concentration was significantly higher in the urine of exposed individuals with skin lesions compared with those who drank iAs-contaminated water but had no skin lesions. These data suggest that urinary levels of MAsIII, the most toxic species among identified metabolites of iAs, may serve as an indicator to identify individuals with increased susceptibility to toxic and cancer-promoting effects of arseniasis. PMID:15743710

Current-induced spin polarization in InGaAs and GaAs epilayers with varying doping densities

DOE PAGES

Luengo-Kovac, Marta; Huang, Simon; Del Gaudio, Davide; ...

2017-11-16

Here, the current-induced spin polarization and momentum-dependent spin-orbit field were measured in In xGa 1-xAs epilayers with varying indium concentrations and silicon doping densities. Samples with higher indium concentrations and carrier concentrations and lower mobilities were found to have larger electrical spin generation efficiencies. Furthermore, current-induced spin polarization was detected in GaAs epilayers despite the absence of measurable spin-orbit fields, indicating that the extrinsic contributions to the spin-polarization mechanism must be considered. Theoretical calculations based on a model that includes extrinsic contributions to the spin dephasing and the spin Hall effect, in addition to the intrinsic Rashba and Dresselhaus spin-orbitmore » coupling, are found to reproduce the experimental finding that the crystal direction with the smaller net spin-orbit field has larger electrical spin generation efficiency and are used to predict how sample parameters affect the magnitude of the current-induced spin polarization.« less

Current-induced spin polarization in InGaAs and GaAs epilayers with varying doping densities

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

Luengo-Kovac, Marta; Huang, Simon; Del Gaudio, Davide

Here, the current-induced spin polarization and momentum-dependent spin-orbit field were measured in In xGa 1-xAs epilayers with varying indium concentrations and silicon doping densities. Samples with higher indium concentrations and carrier concentrations and lower mobilities were found to have larger electrical spin generation efficiencies. Furthermore, current-induced spin polarization was detected in GaAs epilayers despite the absence of measurable spin-orbit fields, indicating that the extrinsic contributions to the spin-polarization mechanism must be considered. Theoretical calculations based on a model that includes extrinsic contributions to the spin dephasing and the spin Hall effect, in addition to the intrinsic Rashba and Dresselhaus spin-orbitmore » coupling, are found to reproduce the experimental finding that the crystal direction with the smaller net spin-orbit field has larger electrical spin generation efficiency and are used to predict how sample parameters affect the magnitude of the current-induced spin polarization.« less

Metabolite profiling in retinoblastoma identifies novel clinicopathological subgroups

PubMed Central

Kohe, Sarah; Brundler, Marie-Anne; Jenkinson, Helen; Parulekar, Manoj; Wilson, Martin; Peet, Andrew C; McConville, Carmel M

2015-01-01

Background: Tumour classification, based on histopathology or molecular pathology, is of value to predict tumour behaviour and to select appropriate treatment. In retinoblastoma, pathology information is not available at diagnosis and only exists for enucleated tumours. Alternative methods of tumour classification, using noninvasive techniques such as magnetic resonance spectroscopy, are urgently required to guide treatment decisions at the time of diagnosis. Methods: High-resolution magic-angle spinning magnetic resonance spectroscopy (HR-MAS MRS) was undertaken on enucleated retinoblastomas. Principal component analysis and cluster analysis of the HR-MAS MRS data was used to identify tumour subgroups. Individual metabolite concentrations were determined and were correlated with histopathological risk factors for each group. Results: Multivariate analysis identified three metabolic subgroups of retinoblastoma, with the most discriminatory metabolites being taurine, hypotaurine, total-choline and creatine. Metabolite concentrations correlated with specific histopathological features: taurine was correlated with differentiation, total-choline and phosphocholine with retrolaminar optic nerve invasion, and total lipids with necrosis. Conclusions: We have demonstrated that a metabolite-based classification of retinoblastoma can be obtained using ex vivo magnetic resonance spectroscopy, and that the subgroups identified correlate with histopathological features. This result justifies future studies to validate the clinical relevance of these subgroups and highlights the potential of in vivo MRS as a noninvasive diagnostic tool for retinoblastoma patient stratification. PMID:26348444

Structural changes in C–S–H gel during dissolution: Small-angle neutron scattering and Si-NMR characterization

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

Trapote-Barreira, Ana, E-mail: anatrapotebarreira@gmail.com; Porcar, Lionel; Large Scale Structure Group, Institut Laue Langevin, Grenoble

2015-06-15

Flow-through experiments were conducted to study the calcium–silicate–hydrate (C–S–H) gel dissolution kinetics. During C–S–H gel dissolution the initial aqueous Ca/Si ratio decreases to reach the stoichiometric value of the Ca/Si ratio of a tobermorite-like phase (Ca/Si = 0.83). As the Ca/Si ratio decreases, the solid C–S–H dissolution rate increases from (4.5 × 10{sup −} {sup 14} to 6.7 × 10{sup −} {sup 12}) mol m{sup −} {sup 2} s{sup −} {sup 1}. The changes in the microstructure of the dissolving C–S–H gel were characterized by small-angle neutron scattering (SANS) and {sup 29}Si magic-angle-spinning nuclear magnetic resonance ({sup 29}Si-MAS NMR). Themore » SANS data were fitted using a fractal model. The SANS specific surface area tends to increase with time and the obtained fit parameters reflect the changes in the nanostructure of the dissolving solid C–S–H within the gel. The {sup 29}Si MAS NMR analyses show that with dissolution the solid C–S–H structure tends to a more ordered tobermorite structure, in agreement with the Ca/Si ratio evolution.« less

Local structures of mesoporous bioactive glasses and their surface alterations in vitro: inferences from solid-state nuclear magnetic resonance

PubMed Central

Gunawidjaja, Philips N.; Mathew, Renny; Lo, Andy Y. H.; Izquierdo-Barba, Isabel; García, Ana; Arcos, Daniel; Mattias Edén, María Vallet-Regí

2012-01-01

We review the benefits of using 29Si and 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy for probing the local structures of both bulk and surface portions of mesoporous bioactive glasses (MBGs) of the CaO–SiO2−(P2O5) system. These mesoporous materials exhibit an ordered pore arrangement, and are promising candidates for improved bone and tooth implants. We discuss experimental MAS NMR results from three MBGs displaying different Ca, Si and P contents: the 29Si NMR spectra were recorded either directly by employing radio-frequency pulses to 29Si, or by magnetization transfers from neighbouring protons using cross polarization, thereby providing quantitative information about the silicate speciation present in the pore wall and at the MBG surface, respectively. The surface modifications were monitored for the three MBGs during their immersion in a simulated body fluid (SBF) for intervals between 30 min and one week. The results were formulated as a reaction sequence describing the interconversions between the distinct silicate species. We generally observed a depletion of Ca2+ ions at the MBG surface, and a minor condensation of the silicate-surface network over one week of SBF soaking. PMID:22349247

Risk factors differentiating mild/moderate from severe meconium aspiration syndrome in meconium-stained neonates

PubMed Central

Choi, Woneui; Jeong, Heejeong; Choi, Suk-Joo; Kim, Jung-Sun; Roh, Cheong-Rae; Kim, Jong-Hwa

2015-01-01

Objective The aim of this study was to compare the risk factors associated with mild/moderate meconium aspiration syndrome (MAS) with those associated with severe in meconium-stained term neonates. Methods Consecutive singleton term neonates (n=671) with meconium staining at birth from all deliveries (n=14,666) in our institution from January 2006 to December 2012 were included. Both maternal and neonatal variables were examined. Among the study population, for women who underwent the trial of labor (n=644), variables associated with labor were also examined. These variables were compared between the mild/moderate MAS group, the severe MAS group, and the MAS-absent group. Results MAS developed in 10.6% (71/671) of neonates with meconium staining at birth. Among the neonates with MAS, 81.7% had mild MAS, 5.6% had moderate MAS, and 12.7% had severe MAS. The presence of minimal variability was significantly increased in both the mild/moderate and the severe MAS groups. The frequencies of nulliparity, fetal tachycardia, and intrapartum fever were significantly increased in the mild/moderate MAS group, but not in the severe MAS group. While a longer duration of the second stage of labor was significantly associated with mild/moderate MAS, severe MAS was associated with a shorter duration of the second stage. Notably, low mean cord pH (7.165 [6.850-7.375]) was significantly associated with mild/moderate MAS, but not with severe MAS (7.220 [7.021-7.407]) compared with the absence of MAS (7.268 [7.265-7.271]). Conclusion Our data suggest the development of severe MAS is not simply a linear extension of the same risk factors driving mild/moderate MAS. PMID:25629015

Spinning angle optical calibration apparatus

DOEpatents

Beer, Stephen K.; Pratt, II, Harold R.

1991-01-01

An optical calibration apparatus is provided for calibrating and reproducing spinning angles in cross-polarization, nuclear magnetic resonance spectroscopy. An illuminated magnifying apparatus enables optical setting an accurate reproducing of spinning "magic angles" in cross-polarization, nuclear magnetic resonance spectroscopy experiments. A reference mark scribed on an edge of a spinning angle test sample holder is illuminated by a light source and viewed through a magnifying scope. When the "magic angle" of a sample material used as a standard is attained by varying the angular position of the sample holder, the coordinate position of the reference mark relative to a graduation or graduations on a reticle in the magnifying scope is noted. Thereafter, the spinning "magic angle" of a test material having similar nuclear properties to the standard is attained by returning the sample holder back to the originally noted coordinate position.

Effect of Freezing Conditions on Distances and Their Distributions Derived from Double Electron Electron Resonance (DEER): A Study of Doubly-Spin-Labeled T4 Lysozyme

PubMed Central

Georgieva, Elka R.; Roy, Aritro S.; Grigoryants, Vladimir M.; Borbat, Petr P.; Earle, Keith A.; Scholes, Charles P.; Freed, Jack H.

2012-01-01

Pulsed dipolar ESR spectroscopy, DEER and DQC, require frozen samples. An important issue in the biological application of this technique is how the freezing rate and concentration of cryoprotectant could possibly affect the conformation of biomacromolecule and/or spin-label. We studied in detail the effect of these experimental variables on the distance distributions obtained by DEER from a series of doubly spin-labeled T4 lysozyme mutants. We found that the rate of sample freezing affects mainly the ensemble of spin-label rotamers, but the distance maxima remain essentially unchanged. This suggests that proteins frozen in a regular manner in liquid nitrogen faithfully maintain the distance-dependent structural properties in solution. We compared the results from rapidly freeze-quenched (≤100 μs) samples to those from commonly shock-frozen (slow freeze, 1s or longer) samples. For all the mutants studied we obtained inter-spin distance distributions, which were broader for rapidly frozen samples than for slowly frozen ones. We infer that rapid freezing trapped a larger ensemble of spin label rotamers; whereas, on the time-scale of slower freezing the protein and spin-label achieve a population showing fewer low-energy conformers. We used glycerol as a cryoprotectant in concentrations of 10% and 30% by weight. With 10% glycerol and slow freezing, we observed an increased slope of background signals, which in DEER is related to increased local spin concentration, in this case due to insufficient solvent vitrification, and therefore protein aggregation. This effect was considerably suppressed in slowly frozen samples containing 30% glycerol and rapidly frozen samples containing 10% glycerol. The assignment of bimodal distributions to tether rotamers as opposed to protein conformations is aided by comparing results using MTSL and 4-Bromo MTSL spin-labels. The latter usually produce narrower distance distributions. PMID:22341208

GIANT METREWAVE RADIO TELESCOPE DETECTION OF TWO NEW H I 21 cm ABSORBERS AT z ≈ 2

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

Kanekar, N., E-mail: nkanekar@ncra.tifr.res.in

2014-12-20

I report the detection of H I 21 cm absorption in two high column density damped Lyα absorbers (DLAs) at z ≈ 2 using new wide-band 250-500 MHz receivers on board the Giant Metrewave Radio Telescope. The integrated H I 21 cm optical depths are 0.85 ± 0.16 km s{sup –1} (TXS1755+578) and 2.95 ± 0.15 km s{sup –1} (TXS1850+402). For the z = 1.9698 DLA toward TXS1755+578, the difference in H I 21 cm and C I profiles and the weakness of the radio core suggest that the H I 21cm absorption arises toward radio components in the jet,more » and that the optical and radio sightlines are not the same. This precludes an estimate of the DLA spin temperature. For the z = 1.9888 DLA toward TXS1850+402, the absorber covering factor is likely to be close to unity, as the background source is extremely compact, with the entire 5 GHz emission arising from a region of ≤ 1.4 mas in size. This yields a DLA spin temperature of T{sub s} = (372 ± 18) × (f/1.0) K, lower than typical T{sub s} values in high-z DLAs. This low spin temperature and the relatively high metallicity of the z = 1.9888 DLA ([Zn/H] =(– 0.68 ± 0.04)) are consistent with the anti-correlation between metallicity and spin temperature that has been found earlier in damped Lyα systems.« less

Characterization of the fluid and solid components of cyanogel systems during the gelation process

NASA Astrophysics Data System (ADS)

Fortmeyer, Ivy Camille

The work in this thesis concerns the sol-gel transformation in cyanogel systems comprised of d8 square planar chlorometalates (M=Pd(II), Pt(II)) and d6 octahedral hexacyanometalates (M=Fe(II), Co(III), Ru(II)). The body of this thesis is split into two chapters. The first chapter examines the physical changes in the solvent phase of the sol-gel network, and the second focuses on the polymer backbone of the gel. Studies on the water component of cyanogel systems during the gelation process were carried out with a variety of in situ spectroscopic techniques. The use of high resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) to identify and characterize different water environments was explored, but was ultimately found to disrupt gelation. Standard solution-phase 1H NMR proved sufficient for calculation and qualitative modeling of spin-spin and spin-lattice relaxations, providing distinct spectral markers of the gelation point and subsequent aging process. Vibrational spectroscopy was used to explore the hydrogen bonding environment of the water during gelation. The kinetics of polymerization of the cyanogel backbone was explored using both in situ and ex situ techniques. Data collected by 13C NMR and 195Pt NMR primarily demonstrated first order kinetics, implying a dissociative substitution mechanism at the chlorometalate center. Rate constants for gelation in the presence of various added monopotassium and nitrate salts were calculated. Added chloride was found to significantly slow gelation and was further explored using NMR and vibrational spectroscopy. A mechanism was proposed for the polymerization taking into account the dissociative substitution and the bridging geometries implied by 13C NMR.

A 13C{31P} REDOR NMR Investigation of the Role of Glutamic Acid Residues in Statherin-Hydroxyapatite Recognition

PubMed Central

Ndao, Moise; Ash, Jason T.; Breen, Nicholas F.; Goobes, Gil; Stayton, Patrick S.; Drobny, Gary P.

2011-01-01

The side chain carboxyl groups of acidic proteins found in the extra-cellular matrix (ECM) of mineralized tissues play a key role in promoting or inhibiting the growth of minerals such as hydroxyapatite (HAP), the principal mineral component of bone and teeth. Among the acidic proteins found in the saliva is statherin, a 43-residue tyrosine-rich peptide that is a potent lubricant in the salivary pellicle and an inhibitor of both HAP crystal nucleation and growth. Three acidic amino acids – D1, E4, and E5 – are located in the N-terminal 15 amino acid segment, with a fourth amino acid, E26, located outside the N-terminus. We have utilized 13C{31P} REDOR NMR to analyze the role played by acidic amino acids in the binding mechanism of statherin to the HAP surface by measuring the distance between the δ-carboxyl 13C spins of the three glutamic acid side chains of statherin (residues E4, E5, E26) and 31P spins of the phosphate groups at the HAP surface. 13C{31P} REDOR studies of glutamic-5-13C acid incorporated at positions E4 and E26 indicate a 13C–31P distance of more than 6.5 Å between the side chain carboxyl 13C spin of E4 and the closest 31P in the HAP surface. In contrast, the carboxyl 13C spin at E5 has a much shorter 13C–31P internuclear distance of 4.25±0.09 Å, indicating that the carboxyl group of this side chain interacts directly with the surface. 13C T1ρ and slow-spinning MAS studies indicate that the motions of the side chains of E4 and E5 are more restricted than that of E26. Together, these results provide further insight into the molecular interactions of statherin with HAP surfaces. PMID:19678690

Improving Statistics Education through Simulations: The Case of the Sampling Distribution.

ERIC Educational Resources Information Center

Earley, Mark A.

This paper presents a summary of action research investigating statistics students' understandings of the sampling distribution of the mean. With four sections of an introductory Statistics in Education course (n=98 students), a computer simulation activity (R. delMas, J. Garfield, and B. Chance, 1999) was implemented and evaluated to show…

Spectroscopic characterization of natural calcite minerals.

PubMed

Gunasekaran, S; Anbalagan, G

2007-11-01

The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm(-1). The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a=4.9781 A, c=17.1188 A. The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.

High field 27Al MAS NMR and TPD studies of active sites in ethanol dehydration using thermally treated transitional aluminas as catalysts

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

Hu, Jian Zhi; Xu, Suochang; Kwak, Ja Hun

Gamma-, sigma- and theta-Al2O3 are well known metastable “transitional” alumina structural polymorphs. Upon heating, Al2O3 transitions to the so-called and Al2O3 polymorphs and finally forms the thermally stable Al2O3. The poorly developed crystallinity and co-existence of the , , and Al2O3 prior to forming all Al2O3, making it difficult to characterize the structures as well as to quantify the various phases of the transition alumina. As a result, there are significant controversies in the literatures. In this work, a detailed NMR analysis was carried out at high magnetic field on three special aluminum oxide samples where the, , , Al2O3more » phases are made dominant, respectively, by controlling the synthesis conditions. The goal is to simplify, including making unambiguous, spectral assignments in 27Al MAS NMR spectra of transition alumina that have not yet been commonly agreed previously. Specifically, quantitative 1D 27Al MAS NMR was used to quantify the ratios of the different alumina structural units, 2D MQMAS 27Al MAS was used for obtaining the highest spectral resolution to guide the analysis of the 1D spectrum, and a saturation pulse sequence was integrated into the 1D NMR to select the amorphous structures, including obtain spectra where the penta-coordinate sites are observed with enhanced relative intensity. Collectively, this study uniquely assigns Al-peaks (both octahedral and tetrahedral) to the Al2O3 and the Al2O3 phases and offers a new way of understanding, including quantifying, the different structural units and sites in transition alumina samples.« less

Spinning angle optical calibration apparatus

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

Beer, S.K.; Pratt, H.R. II.

1989-09-12

An optical calibration apparatus is provided for calibrating and reproducing spinning angles in cross-polarization, nuclear magnetic resonance spectroscopy. An illuminated magnifying apparatus enables optical setting and accurate reproducing of spinning magic angles in cross-polarization, nuclear magnetic resonance spectroscopy experiments. A reference mark scribed on an edge of a spinning angle test sample holder is illuminated by a light source and viewed through a magnifying scope. When the magic angle of a sample material used as a standard is attained by varying the angular position of the sample holder, the coordinate position of the reference mark relative to a graduation ormore » graduations on a reticle in the magnifying scope is noted. Thereafter, the spinning magic angle of a test material having similar nuclear properties to the standard is attained by returning the sample holder back to the originally noted coordinate position. 2 figs.« less

1H-MRSI pattern perturbation in a mouse glioma: the effects of acute hyperglycemia and moderate hypothermia.

PubMed

Simões, R V; Delgado-Goñi, T; Lope-Piedrafita, S; Arús, C

2010-01-01

MR spectroscopic Imaging (MRSI), with PRESS localization, is used here to monitor the effects of acute hyperglycemia in the spectral pattern of 11 mice bearing GL261 gliomas at normothermia (36.5-37.5 degrees C) and at hypothermia (28.5-29.5 degrees C). These in vivo studies were complemented by ex vivo high resolution magic angle spinning (HR-MAS) analysis of GL261 tumor samples from 6 animals sacrificed by focused microwave irradiation, and blood glucose measurements in 12 control mice. Apparent glucose levels, monitored by in vivo MRSI in brain tumors during acute hyperglycemia, rose to an average of 1.6-fold during hypothermia (p < 0.05), while no significant changes were detected at normothermia, or in control experiments performed at euglycemia, or in normal/peritumoral brain regions. Ex vivo analysis of glioma-bearing mouse brains at hypothermia revealed higher glucose increases in distinct regions during the acute hyperglycemic challenge (up to 6.6-fold at the tumor center), in agreement with maximal in vivo blood glucose changes (5-fold). Phantom studies on taurine plus glucose containing solutions explained the differences between in vivo and ex vivo measurements. Our results also indicate brain tumor heterogeneity in the four animal tumors investigated in response to a defined metabolic challenge.

Metabolic Profiling of IDH Mutation and Malignant Progression in Infiltrating Glioma

NASA Astrophysics Data System (ADS)

Jalbert, Llewellyn E.; Elkhaled, Adam; Phillips, Joanna J.; Neill, Evan; Williams, Aurelia; Crane, Jason C.; Olson, Marram P.; Molinaro, Annette M.; Berger, Mitchel S.; Kurhanewicz, John; Ronen, Sabrina M.; Chang, Susan M.; Nelson, Sarah J.

2017-03-01

Infiltrating low grade gliomas (LGGs) are heterogeneous in their behavior and the strategies used for clinical management are highly variable. A key factor in clinical decision-making is that patients with mutations in the isocitrate dehydrogenase 1 and 2 (IDH1/2) oncogenes are more likely to have a favorable outcome and be sensitive to treatment. Because of their relatively long overall median survival, more aggressive treatments are typically reserved for patients that have undergone malignant progression (MP) to an anaplastic glioma or secondary glioblastoma (GBM). In the current study, ex vivo metabolic profiles of image-guided tissue samples obtained from patients with newly diagnosed and recurrent LGG were investigated using proton high-resolution magic angle spinning spectroscopy (1H HR-MAS). Distinct spectral profiles were observed for lesions with IDH-mutated genotypes, between astrocytoma and oligodendroglioma histologies, as well as for tumors that had undergone MP. Levels of 2-hydroxyglutarate (2HG) were correlated with increased mitotic activity, axonal disruption, vascular neoplasia, and with several brain metabolites including the choline species, glutamate, glutathione, and GABA. The information obtained in this study may be used to develop strategies for in vivo characterization of infiltrative glioma, in order to improve disease stratification and to assist in monitoring response to therapy.

Thermo-Physical Properties of B2O3-Containing Mold Flux for High Carbon Steels in Thin Slab Continuous Casters: Structure, Viscosity, Crystallization, and Wettability

NASA Astrophysics Data System (ADS)

Park, Jun-Yong; Kim, Gi Hyun; Kim, Jong Bae; Park, Sewoong; Sohn, Il

2016-08-01

The effect of B2O3 on the thermo-physical properties of commercial mold fluxes, including the viscosity, crystallization behavior, and wettability, was investigated. Viscosity was measured using the rotating spindle method, and CCT (continuous cooling transformation) diagrams were obtained to investigate the crystallization behavior at various cooling rates using CLSM (confocal laser scanning microscope). The wettability of the fluxes was determined by measuring the contact angles at 1573 K (1300 °C) using the digital images generated by the sessile drop method and were used to calculate the surface tension, interfacial tension, and work of adhesion for Flux A (existing flux) and B (modified flux). These thermo-physical properties were correlated with the structural analysis obtained using FT-IR (Fourier transform-infrared), Raman and MAS-NMR (magic angle spin-nuclear magnetic resonance) spectroscopy. In addition, DTA (differential thermal analysis) was performed on the samples to measure the liquidus temperatures. Higher B2O3 concentrations resulted in lower liquidus temperatures, consequently decreasing the viscosity, the break temperature, and the crystallization temperature. However, B2O3 addition accelerated crystal growth owing to the higher diffusion kinetics of the cations, which also reduced the size of the liquid/solid co-existing region.

Moisture induced polymorphic transition of mannitol and its morphological transformation.

PubMed

Yoshinari, Tomohiro; Forbes, Robert T; York, Peter; Kawashima, Yoshiaki

2002-10-24

The effects of moisture on the polymorphic transition of crystalline mannitol were investigated. Mannitol has three polymorphic forms, and was classified as alpha, beta, and delta form, respectively, by Walter-Lévy (C.R. Acad. Sc. Paris Ser. C (1968) 267, 1779). The water uptake of delta form crystalline was greater than that of the beta form when each crystalline form was stored at 97%RH (25 degrees C). The different powder X-ray diffraction patterns obtained before and after humidification confirmed that a moisture induced polymorphic transition from the delta to beta form had occurred. Morphological changes were also observed with an increase in the specific surface area of the delta sample from 0.4 to 2.3 m(2)/g being found on exposure to humidity. Thus it was suggested that the observed higher hygroscopicity of the newly formed beta form arose from the gradual increase in the surface area with the polymorphic transition from the delta to beta form. When considering the mechanism of this polymorphic transition, the results from molecular modelling, cross-polarisation/magic angle spinning (CP/MAS) solid-state NMR spectra and scanning electron-micrographs suggest that water molecules act as a molecular loosener to facilitate conversion from delta to the beta form as a result of multi-nucleation. Copyright 2002 Elsevier Science B.V.

In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO4)2 during Heating by High Temperature Raman and 27Al NMR Spectroscopies

PubMed Central

Wang, Min; You, Jinglin; Sobol, Alexander; Lu, Liming; Wang, Jian; Xie, Yingfang

2017-01-01

Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO4)2 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO4)2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples. PMID:28772669

In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO₄)₂ during Heating by High Temperature Raman and 27Al NMR Spectroscopies.

PubMed

Wang, Min; You, Jinglin; Sobol, Alexander; Lu, Liming; Wang, Jian; Xie, Yingfang

2017-03-17

Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family M I M III (M VI O₄)₂ (M I = alkali metal, M III = Al, In, Sc, Fe, Bi, lanthanide; M VI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO₄)₂ have been investigated by in-situ high temperature Raman scattering and 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO₆] octahedra in both KAl(MoO₄)₂ glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K⁺, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.

Spin-polarized scanning tunneling microscopy experiments on the rough surface of a polycrystalline NiFe film with a fine magnetic tip sensitive to a well-defined magnetization component

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

Matsuyama, H., E-mail: matsu@phys.sci.hokudai.ac.jp; Nara, D.; Kageyama, R.

We developed a micrometer-sized magnetic tip integrated onto the write head of a hard disk drive for spin-polarized scanning tunneling microscopy (SP-STM) in the modulated tip magnetization mode. Using SP-STM, we measured a well-defined in-plane spin-component of the tunneling current of the rough surface of a polycrystalline NiFe film. The spin asymmetry of the NiFe film was about 1.3% within the bias voltage range of -3 to 1 V. We obtained the local spin component image of the sample surface, switching the magnetic field of the sample to reverse the sample magnetization during scanning. We also obtained a spin imagemore » of the rough surface of a polycrystalline NiFe film evaporated on the recording medium of a hard disk drive.« less

Reverse Induced Fit-Driven MAS-Downstream Transduction: Looking for Metabotropic Agonists.

PubMed

Pernomian, Larissa; Gomes, Mayara S; de Paula da Silva, Carlos H Tomich; Rosa, Joaquin M C

2017-01-01

Protective effects of MAS activation have spurred clinical interests in developing MAS agonists. However, current bases that drive this process preclude that physiological concentrations of peptide MAS agonists induce an atypical signaling that does not reach the metabotropic efficacy of constitutive activation. Canonical activation of MAS-coupled G proteins is only achieved by supraphysiological concentrations of peptide MAS agonists or physiological concentrations of chemically modified analogues. These pleiotropic differences are because of two overlapped binding domains: one non-metabotropic site that recognizes peptide agonists and one metabotropic domain that recognizes modified analogues. It is feasible that supraphysiological concentrations of peptide MAS agonists undergo to chemical modifications required for binding to metabotropic domain. Receptor oligomerization enhances pharmacological parameters coupled to metabotropic signaling. The formation of receptor-signalosome complex makes the transduction of agonists more adaptive. Considering the recent identification of MAS-signalosome, we aimed to postulate the reverse induced fit hypothesis in which MAS-signalosome would trigger chemical modifications required for agonists bind to MAS metabotropic domain. Here we cover rational perspectives for developing novel metabotropic MAS agonists in the view of the reverse induced-fit hypothesis. Predicting a 3D model of MAS metabotropic domain may guide the screening of chemical modifications required for metabotropic efficacy. Pharmacophore-based virtual screening would select potential metabotropic MAS agonists from virtual libraries from human proteome. Rational perspectives that consider reverse induced fit hypothesis during MAS activation for developing metabotropic MAS agonists represents the best approach in providing MAS ligands with constitutive efficacy at physiological concentrations. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Interferometrically stable, enclosed, spinning sample cell for spectroscopic experiments on air-sensitive samples

NASA Astrophysics Data System (ADS)

Baranov, Dmitry; Hill, Robert J.; Ryu, Jisu; Park, Samuel D.; Huerta-Viga, Adriana; Carollo, Alexa R.; Jonas, David M.

2017-01-01

In experiments with high photon flux, it is necessary to rapidly remove the sample from the beam and to delay re-excitation until the sample has returned to equilibrium. Rapid and complete sample exchange has been a challenge for air-sensitive samples and for vibration-sensitive experiments. Here, a compact spinning sample cell for air and moisture sensitive liquid and thin film samples is described. The principal parts of the cell are a copper gasket sealed enclosure, a 2.5 in. hard disk drive motor, and a reusable, chemically inert glass sandwich cell. The enclosure provides an oxygen and water free environment at the 1 ppm level, as demonstrated by multi-day tests with sodium benzophenone ketyl radical. Inside the enclosure, the glass sandwich cell spins at ≈70 Hz to generate tangential speeds of 7-12 m/s that enable complete sample exchange at 100 kHz repetition rates. The spinning cell is acoustically silent and compatible with a ±1 nm rms displacement stability interferometer. In order to enable the use of the spinning cell, we discuss centrifugation and how to prevent it, introduce the cycle-averaged resampling rate to characterize repetitive excitation, and develop a figure of merit for a long-lived photoproduct buildup.

Interferometrically stable, enclosed, spinning sample cell for spectroscopic experiments on air-sensitive samples.

PubMed

Baranov, Dmitry; Hill, Robert J; Ryu, Jisu; Park, Samuel D; Huerta-Viga, Adriana; Carollo, Alexa R; Jonas, David M

2017-01-01

In experiments with high photon flux, it is necessary to rapidly remove the sample from the beam and to delay re-excitation until the sample has returned to equilibrium. Rapid and complete sample exchange has been a challenge for air-sensitive samples and for vibration-sensitive experiments. Here, a compact spinning sample cell for air and moisture sensitive liquid and thin film samples is described. The principal parts of the cell are a copper gasket sealed enclosure, a 2.5 in. hard disk drive motor, and a reusable, chemically inert glass sandwich cell. The enclosure provides an oxygen and water free environment at the 1 ppm level, as demonstrated by multi-day tests with sodium benzophenone ketyl radical. Inside the enclosure, the glass sandwich cell spins at ≈70 Hz to generate tangential speeds of 7-12 m/s that enable complete sample exchange at 100 kHz repetition rates. The spinning cell is acoustically silent and compatible with a ±1 nm rms displacement stability interferometer. In order to enable the use of the spinning cell, we discuss centrifugation and how to prevent it, introduce the cycle-averaged resampling rate to characterize repetitive excitation, and develop a figure of merit for a long-lived photoproduct buildup.

The Camera of the MASCOT Asteroid Lander on Board Hayabusa 2

NASA Astrophysics Data System (ADS)

Jaumann, R.; Schmitz, N.; Koncz, A.; Michaelis, H.; Schroeder, S. E.; Mottola, S.; Trauthan, F.; Hoffmann, H.; Roatsch, T.; Jobs, D.; Kachlicki, J.; Pforte, B.; Terzer, R.; Tschentscher, M.; Weisse, S.; Mueller, U.; Perez-Prieto, L.; Broll, B.; Kruselburger, A.; Ho, T.-M.; Biele, J.; Ulamec, S.; Krause, C.; Grott, M.; Bibring, J.-P.; Watanabe, S.; Sugita, S.; Okada, T.; Yoshikawa, M.; Yabuta, H.

2017-07-01

The MASCOT Camera (MasCam) is part of the Mobile Asteroid Surface Scout (MASCOT) lander's science payload. MASCOT has been launched to asteroid (162173) Ryugu onboard JAXA's Hayabusa 2 asteroid sample return mission on Dec 3rd, 2014. It is scheduled to arrive at Ryugu in 2018, and return samples to Earth by 2020. MasCam was designed and built by DLR's Institute of Planetary Research, together with Airbus-DS Germany. The scientific goals of the MasCam investigation are to provide ground truth for the orbiter's remote sensing observations, provide context for measurements by the other lander instruments (radiometer, spectrometer and magnetometer), the orbiter sampling experiment, and characterize the geological context, compositional variations and physical properties of the surface (e.g. rock and regolith particle size distributions). During daytime, clear filter images will be acquired. During night, illumination of the dark surface is performed by an LED array, equipped with 4×36 monochromatic light-emitting diodes (LEDs) working in four spectral bands. Color imaging will allow the identification of spectrally distinct surface units. Continued imaging during the surface mission phase and the acquisition of image series at different sun angles over the course of an asteroid day will contribute to the physical characterization of the surface and also allow the investigation of time-dependent processes and to determine the photometric properties of the regolith. The MasCam observations, combined with the MASCOT hyperspectral microscope (MMEGA) and radiometer (MARA) thermal observations, will cover a wide range of observational scales and serve as a strong tie point between Hayabusa 2's remote-sensing scales (103-10^{-3} m) and sample scales (10^{-3}-10^{-6} m). The descent sequence and the close-up images will reveal the surface features over a broad range of scales, allowing an assessment of the surface's diversity and close the gap between the orbital observations and those made by the in-situ measurements. The MasCam is mounted inside the lander slightly tilted, such that the center of its 54.8° square field-of-view is directed towards the surface at an angle of 22° with respect to the surface plane. This is to ensure that both the surface close to the lander and the horizon are observable. The camera optics is designed according to the Scheimpflug principle, thus that the entire scene along the camera's depth of field (150 mm to infinity) is in focus. The camera utilizes a 1024×1024 pixel CMOS sensor sensitive in the 400-1000 nm wavelength range, peaking at 600-700 nm. Together with the f-16 optics, this yields a nominal ground resolution of 150 micron/px at 150 mm distance (diffraction limited). The camera flight model has undergone standard radiometric and geometric calibration both at the component and system (lander) level. MasCam relies on the use of wavelet compression to maximize data return within stringent mission downlink limits. All calibration and flight data products will be generated and archived in the Planetary Data System in PDS image format.

Prediction of recrystallization behavior of troglitazone/polyvinylpyrrolidone solid dispersion by solid-state NMR.

PubMed

Ito, Atsutoshi; Watanabe, Tomoyuki; Yada, Shuichi; Hamaura, Takeshi; Nakagami, Hiroaki; Higashi, Kenjirou; Moribe, Kunikazu; Yamamoto, Keiji

2010-01-04

The purpose of this study was to elaborate the relationship between the (13)C CP/MAS NMR spectra and the recrystallization behavior during the storage of troglitazone solid dispersions. The solid dispersions were prepared by either the solvent method or by co-grinding. The recrystallization behavior under storage conditions at 40 degrees C/94% RH was evaluated by the Kolmogorov-Johnson-Mehl-Avrami (KJMA) equation. Solid dispersions prepared by the solvent method or by prolonged grinding brought about inhibition of the nucleation and the nuclei growth at the same time. No differences in the PXRD profiles were found in the samples prepared by the co-grinding and solvent methods, however, (13)C CP/MAS NMR showed significant differences in the spectra. The correlation coefficients using partial least square regression analysis between the PXRD profiles and the apparent nuclei-growth constant or induction period to nucleation were 0.1305 or 0.6350, respectively. In contrast, those between the (13)C CP/MAS NMR spectra and the constant or the period were 0.9916 or 0.9838, respectively. The (13)C CP/MAS NMR spectra had good correlation with the recrystallization kinetic parameters evaluated by the KJMA equation. Consequently, solid-state NMR was judged to be a useful tool for the prediction of the recrystallization behavior of solid dispersions.

Genomic deletion of CNGB3 is identical by descent in multiple canine breeds and causes achromatopsia

PubMed Central

2013-01-01

Background Achromatopsia is an autosomal recessive disease characterized by the loss of cone photoreceptor function that results in day-blindness, total colorblindness, and decreased central visual acuity. The most common causes for the disease are mutations in the CNGB3 gene, coding for the beta subunit of the cyclic nucleotide-gated channels in cones. CNGB3-achromatopsia, or cone degeneration (cd), is also known to occur in two canine breeds, the Alaskan malamute (AM) and the German shorthaired pointer. Results Here we report an in-depth characterization of the achromatopsia phenotype in a new canine breed, the miniature Australian shepherd (MAS). Genotyping revealed that the dog was homozygous for a complete genomic deletion of the CNGB3 gene, as has been previously observed in the AM. Identical breakpoints on chromosome 29 were identified in both the affected AM and MAS with a resulting deletion of 404,820 bp. Pooled DNA samples of unrelated purebred Australian shepherd, MAS, Siberian husky, Samoyed and Alaskan sled dogs were screened for the presence of the affected allele; one Siberian husky and three Alaskan sled dogs were identified as carriers. The affected chromosomes from the AM, MAS, and Siberian husky were genotyped for 147 SNPs in a 3.93 Mb interval within the cd locus. An identical shared affected haplotype, 0.5 Mb long, was observed in all three breeds and defined the minimal linkage disequilibrium (LD) across breeds. This supports the idea that the mutated allele was identical by descent (IBD). Conclusion We report the occurrence of CNGB3-achromatopsia in a new canine breed, the MAS. The CNGB3-deletion allele previously described in the AM was also observed in a homozygous state in the affected MAS, as well as in a heterozygous carrier state in a Siberian husky and Alaskan sled dogs. All affected alleles were shown to be IBD, strongly suggesting an affected founder effect. Since the MAS is not known to be genetically related to the AM, other breeds may potentially carry the same cd-allele and be affected by achromatopsia. PMID:23601474

FIRE_ACE_ER2_MAS

Atmospheric Science Data Center

2017-04-26

... Moderate Resolution Imaging Spectrometer (MODIS) Airborne Simulator (MAS) Data Project Title:  MAS ... IDL Code ER2 Flight Tracks Related Data:  MAS Additional Info:  ER-2 MODIS Airborne Simulator (MAS) Image Gallery:  ...

Mesoscopic spin Hall effect in semiconductor nanostructures

NASA Astrophysics Data System (ADS)

Zarbo, Liviu

The spin Hall effect (SHE) is a name given to a collection of diverse phenomena which share two principal features: (i) longitudinal electric current flowing through a paramagnetic semiconductor or metallic sample leads to transverse spin current and spin accumulation of opposite sign at opposing lateral edges; (ii) SHE does not require externally applied magnetic field or magnetic ordering in the equilibrium state of the sample, instead it relies on the presence of spin-orbit (SO) couplings within the sample. This thesis elaborates on a new type of phenomenon within the SHE family, predicted in our recent studies [Phys. Rev. B 72, 075361 (2005); Phys. Rev. Lett. 95, 046601 (2005); Phys. Rev. B 72, 075335 (2005); Phys. Rev. B 73 , 075303 (2006); and Europhys. Lett. 77, 47004 (2007)], where pure spin current flows through the transverse electrodes attached to a clean finitesize two-dimensional electron gas (2DEG) due to unpolarized charge current injected through its longitudinal leads. If transverse leads are removed, the effect manifests as nonequilibrium spin Hall accumulation at the lateral edges of 2DEG wires. The SO coupling driving this SHE effect is of the Rashba type, which arises due to structural inversion asymmetry of semiconductor heterostructure hosting the 2DEG. We term the effect "mesoscopic" because the spin Hall currents and accumulations reach optimal value in samples of the size of the spin precession length---the distance over which the spin of an electron precesses by an angle pi. In strongly SO-coupled structures this scale is of the order of ˜100 nm, and, therefore, mesoscopic in the sense of being much larger than the characteristic microscopic scales (such as the Fermi wavelength, screening length, or the mean free path in disordered systems), but still much smaller than the macroscopic ones. Although the first theoretical proposal for SHE, driven by asymmetry in SO-dependent scattering of spin-up and spin-down electrons off impurities, appeared in 1970s, it is only in the past few years that advances in optical detection of nonequilibrium magnetization in semiconductors have made possible the detection of such extrinsic SHE in groundbreaking experiments. The experimental pursuits of SHE have, in fact, been largely motivated by very recent theoretical speculations for several order of magnitude greater spin Hall currents driven by intrinsic SO mechanisms due to SO couplings existing not only around the impurity but also throughout the sample. The homogeneous intrinsic SO couplings are capable of spin-splitting the band structure and appear as momentum-dependent magnetic field within the sample which causes spin non-conservation due to precession of injected spins which are not in the eigenstates of the corresponding Zeeman term. Besides deepening our understanding of subtle relativistic effects in solids, SHE has attracted a lot of attention since it offers an all-electrical way of generating pure spin currents in semiconductors. (Abstract shortened by UMI.)

Structural Masquerade of Plesiomonas shigelloides Strain CNCTC 78/89 O-Antigen-High-Resolution Magic Angle Spinning NMR Reveals the Modified d-galactan I of Klebsiella pneumoniae.

PubMed

Ucieklak, Karolina; Koj, Sabina; Pawelczyk, Damian; Niedziela, Tomasz

2017-11-29

The high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (HR-MAS NMR) analysis of Plesiomonas shigelloides 78/89 lipopolysaccharide directly on bacteria revealed the characteristic structural features of the O -acetylated polysaccharide in the NMR spectra. The O -antigen profiles were unique, yet the pattern of signals in the, spectra along with their ¹H, 13 C chemical shift values, resembled these of d-galactan I of Klebsiella pneumoniae . The isolated O- specific polysaccharide (O-PS) of P. shigelloides strain CNCTC 78/89 was investigated by ¹H and 13 C NMR spectroscopy, mass spectrometry and chemical methods. The analyses demonstrated that the P. shigelloides 78/89 O- PS is composed of →3)-α-d-Gal p -(1→3)-β-d-Gal f 2OAc-(1→ disaccharide repeating units. The O- acetylation was incomplete and resulted in a microheterogeneity of the O- antigen. This O- acetylation generates additional antigenic determinants within the O- antigen, forms a new chemotype, and contributes to the epitopes recognized by the O- serotype specific antibodies. The serological cross-reactivities further confirmed the inter-specific structural similarity of these O- antigens.

Resolution enhancement using a new multiple-pulse decoupling sequence for quadrupolar nuclei.

PubMed

Delevoye, L; Trébosc, J; Gan, Z; Montagne, L; Amoureux, J-P

2007-05-01

A new decoupling composite pulse sequence is proposed to remove the broadening on spin S=1/2 magic-angle spinning (MAS) spectra arising from the scalar coupling with a quadrupolar nucleus I. It is illustrated on the (31)P spectrum of an aluminophosphate, AlPO(4)-14, which is broadened by the presence of (27)Al/(31)P scalar couplings. The multiple-pulse (MP) sequence has the advantage over the continuous wave (CW) irradiation to efficiently annul the scalar dephasing without reintroducing the dipolar interaction. The MP decoupling sequence is first described in a rotor-synchronised version (RS-MP) where one parameter only needs to be adjusted. It clearly avoids the dipolar recoupling in order to achieve a better resolution than using the CW sequence. In a second improved version, the MP sequence is experimentally studied in the vicinity of the perfect rotor-synchronised conditions. The linewidth at half maximum (FWHM) of 65 Hz using (27)Al CW decoupling decreases to 48 Hz with RS-MP decoupling and to 30 Hz with rotor-asynchronised MP (RA-MP) decoupling. The main phenomena are explained using both experimental results and numerical simulations.

Genetic algorithm optimized triply compensated pulses in NMR spectroscopy

NASA Astrophysics Data System (ADS)

Manu, V. S.; Veglia, Gianluigi

2015-11-01

Sensitivity and resolution in NMR experiments are affected by magnetic field inhomogeneities (of both external and RF), errors in pulse calibration, and offset effects due to finite length of RF pulses. To remedy these problems, built-in compensation mechanisms for these experimental imperfections are often necessary. Here, we propose a new family of phase-modulated constant-amplitude broadband pulses with high compensation for RF inhomogeneity and heteronuclear coupling evolution. These pulses were optimized using a genetic algorithm (GA), which consists in a global optimization method inspired by Nature's evolutionary processes. The newly designed π and π / 2 pulses belong to the 'type A' (or general rotors) symmetric composite pulses. These GA-optimized pulses are relatively short compared to other general rotors and can be used for excitation and inversion, as well as refocusing pulses in spin-echo experiments. The performance of the GA-optimized pulses was assessed in Magic Angle Spinning (MAS) solid-state NMR experiments using a crystalline U-13C, 15N NAVL peptide as well as U-13C, 15N microcrystalline ubiquitin. GA optimization of NMR pulse sequences opens a window for improving current experiments and designing new robust pulse sequences.

A generalized theoretical framework for the description of spin decoupling in solid-state MAS NMR: Offset effect on decoupling performance

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

Tan, Kong Ooi; Meier, Beat H., E-mail: beme@ethz.ch, E-mail: maer@ethz.ch; Ernst, Matthias, E-mail: beme@ethz.ch, E-mail: maer@ethz.ch

2016-09-07

We present a generalized theoretical framework that allows the approximate but rapid analysis of residual couplings of arbitrary decoupling sequences in solid-state NMR under magic-angle spinning conditions. It is a generalization of the tri-modal Floquet analysis of TPPM decoupling [Scholz et al., J. Chem. Phys. 130, 114510 (2009)] where three characteristic frequencies are used to describe the pulse sequence. Such an approach can be used to describe arbitrary periodic decoupling sequences that differ only in the magnitude of the Fourier coefficients of the interaction-frame transformation. It allows a ∼100 times faster calculation of second-order residual couplings as a function ofmore » pulse sequence parameters than full spin-dynamics simulations. By comparing the theoretical calculations with full numerical simulations, we show the potential of the new approach to examine the performance of decoupling sequences. We exemplify the usefulness of this framework by analyzing the performance of commonly used high-power decoupling sequences and low-power decoupling sequences such as amplitude-modulated XiX (AM-XiX) and its super-cycled variant SC-AM-XiX. In addition, the effect of chemical-shift offset is examined for both high- and low-power decoupling sequences. The results show that the cross-terms between the dipolar couplings are the main contributions to the line broadening when offset is present. We also show that the SC-AM-XIX shows a better offset compensation.« less

A generalized theoretical framework for the description of spin decoupling in solid-state MAS NMR: Offset effect on decoupling performance.

PubMed

Tan, Kong Ooi; Agarwal, Vipin; Meier, Beat H; Ernst, Matthias

2016-09-07

We present a generalized theoretical framework that allows the approximate but rapid analysis of residual couplings of arbitrary decoupling sequences in solid-state NMR under magic-angle spinning conditions. It is a generalization of the tri-modal Floquet analysis of TPPM decoupling [Scholz et al., J. Chem. Phys. 130, 114510 (2009)] where three characteristic frequencies are used to describe the pulse sequence. Such an approach can be used to describe arbitrary periodic decoupling sequences that differ only in the magnitude of the Fourier coefficients of the interaction-frame transformation. It allows a ∼100 times faster calculation of second-order residual couplings as a function of pulse sequence parameters than full spin-dynamics simulations. By comparing the theoretical calculations with full numerical simulations, we show the potential of the new approach to examine the performance of decoupling sequences. We exemplify the usefulness of this framework by analyzing the performance of commonly used high-power decoupling sequences and low-power decoupling sequences such as amplitude-modulated XiX (AM-XiX) and its super-cycled variant SC-AM-XiX. In addition, the effect of chemical-shift offset is examined for both high- and low-power decoupling sequences. The results show that the cross-terms between the dipolar couplings are the main contributions to the line broadening when offset is present. We also show that the SC-AM-XIX shows a better offset compensation.

Features, Treatment, and Outcomes of Macrophage Activation Syndrome in Childhood-Onset Systemic Lupus Erythematosus.

PubMed

Borgia, R Ezequiel; Gerstein, Maya; Levy, Deborah M; Silverman, Earl D; Hiraki, Linda T

2018-04-01

To describe the features and treatment of macrophage activation syndrome (MAS) in a single-center cohort of patients with childhood-onset systemic lupus erythematosus (SLE), and to compare childhood-onset SLE manifestations and outcomes between those with and those without MAS. We included all patients with childhood-onset SLE followed up at The Hospital for Sick Children from 2002 to 2012, and identified those also diagnosed as having MAS. Demographic, clinical, and laboratory features of MAS and SLE, medication use, hospital and pediatric intensive care unit (PICU) admissions, as well as damage indices and mortality data were extracted from the Lupus database. Student's t-tests and Fisher's exact tests were used to compare continuous and categorical variables, respectively. We calculated incidence rate ratios of hospital and PICU admissions comparing patients with and those without MAS, using Poisson models. Kaplan-Meier survival analysis was used to examine the time to disease damage accrual. Of the 403 patients with childhood-onset SLE, 38 (9%) had MAS. The majority (68%) had concomitant MAS and SLE diagnoses. Fever was the most common MAS clinical feature. The frequency of renal and central nervous system disease, hospital admissions, the average daily dose of steroids, and time to disease damage were similar between those with and those without MAS. We observed a higher mortality rate among those with MAS (5%) than those without MAS (0.2%) (P = 0.02). MAS was most likely to develop concomitantly with childhood-onset SLE diagnosis. The majority of the MAS patients were successfully treated with corticosteroids with no MAS relapses. Although the numbers were small, there was a higher risk of death associated with MAS compared to SLE without MAS. © 2018, American College of Rheumatology.

Direct Measurement of the Flip-Flop Rate of Electron Spins in the Solid State

NASA Astrophysics Data System (ADS)

Dikarov, Ekaterina; Zgadzai, Oleg; Artzi, Yaron; Blank, Aharon

2016-10-01

Electron spins in solids have a central role in many current and future spin-based devices, ranging from sensitive sensors to quantum computers. Many of these apparatuses rely on the formation of well-defined spin structures (e.g., a 2D array) with controlled and well-characterized spin-spin interactions. While being essential for device operation, these interactions can also result in undesirable effects, such as decoherence. Arguably, the most important pure quantum interaction that causes decoherence is known as the "flip-flop" process, where two interacting spins interchange their quantum state. Currently, for electron spins, the rate of this process can only be estimated theoretically, or measured indirectly, under limiting assumptions and approximations, via spin-relaxation data. This work experimentally demonstrates how the flip-flop rate can be directly and accurately measured by examining spin-diffusion processes in the solid state for physically fixed spins. Under such terms, diffusion can occur only through this flip-flop-mediated quantum-state exchange and not via actual spatial motion. Our approach is implemented on two types of samples, phosphorus-doped 28Si and nitrogen vacancies in diamond, both of which are significantly relevant to quantum sensors and information processing. However, while the results for the former sample are conclusive and reveal a flip-flop rate of approximately 12.3 Hz, for the latter sample only an upper limit of approximately 0.2 Hz for this rate can be estimated.

Chemical characterization and sorption capacity measurements of degraded newsprint from a landfill

USGS Publications Warehouse

Chen, Lixia; Nanny, Mark A.; Knappe, Detlef R. U.; Wagner, Travis B.; Ratasuk, Nopawan

2004-01-01

Newsprint samples collected from 12−16 ft (top layer (TNP)), 20−24 ft (middle layer (MNP)), and 32−36 ft (bottom layer (BNP)) below the surface of the Norman Landfill (NLF) were characterized by infrared (IR) spectroscopy, cross-polarization, magic-angle spinning 13C nuclear magnetic resonance (CP-MAS 13C NMR) spectroscopy, and tetramethylammonium hydroxide (TMAH) thermochemolysis gas chromatography/mass spectrometry (GC/MS). The extent of NLF newsprint degradation was evaluated by comparing the chemical composition of NLF newsprint to that of fresh newsprint (FNP) and newsprint degraded in the laboratory under methanogenic conditions (DNP). The O-alkyl/alkyl, cellulose/lignin, and lignin/resin acid ratios showed that BNP was the most degraded, and that all three NLF newsprint samples were more degraded than DNP. 13C NMR and TMAH thermochemolysis data demonstrated selective enrichment of lignin over cellulose, and TMAH thermochemolysis further exhibited selective enrichment of resin acids over lignin. In addition, the crystallinity of cellulose in NLF newsprint samples was significantly lower relative to that of FNP and DNP as shown by 13C NMR spectra. The yield of lignin monomers from TMAH thermochemolysis suggested that hydroxyl groups were removed from the propyl side chain of lignin during the anaerobic decomposition of newsprint in the NLF. Moreover, the vanillyl acid/aldehyde ratio, which successfully describes aerobic lignin degradation, was not a good indicator of the anaerobic degradation of lignin on the basis of the TMAH data. The toluene sorption capacity increased as the degree of newsprint degradation increased or as the O-alkyl/alkyl ratio of newsprint decreased. The results of this study further verified that the sorbent O-alkyl/alkyl ratio is useful for predicting sorption capacities of natural organic materials for hydrophobic organic contaminants.

Variations of Solar Radius Observed with RHESSI

NASA Astrophysics Data System (ADS)

Fivian, M. D.; Hudson, H. S.; Lin, R. P.

2003-12-01

The Solar Aspect System (SAS) of the rotating (at 15 rpm) RHESSI spacecraft has three subsystems. Each of these measures the position of the limb by sampling the full solar chord profile with a linear CCD using a narrow bandwidth filter at 670 nm. With a resolution of each CCD of 1.7 arcsec/pixel, the accuracy of each of the 6 limb positions is theoretically better than 50 mas using 4 pixels at each limb. Since the launch of RHESSI early 2002, solar limbs are sampled with at least 100 Hz. That provides a database of currently 4 x 109 single radius measurements. The main function of SAS is to determine the RHESSI pointing relative to Sun center. The observed precision of this determination has a typical instantaneous (16 Hz) value of about 200 mas (rms). We show and discuss first results of variations of solar radius observed with RHESSI.

Chemical Makeup and Hydrophilic Behavior of Graphene Oxide Nanoribbons after Low-Temperature Fluorination.

PubMed

Romero Aburto, Rebeca; Alemany, Lawrence B; Weldeghiorghis, Thomas K; Ozden, Sehmus; Peng, Zhiwei; Lherbier, Aurélien; Botello Méndez, Andrés Rafael; Tiwary, Chandra Sekhar; Taha-Tijerina, Jaime; Yan, Zheng; Tabata, Mika; Charlier, Jean-Christophe; Tour, James M; Ajayan, Pulickel M

2015-07-28

Here we investigated the fluorination of graphene oxide nanoribbons (GONRs) using H2 and F2 gases at low temperature, below 200 °C, with the purpose of elucidating their structure and predicting a fluorination mechanism. The importance of this study is the understanding of how fluorine functional groups are incorporated in complex structures, such as GONRs, as a function of temperature. The insight provided herein can potentially help engineer application-oriented materials for several research and industrial sectors. Direct (13)C pulse magic angle spinning (MAS) nuclear magnetic resonance (NMR) confirmed the presence of epoxy, hydroxyl, ester and ketone carbonyl, tertiary alkyl fluorides, as well as graphitic sp(2)-hybridized carbon. Moreover, (19)F-(13)C cross-polarization MAS NMR with (1)H and (19)F decoupling confirmed the presence of secondary alkyl fluoride (CF2) groups in the fluorinated graphene oxide nanoribbon (FGONR) structures fluorinated above 50 °C. First-principles density functional theory calculations gained insight into the atomic arrangement of the most dominant chemical groups. The fluorinated GONRs present atomic fluorine percentages in the range of 6-35. Interestingly, the FGONRs synthesized up to 100 °C, with 6-19% of atomic fluorine, exhibit colloidal similar stability in aqueous environments when compared to GONRs. This colloidal stability is important because it is not common for materials with up to 19% fluorine to have a high degree of hydrophilicity.

The Effect of Antitumor Glycosides on Glioma Cells and Tissues as Studied by Proton HR-MAS NMR Spectroscopy

PubMed Central

García-Álvarez, Isabel; Garrido, Leoncio; Romero-Ramírez, Lorenzo; Nieto-Sampedro, Manuel; Fernández-Mayoralas, Alfonso; Campos-Olivas, Ramón

2013-01-01

The effect of the treatment with glycolipid derivatives on the metabolic profile of intact glioma cells and tumor tissues, investigated using proton high resolution magic angle spinning (1H HR-MAS) nuclear magnetic resonance (NMR) spectroscopy, is reported here. Two compounds were used, a glycoside and its thioglycoside analogue, both showing anti-proliferative activity on glioma C6 cell cultures; however, only the thioglycoside exhibited antitumor activity in vivo. At the drug concentrations showing anti-proliferative activity in cell culture (20 and 40 µM), significant increases in choline containing metabolites were observed in the 1H NMR spectra of the same intact cells. In vivo experiments in nude mice bearing tumors derived from implanted C6 glioma cells, showed that reduction of tumor volume was associated with significant changes in the metabolic profile of the same intact tumor tissues; and were similar to those observed in cell culture. Specifically, the activity of the compounds is mainly associated with an increase in choline and phosphocholine, in both the cell cultures and tumoral tissues. Taurine, a metabolite that has been considered a biomarker of apoptosis, correlated with the reduction of tumor volume. Thus, the results indicate that the mode of action of the glycoside involves, at least in part, alteration of phospholipid metabolism, resulting in cell death. PMID:24194925

Gas-Phase Synthesis and Characterization of CH4-Loaded Hydroquinone Clathrates

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

Lee, J.; Lee, Y; Takeya, S

2010-01-01

A CH{sub 4}-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the {alpha}-form of crystalline HQ and CH{sub 4} gas at 12 MPa and room temperature. Solid-state {sup 13}C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH{sub 4} molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH{sub 4} molecules, that is, 0.69 CH{sub 4} per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH{sub 4}-loaded HQ clathrate adopts the {beta}-form ofmore » HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 {angstrom} and c = 5.5038 {angstrom}. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH{sub 4}-loaded HQ clathrate is stable up to 368 K and gradually transforms to the {alpha}-form by releasing the confined CH{sub 4} gases between 368-378 K. Using solid-state {sup 13}C CP/MAS NMR, the reaction kinetics between the {alpha}-form HQ and CH{sub 4} gas is qualitatively described in terms of the particle size of the crystalline HQ.« less

Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi1-y-zCoyAlzO2 and Al-Doped LiNixMnyCozO2 via (27)Al MAS NMR Spectroscopy.

PubMed

Dogan, Fulya; Vaughey, John T; Iddir, Hakim; Key, Baris

2016-07-06

Direct observations of local lattice aluminum environments have been a major challenge for aluminum-bearing Li ion battery materials, such as LiNi1-y-zCoyAlzO2 (NCA) and aluminum-doped LiNixMnyCozO2 (NMC). (27)Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can qualitatively and quantitatively characterize lattice and nonlattice (i.e., surface, coatings, segregation, secondary phase etc.) aluminum coordination and provide information that helps discern its effect in the lattice. In the present study, we use NMR to gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice aluminum sites upon cycling. With the aid of first-principles DFT calculations, we show direct evidence of lattice Al sites, nonpreferential Ni/Co-O-Al ordering in NCA, and the lack of bulk lattice aluminum in aluminum-"doped" NMC. Aluminum coordination of the paramagnetic (lattice) and diamagnetic (nonlattice) nature is investigated for Al-doped NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also studied. A clear reordering of lattice aluminum environments due to nickel migration is observed in NCA upon extended cycling.

Chitosan-magnesium aluminum silicate composite dispersions: characterization of rheology, flocculate size and zeta potential.

PubMed

Khunawattanakul, Wanwisa; Puttipipatkhachorn, Satit; Rades, Thomas; Pongjanyakul, Thaned

2008-03-03

Composite dispersions of chitosan (CS), a positively charged polymer, and magnesium aluminum silicate (MAS), a negatively charged clay, were prepared and rheology, flocculate size and zeta potential of the CS-MAS dispersions were investigated. High and low molecular weights of CS (HCS and LCS, respectively) were used in this study. Moreover, the effects of heat treatment at 60 degrees C on the characteristics of the CS-MAS dispersions and the zeta potential of MAS upon addition of CS at different pHs were examined. Incorporation of MAS into CS dispersions caused an increase in viscosity and a shift of CS flow type from Newtonian to pseudoplastic flow with thixotropic properties. Heat treatment brought about a significant decrease in viscosity and hysteresis area of the composite dispersions. Microscopic studies showed that flocculation of MAS occurred after mixing with CS. The size and polydispersity index of the HCS-MAS flocculate were greater than those of the LCS-MAS flocculate. However, a narrower size distribution and the smaller size of the HCS-MAS flocculate were found after heating at 60 degrees C. Zeta potentials of the CS-MAS flocculates were positive and slightly increased with increasing MAS content. In the zeta potential studies, the negative charge of the MAS could be neutralized by the addition of CS. Increasing the pH and molecular weight of CS resulted in higher CS concentrations required to neutralize the charge of MAS. These findings suggest that the electrostatic interaction between CS and MAS caused a change in flow behavior and flocculation of the composite dispersions, depending on the molecular weight of CS. Heat treatment affected the rheological properties and the flocculate size of the composite dispersions. Moreover, pH of medium and molecular weight of CS influence the zeta potential of MAS.

Complementary Response of Static Spin-Stripe Order and Superconductivity to Nonmagnetic Impurities in Cuprates

DOE PAGES

Guguchia, Z.; Roessli, B.; Khasanov, R.; ...

2017-08-22

Here, we report muon-spin rotation and neutron-scattering experiments on nonmagnetic Zn impurity effects on the static spin-stripe order and superconductivity of the La214 cuprates. Remarkably, it was found that, for samples with hole doping x≈1/8, the spin-stripe ordering temperature T so decreases linearly with Zn doping y and disappears at y≈4%, demonstrating a high sensitivity of static spin-stripe order to impurities within a CuO 2 plane. Moreover, Tso is suppressed by Zn in the same manner as the superconducting transition temperature Tc for samples near optimal hole doping. This surprisingly similar sensitivity suggests that the spin-stripe order is dependent onmore » intertwining with superconducting correlations.« less

Complementary Response of Static Spin-Stripe Order and Superconductivity to Nonmagnetic Impurities in Cuprates

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

Guguchia, Z.; Roessli, B.; Khasanov, R.

Here, we report muon-spin rotation and neutron-scattering experiments on nonmagnetic Zn impurity effects on the static spin-stripe order and superconductivity of the La214 cuprates. Remarkably, it was found that, for samples with hole doping x≈1/8, the spin-stripe ordering temperature T so decreases linearly with Zn doping y and disappears at y≈4%, demonstrating a high sensitivity of static spin-stripe order to impurities within a CuO 2 plane. Moreover, Tso is suppressed by Zn in the same manner as the superconducting transition temperature Tc for samples near optimal hole doping. This surprisingly similar sensitivity suggests that the spin-stripe order is dependent onmore » intertwining with superconducting correlations.« less

Spin-resolved photoemission study of epitaxially grown MoSe 2 and WSe 2 thin films

DOE PAGES

Mo, Sung-Kwan; Hwang, Choongyu; Zhang, Yi; ...

2016-09-12

Few-layer thick MoSe 2 and WSe 2 possess non-trivial spin textures with sizable spin splitting due to the inversion symmetry breaking embedded in the crystal structure and strong spin–orbit coupling. Here, we report a spin-resolved photoemission study of MoSe 2 and WSe 2 thin film samples epitaxially grown on a bilayer graphene substrate. Furthermore, we only found spin polarization in the single- and trilayer samples—not in the bilayer sample—mostly along the out-of-plane direction of the sample surface. The measured spin polarization is found to be strongly dependent on the light polarization as well as the measurement geometry, which reveals intricatemore » coupling between the spin and orbital degrees of freedom in this class of material.« less

Species identification in forensic samples using the SPInDel approach: A GHEP-ISFG inter-laboratory collaborative exercise.

PubMed

Alves, Cíntia; Pereira, Rui; Prieto, Lourdes; Aler, Mercedes; Amaral, Cesar R L; Arévalo, Cristina; Berardi, Gabriela; Di Rocco, Florencia; Caputo, Mariela; Carmona, Cristian Hernandez; Catelli, Laura; Costa, Heloísa Afonso; Coufalova, Pavla; Furfuro, Sandra; García, Óscar; Gaviria, Anibal; Goios, Ana; Gómez, Juan José Builes; Hernández, Alexis; Hernández, Eva Del Carmen Betancor; Miranda, Luís; Parra, David; Pedrosa, Susana; Porto, Maria João Anjos; Rebelo, Maria de Lurdes; Spirito, Matteo; Torres, María Del Carmen Villalobos; Amorim, António; Pereira, Filipe

2017-05-01

DNA is a powerful tool available for forensic investigations requiring identification of species. However, it is necessary to develop and validate methods able to produce results in degraded and or low quality DNA samples with the high standards obligatory in forensic research. Here, we describe a voluntary collaborative exercise to test the recently developed Species Identification by Insertions/Deletions (SPInDel) method. The SPInDel kit allows the identification of species by the generation of numeric profiles combining the lengths of six mitochondrial ribosomal RNA (rRNA) gene regions amplified in a single reaction followed by capillary electrophoresis. The exercise was organized during 2014 by a Working Commission of the Spanish and Portuguese-Speaking Working Group of the International Society for Forensic Genetics (GHEP-ISFG), created in 2013. The 24 participating laboratories from 10 countries were asked to identify the species in 11 DNA samples from previous GHEP-ISFG proficiency tests using a SPInDel primer mix and control samples of the 10 target species. A computer software was also provided to the participants to assist the analyses of the results. All samples were correctly identified by 22 of the 24 laboratories, including samples with low amounts of DNA (hair shafts) and mixtures of saliva and blood. Correct species identifications were obtained in 238 of the 241 (98.8%) reported SPInDel profiles. Two laboratories were responsible for the three cases of misclassifications. The SPInDel was efficient in the identification of species in mixtures considering that only a single laboratory failed to detect a mixture in one sample. This result suggests that SPInDel is a valid method for mixture analyses without the need for DNA sequencing, with the advantage of identifying more than one species in a single reaction. The low frequency of wrong (5.0%) and missing (2.1%) alleles did not interfere with the correct species identification, which demonstrated the advantage of using a method based on the analysis of multiple loci. Overall, the SPInDel method was easily implemented by laboratories using different genotyping platforms, the interpretation of results was straightforward and the SPInDel software was used without any problems. The results of this collaborative exercise indicate that the SPInDel method can be applied successfully in forensic casework investigations. Copyright © 2017 Elsevier B.V. All rights reserved.

NMR study of methane + ethane structure I hydrate decomposition.

PubMed

Dec, Steven F; Bowler, Kristen E; Stadterman, Laura L; Koh, Carolyn A; Sloan, E Dendy

2007-05-24

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

Separating para and ortho water.

PubMed

Horke, Daniel A; Chang, Yuan-Pin; Długołęcki, Karol; Küpper, Jochen

2014-10-27

Water exists as two nuclear-spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules, the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separated, and no pure para sample has been produced. Accordingly, little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. The production of isolated samples of both spin isomers is demonstrated in pure beams of para and ortho water in their respective absolute ground state. These single-quantum-state samples are ideal targets for unraveling spin-conversion mechanisms, for precision spectroscopy and fundamental symmetry-breaking studies, and for spin-enhanced applications, for example laboratory astrophysics and astrochemistry or hypersensitized NMR experiments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Successful control of juvenile dermatomyositis-associated macrophage activation syndrome and interstitial pneumonia: distinct kinetics of interleukin-6 and -18 levels.

PubMed

Wakiguchi, Hiroyuki; Hasegawa, Shunji; Hirano, Reiji; Kaneyasu, Hidenobu; Wakabayashi-Takahara, Midori; Ohga, Shouichi

2015-11-18

Macrophage activation syndrome (MAS) is the secondary hemophagocytic lymphohistiocytosis associated with rheumatic diseases. Recently, the different cytokine profiles between systemic juvenile idiopathic arthritis (sJIA)-associated MAS (sJIA-MAS) and juvenile systemic lupus erythematosus (JSLE)-associated MAS (JSLE-MAS) were reported. However, there is little information about juvenile dermatomyositis (JDM)-associated MAS (JDM-MAS). A 4-year-old girl with JDM was hospitalized because of fever, erythema, hepatosplenomegaly, cytopenia, liver dysfunction and coagulopathy. Bone marrow aspiration revealed appreciable numbers of activated and hemophagocytosing macrophages. She was diagnosed as having JDM-MAS complicated with interstitial pneumonia (IP) based on the findings of the elevation of serum Krebs von den Lungen-6 (KL-6) levels and chest computed tomography findings. We analyzed circulating levels of interleukin (IL)-2,4,6,10,18, tumor necrosis factor-α and interferon-γ in the patient. Hypercytokinemia occurred at the diagnosis of MAS and IP, showing with the prominent elevations of IL-6 and IL-18 levels. The cytokine profiles were distinct from those reported in patients with sJIA-MAS or JSLE-MAS. High-dose corticosteroid and cyclosporine therapy led to a drastic improvement of MAS with decreased IL-6 levels. Subsequent cyclophosphamide therapy successfully controlled IP, paralleled with the declining pattern of IL-18 and KL-6 levels. This is the first report to describe a successful treatment and the cytokine profile of JDM-MAS and IP. Serum IL-6 and IL-18 levels may be useful for predicting the disease activity of JDM-MAS and IP, respectively.

Single-crystal X-ray diffraction and NMR crystallography of a 1:1 cocrystal of di­thia­non and pyrimethanil

PubMed Central

Pöppler, Ann-Christin; Corlett, Emily K.; Pearce, Harriet; Seymour, Mark P.; Reid, Matthew; Montgomery, Mark G.

2017-01-01

A single-crystal X-ray diffraction structure of a 1:1 cocrystal of two fungicides, namely di­thia­non (DI) and pyrimethanil (PM), is reported [systematic name: 5,10-dioxo-5H,10H-naphtho­[2,3-b][1,4]dithiine-2,3-dicarbo­nitrile–4,6-dimethyl-N-phenyl­pyrimidin-2-amine (1/1), C14H4N2O2S2·C12H13N2]. Following an NMR crystallography approach, experimental solid-state magic angle spinning (MAS) NMR spectra are presented together with GIPAW (gauge-including projector augmented wave) calculations of NMR chemical shieldings. Specifically, experimental 1H and 13C chemical shifts are determined from two-dimensional 1H–13C MAS NMR correlation spectra recorded with short and longer contact times so as to probe one-bond C—H connectivities and longer-range C⋯H proximities, whereas H⋯H proximities are identified in a 1H double-quantum (DQ) MAS NMR spectrum. The performing of separate GIPAW calculations for the full periodic crystal structure and for isolated mol­ecules allows the determination of the change in chemical shift upon going from an isolated mol­ecule to the full crystal structure. For the 1H NMR chemical shifts, changes of 3.6 and 2.0 ppm correspond to inter­molecular N—H⋯O and C—H⋯O hydrogen bonding, while changes of −2.7 and −1.5 ppm are due to ring current effects associated with C—H⋯π inter­actions. Even though there is a close inter­molecular S⋯O distance of 3.10 Å, it is of note that the mol­ecule-to-crystal chemical shifts for the involved sulfur or oxygen nuclei are small. PMID:28257008

In situ lignocellulosic unlocking mechanism for carbohydrate hydrolysis in termites: crucial lignin modification

PubMed Central

2011-01-01

Background Termites are highly effective at degrading lignocelluloses, and thus can be used as a model for studying plant cell-wall degradation in biological systems. However, the process of lignin deconstruction and/or degradation in termites is still not well understood. Methods We investigated the associated structural modification caused by termites in the lignin biomolecular assembly in softwood tissues crucial for cell-wall degradation. We conducted comparative studies on the termite-digested (i.e. termite feces) and native (control) softwood tissues with the aid of advanced analytical techniques: 13C crosspolarization magic angle spinning and nuclear magnetic resonance (CP-MAS-NMR) spectroscopy, flash pyrolysis with gas chromatography mass spectrometry (Py-GC/MS), and Py-GC-MS in the presence of tetramethylammonium hydroxide (Py-TMAH)-GC/MS. Results The 13C CP/MAS NMR spectroscopic analysis revealed an increased level of guaiacyl-derived (G unit) polymeric framework in the termite-digested softwood (feces), while providing specific evidence of cellulose degradation. The Py-GC/MS data were in agreement with the 13C CP/MAS NMR spectroscopic studies, thus indicating dehydroxylation and modification of selective intermonomer side-chain linkages in the lignin in the termite feces. Moreover, Py-TMAH-GC/MS analysis showed significant differences in the product distribution between control and termite feces. This strongly suggests that the structural modification in lignin could be associated with the formation of additional condensed interunit linkages. Conclusion Collectively, these data further establish: 1) that the major β-O-4' (β-aryl ether) was conserved, albeit with substructure degeneracy, and 2) that the nature of the resulting polymer in termite feces retained most of its original aromatic moieties (G unit-derived). Overall, these results provide insight into lignin-unlocking mechanisms for understanding plant cell-wall deconstruction, which could be useful in development of new enzymatic pretreatment processes mimicking the termite system for biochemical conversion of lignocellulosic biomass to fuels and chemicals. PMID:21672247

Structural Changes and Proapoptotic Peroxidase Activity of Cardiolipin-Bound Mitochondrial Cytochrome c

PubMed Central

Mandal, Abhishek; Hoop, Cody L.; DeLucia, Maria; Kodali, Ravindra; Kagan, Valerian E.; Ahn, Jinwoo; van der Wel, Patrick C.A.

2015-01-01

The cellular process of intrinsic apoptosis relies on the peroxidation of mitochondrial lipids as a critical molecular signal. Lipid peroxidation is connected to increases in mitochondrial reactive oxygen species, but there is also a required role for mitochondrial cytochrome c (cyt-c). In apoptotic mitochondria, cyt-c gains a new function as a lipid peroxidase that catalyzes the reactive oxygen species-mediated chemical modification of the mitochondrial lipid cardiolipin (CL). This peroxidase activity is caused by a conformational change in the protein, resulting from interactions between cyt-c and CL. The nature of the conformational change and how it causes this gain-of-function remain uncertain. Via a combination of functional, structural, and biophysical experiments we investigate the structure and peroxidase activity of cyt-c in its membrane-bound state. We reconstituted cyt-c with CL-containing lipid vesicles, and determined the increase in peroxidase activity resulting from membrane binding. We combined these assays of CL-induced proapoptotic activity with structural and dynamic studies of the membrane-bound protein via solid-state NMR and optical spectroscopy. Multidimensional magic angle spinning (MAS) solid-state NMR of uniformly 13C,15N-labeled protein was used to detect site-specific conformational changes in oxidized and reduced horse heart cyt-c bound to CL-containing lipid bilayers. MAS NMR and Fourier transform infrared measurements show that the peripherally membrane-bound cyt-c experiences significant dynamics, but also retains most or all of its secondary structure. Moreover, in two-dimensional and three-dimensional MAS NMR spectra the CL-bound cyt-c displays a spectral resolution, and thus structural homogeneity, that is inconsistent with extensive membrane-induced unfolding. Cyt-c is found to interact primarily with the membrane interface, without significantly disrupting the lipid bilayer. Thus, membrane binding results in cyt-c gaining the increased peroxidase activity that represents its pivotal proapoptotic function, but we do not observe evidence for large-scale unfolding or penetration into the membrane core. PMID:26536264

Spinning angle optical calibration apparatus

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

Beer, S.K.; Pratt, H.R.

1991-02-26

This patent describes an optical calibration apparatus provided for calibrating and reproducing spinning angles in cross-polarization, nuclear magnetic resonance spectroscopy. An illuminated magnifying apparatus enables optical setting an accurate reproducing of spinning magic angles in cross-polarization, nuclear magnetic resonance spectroscopy experiments. A reference mark scribed on an edge of a spinning angle test sample holder is illuminated by a light source and viewed through a magnifying scope. When the magic angle of a sample material used as a standard is attained by varying the angular position of the sample holder, the coordinate position of the reference mark relative to amore » graduation or graduations on a reticle in the magnifying scope is noted.« less

Training effect of the exchange bias in sputter deposited Fe3O4 thin films with varying thickness

NASA Astrophysics Data System (ADS)

Muhammed Shameem, P. V.; Senthil Kumar, M.

2018-07-01

The training effect property of the exchange bias in the reactively sputtered polycrystalline Fe3O4 thin films of varying thicknesses in the range 25-200 nm are studied. Structural studies by X-ray diffraction, X-ray photoelectron spectroscopy and selected area electron diffraction confirm the formation of single phase Fe3O4. The scanning electron spectroscopy images show that the grains are uniformly distributed. All the samples show clear and consistent exchange bias training behaviour due to the dynamics of the spins at the interface of the ferrimagnetic core and the spin glass-like surface of the grains. The analysis of the training effect data of the exchange bias field HE measured at 2 K by using three different models show that the model based on the relaxation of the frozen and rotatable spin components at the interface gives the best description for all the samples. From this model, it is found that the reversible interface spins relax around 7 times faster than the frozen interface spins at 2 K for all the samples and that their relative relaxation rates are independent of the sample thickness. This constancy show that the relative relaxation rates of the interfacial frozen and rotatable spin components is a material dependent property. The frozen component of the interfacial spins of each sample is found to be dominated at the initial stage of the training. A direct equivalence between the HE and remanence asymmetry ME is observed. Above the spin freezing temperature, the training effect measurements at 75 K show that the HE decreases sharply with successive field cycling as compared to the measurements made at 2 K and the HE vanishes after first few cycles.

Morphological alterations in the liver of yellow perch (Perca flavescens) from a biological mercury hotspot.

PubMed

Müller, Anne-Katrin; Brinkmann, Markus; Baumann, Lisa; Stoffel, Michael H; Segner, Helmut; Kidd, Karen A; Hollert, Henner

2015-11-01

Mercury (Hg) contamination is a global issue due to its anthropogenic release, long-range transport, and deposition in remote areas. In Kejimkujik National Park and National Historic Site, Nova Scotia, Canada, high concentrations of total mercury (THg) were found in tissues of yellow perch (Perca flavescens). The aim of this study was to evaluate a possible relationship between THg concentrations and the morphology of perch liver as a main site of metal storage and toxicity. Yellow perch were sampled from five lakes known to contain fish representing a wide range in Hg concentrations in fall 2013. The ultrastructure of hepatocytes and the distribution of Hg within the liver parenchyma were analyzed by transmission electron microscopy (TEM) and electron energy loss spectrometry (EELS). The relative area of macrophage aggregates (MAs) in the liver was determined using image analysis software and fluorescence microscopy. No relation between general health indicators (Fulton's condition index) and THg was observed. In line with this, TEM examination of the liver ultrastructure revealed no prominent pathologies related to THg accumulation. However, a morphological parameter that appeared to increase with muscle THg was the relative area of MAs in the liver. The hepatic lysosomes appeared to be enlarged in samples with the highest THg concentrations. Interestingly, EELS analysis revealed that the MAs and hepatic lysosomes contained Hg.

Beneficial Effects of the Activation of the Angiotensin-(1–7) Mas Receptor in a Murine Model of Adriamycin-Induced Nephropathy

PubMed Central

Silveira, Kátia Daniela; Barroso, Lívia Corrêa; Vieira, Angélica Thomáz; Cisalpino, Daniel; Lima, Cristiano Xavier; Bader, Michael; Arantes, Rosa Maria Esteves; dos Santos, Robson Augusto Souza

2013-01-01

Angiotensin-(1–7) [Ang-(1–7)] is a biologically active heptapeptide that may counterbalance the physiological actions of angiotensin II (Ang II) within the renin-angiotensin system (RAS). Here, we evaluated whether activation of the Mas receptor with the oral agonist, AVE 0991, would have renoprotective effects in a model of adriamycin (ADR)-induced nephropathy. We also evaluated whether the Mas receptor contributed for the protective effects of treatment with AT1 receptor blockers. ADR (10 mg/kg) induced significant renal injury and dysfunction that was maximal at day 14 after injection. Treatment with the Mas receptor agonist AVE 0991 improved renal function parameters, reduced urinary protein loss and attenuated histological changes. Renoprotection was associated with reduction in urinary levels of TGF-β. Similar renoprotection was observed after treatment with the AT1 receptor antagonist, Losartan. AT1 and Mas receptor mRNA levels dropped after ADR administration and treatment with losartan reestablished the expression of Mas receptor and increased the expression of ACE2. ADR-induced nephropathy was similar in wild type (Mas+/+) and Mas knockout (Mas −/−) mice, suggesting there was no endogenous role for Mas receptor activation. However, treatment with Losartan was able to reduce renal injury only in Mas+/+, but not in Mas −/− mice. Therefore, these findings suggest that exogenous activation of the Mas receptor protects from ADR-induced nephropathy and contributes to the beneficial effects of AT1 receptor blockade. Medications which target specifically the ACE2/Ang-(1–7)/Mas axis may offer new therapeutic opportunities to treat human nephropathies. PMID:23762470

A Vision in Jeopardy: Royal Navy Maritime Autonomous Systems (MAS)

DTIC Science & Technology

2017-03-31

Chapter 6 will propose a new MAS vision for the RN. However, before doing so, a fresh look at the problem is required. Consensus of the Problem, Not the... assessment , the RN has failed to deliver any sustainable MAS operational capability. A vision for MAS finally materialized in 2014. Yet, the vision...continuous investment and assessment , the RN has failed to deliver any sustainable MAS operational capability. A vision for MAS finally materialized in

Mexican Americans Receive Less Intensive Stroke Rehabilitation Than Non-Hispanic Whites.

PubMed

Morgenstern, Lewis B; Sais, Emma; Fuentes, Michael; Ifejika, Nneka L; Jiang, Xiaqing; Horn, Susan D; Case, Erin; Lisabeth, Lynda D

2017-06-01

Mexican Americans (MAs) have worse neurological, functional, and cognitive outcomes after stroke. Stroke rehabilitation is important for good outcome. In a population-based study, we sought to determine whether allocation of stroke rehabilitation services differed by ethnicity. Patients with stroke were identified as part of the Brain Attack Surveillance in Corpus Christi (BASIC) project, TX, USA. Cases were validated by physicians using source documentation. Patients were followed prospectively for 3 months after stroke to determine rehabilitation services and transitions. Descriptive statistics were used to depict the study population. Continuous baseline variables were compared using 2 sample t tests or Wilcoxon rank-sum tests by ethnicity. Categorical baseline variables were compared using χ 2 tests. Ethnic comparisons of rehabilitation services were compared using χ 2 tests, Fisher's exact tests, and logistic regression. Seventy-two subjects (50 MA and 22 non-Hispanic white [NHW]) were followed. Mean age, NHW-69 (SD 13), MA-66 (SD 11) years, sex (NHW 55% male, MA 50% male) and median presenting National Institutes of Health Stroke Scale did not differ significantly. There were no ethnic differences among the proportion of patients who were sent home without any rehabilitation services ( P =0.9). Among those who received rehabilitation, NHWs were more likely to get inpatient rehabilitation (73%) compared with MAs (30%), P =0.016. MAs (51%) were much more likely to receive home rehabilitation services compared with NHWs (0%) ( P =0.0017). In this population-based study, MAs were more likely to receive home-based rehabilitation, whereas NHWs were more likely to get inpatient rehabilitation. This disparity may, in part, explain the worse stroke outcome in MAs. © 2017 American Heart Association, Inc.

Mexican Americans receive less intensive stroke rehabilitation than non Hispanic whites

PubMed Central

Morgenstern, Lewis B.; Sais, Emma; Fuentes, Michael; Ifejika, Nneka L.; Jiang, Xiaqing; Horn, Susan D.; Case, Erin; Lisabeth, Lynda D.

2017-01-01

Background and Purpose Mexican Americans (MAs) have worse neurologic, functional and cognitive outcomes after stroke. Stroke rehabilitation is important for good outcome. In a population-based study, we sought to determine if allocation of stroke rehabilitation services differed by ethnicity. Methods Stroke patients were identified as part of the Brain Attack Surveillance in Corpus Christi (BASIC) project, Texas, USA. Cases were validated by physicians using source documentation. Patients were followed prospectively for three months following stroke to determine rehabilitation services and transitions. Descriptive statistics were used to depict the study population. Continuous baseline variables were compared using two sample t-tests or Wilcoxon rank-sum tests by ethnicity. Categorical baseline variables were compared using chi-squared tests. Ethnic comparisons of rehabilitation services were compared using chi-squared tests, Fisher’s exact tests and logistic regression. Results Seventy-two subjects (50 MA and 22 non-Hispanic white [NHW]) were followed. Mean age, NHW-69 (sd-13), MA-66 (sd-11) years, sex (NHW 55% male, MA 50% male) and median presenting NIHSS did not differ significantly. There were no ethnic differences among the proportion of patients who were sent home without any rehabilitation services (p=0.9). Among those who received rehabilitation NHWs were more likely to get inpatient rehabilitation (73%) compared with MAs (30%), p=0.016. MAs (51%) were much more likely to receive home rehabilitation services compared with NHWs (0%) (p=0.0017). Conclusions In this population-based study, MAs were more likely to receive home-based rehabilitation while NHWs more likely to get inpatient rehabilitation. This disparity may, in part, explain the worse stroke outcome in MAs. PMID:28386042

Large Spin-Wave Bullet in a Ferrimagnetic Insulator Driven by the Spin Hall Effect

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

Jungfleisch, M. B.; Zhang, W.; Sklenar, J.

2016-02-01

Due to its transverse nature, spin Hall effects (SHE) provide the possibility to excite and detect spin currents and magnetization dynamics even in magnetic insulators. Magnetic insulators are outstanding materials for the investigation of nonlinear phenomena and for novel low power spintronics applications because of their extremely low Gilbert damping. Here, we report on the direct imaging of electrically driven spin-torque ferromagnetic resonance (ST-FMR) in the ferrimagnetic insulator Y 3Fe 5O 12 based on the excitation and detection by SHEs. The driven spin dynamics in Y 3Fe 5O 12 is directly imaged by spatially-resolved microfocused Brillouin light scattering (BLS) spectroscopy.more » Previously, ST-FMR experiments assumed a uniform precession across the sample, which is not valid in our measurements. A strong spin-wave localization in the center of the sample is observed indicating the formation of a nonlinear, self-localized spin-wave `bullet'.« less

Generation of propagating spin waves from regions of increased dynamic demagnetising field near magnetic antidots

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

Davies, C. S., E-mail: csd203@exeter.ac.uk; Kruglyak, V. V.; Sadovnikov, A. V.

We have used Brillouin Light Scattering and micromagnetic simulations to demonstrate a point-like source of spin waves created by the inherently nonuniform internal magnetic field in the vicinity of an isolated antidot formed in a continuous film of yttrium-iron-garnet. The field nonuniformity ensures that only well-defined regions near the antidot respond in resonance to a continuous excitation of the entire sample with a harmonic microwave field. The resonantly excited parts of the sample then served as reconfigurable sources of spin waves propagating (across the considered sample) in the form of caustic beams. Our findings are relevant to further development ofmore » magnonic circuits, in which point-like spin wave stimuli could be required, and as a building block for interpretation of spin wave behavior in magnonic crystals formed by antidot arrays.« less

Alkaline modified oil shale fly ash: optimal synthesis conditions and preliminary tests on CO2 adsorption.

PubMed

Reinik, Janek; Heinmaa, Ivo; Kirso, Uuve; Kallaste, Toivo; Ritamäki, Johannes; Boström, Dan; Pongrácz, Eva; Huuhtanen, Mika; Larsson, William; Keiski, Riitta; Kordás, Krisztián; Mikkola, Jyri-Pekka

2011-11-30

Environmentally friendly product, calcium-silica-aluminum hydrate, was synthesized from oil shale fly ash, which is rendered so far partly as an industrial waste. Reaction conditions were: temperature 130 and 160°C, NaOH concentrations 1, 3, 5 and 8M and synthesis time 24h. Optimal conditions were found to be 5M at 130°C at given parameter range. Original and activated ash samples were characterized by XRD, XRF, SEM, EFTEM, (29)Si MAS-NMR, BET and TGA. Semi-quantitative XRD and MAS-NMR showed that mainly tobermorites and katoite are formed during alkaline hydrothermal treatment. Physical adsorption of CO(2) on the surface of the original and activated ash samples was measured with thermo-gravimetric analysis. TGA showed that the physical adsorption of CO(2) on the oil shale fly ash sample increases from 0.06 to 3-4 mass% after alkaline hydrothermal activation with NaOH. The activated product has a potential to be used in industrial processes for physical adsorption of CO(2) emissions. Copyright © 2011 Elsevier B.V. All rights reserved.

Heterogenous Distribution of MTHFR Gene Variants among Mestizos and Diverse Amerindian Groups from Mexico

PubMed Central

Contreras-Cubas, Cecilia; Sánchez-Hernández, Beatríz E.; García-Ortiz, Humberto; Martínez-Hernández, Angélica; Barajas-Olmos, Francisco; Cid, Miguel; Mendoza-Caamal, Elvia C.; Centeno-Cruz, Federico; Ortiz-Cruz, Gabriela; Jiménez-López, José Concepción; Córdova, Emilio J.; Salas-Bautista, Eva Gabriela; Saldaña-Alvarez, Yolanda; Fernández-López, Juan Carlos; Mutchinick, Osvaldo M.

2016-01-01

Methylenetetrahydrofolate reductase (MTHFR) is a key enzyme in folate metabolism. Folate deficiency has been related to several conditions, including neural tube defects (NTDs) and cardiovascular diseases. Hence, MTHFR genetic variants have been studied worldwide, particularly the C677T and A1298C. We genotyped the C677T and A1298C MTHFR polymorphisms in Mexican Amerindians (MAs), from the largest sample included in a genetic study (n = 2026, from 62 ethnic groups), and in a geographically-matched Mexican Mestizo population (MEZ, n = 638). The 677T allele was most frequent in Mexican individuals, particularly in MAs. The frequency of this allele in both MAs and MEZs was clearly enriched in the South region of the country, followed by the Central East and South East regions. In contrast, the frequency of the 1298C risk allele in Mexicans was one of the lowest in the world. Both in MAs and MEZs the variants 677T and 1298C displayed opposite allele frequency gradients from southern to northern Mexico. Our findings suggest that in Mestizos the 677T allele was derived from Amerindians while the 1298C allele was a European contribution. Some subgroups showed an allele frequency distribution that highlighted their genetic diversity. Notably, the distribution of the frequency of the 677T allele was consistent with that of the high incidence of NTDs reported in MEZ. PMID:27649570

MAS1 Receptor Trafficking Involves ERK1/2 Activation Through a β-Arrestin2-Dependent Pathway.

PubMed

Cerniello, Flavia M; Carretero, Oscar A; Longo Carbajosa, Nadia A; Cerrato, Bruno D; Santos, Robson A; Grecco, Hernán E; Gironacci, Mariela M

2017-11-01

The MAS1 receptor (R) exerts protective effects in the brain, heart, vessels, and kidney. R trafficking plays a critical function in signal termination and propagation and in R resensitization. We examined MAS1R internalization and trafficking on agonist stimulation and the role of β-arrestin2 in the activation of ERK1/2 (extracellular signal-regulated kinase 1/2) and Akt after MAS1R stimulation. Human embryonic kidney 293T cells were transfected with the coding sequence for MAS1R-YFP (MAS1R fused to yellow fluorescent protein). MAS1R internalization was evaluated by measuring the MAS1R present in the plasma membrane after agonist stimulation using a ligand-binding assay. MAS1R trafficking was evaluated by its colocalization with trafficking markers. MAS1R internalization was blocked in the presence of shRNAcaveolin-1 and with dominant negatives for Eps15 (a protein involved in endocytosed Rs by clathrin-coated pits) and for dynamin. After stimulation, MAS1R colocalized with Rab11-a slow recycling vesicle marker-and not with Rab4-a fast recycling vesicle marker-or LysoTracker-a lysosome marker. Cells transfected with MAS1R showed an increase in Akt and ERK1/2 activation on angiotensin-(1-7) stimulation, which was blocked when the clathrin-coated pits pathway was blocked. Suppression of β-arrestin2 by shRNA reduced the angiotensin-(1-7)-induced ERK1/2 activation, whereas Akt activation was not modified. We conclude that on agonist stimulation, MAS1R is internalized through clathrin-coated pits and caveolae in a dynamin-dependent manner and is then slowly recycled back to the plasma membrane. MAS1R induced Akt and ERK1/2 activation from early endosomes, and the activation of ERK1/2 was mediated by β-arrestin2. Thus, MAS1R activity and density may be tightly controlled by the cell. © 2017 American Heart Association, Inc.

Exploring the salt–cocrystal continuum with solid-state NMR using natural-abundance samples: implications for crystal engineering

PubMed Central

Rajput, Lalit; Banik, Manas; Yarava, Jayasubba Reddy; Joseph, Sumy; Pandey, Manoj Kumar

2017-01-01

There has been significant recent interest in differentiating multicomponent solid forms, such as salts and cocrystals, and, where appropriate, in determining the position of the proton in the X—H⋯A—Y X −⋯H—A +—Y continuum in these systems, owing to the direct relationship of this property to the clinical, regulatory and legal requirements for an active pharmaceutical ingredient (API). In the present study, solid forms of simple cocrystals/salts were investigated by high-field (700 MHz) solid-state NMR (ssNMR) using samples with naturally abundant 15N nuclei. Four model compounds in a series of prototypical salt/cocrystal/continuum systems exhibiting {PyN⋯H—O—}/{PyN+—H⋯O−} hydrogen bonds (Py is pyridine) were selected and prepared. The crystal structures were determined at both low and room temperature using X-ray diffraction. The H-atom positions were determined by measuring the 15N—1H distances through 15N-1H dipolar interactions using two-dimensional inversely proton-detected cross polarization with variable contact-time (invCP-VC) 1H→15N→1H experiments at ultrafast (νR ≥ 60–70 kHz) magic angle spinning (MAS) frequency. It is observed that this method is sensitive enough to determine the proton position even in a continuum where an ambiguity of terminology for the solid form often arises. This work, while carried out on simple systems, has implications in the pharmaceutical industry where the salt/cocrystal/continuum condition of APIs is considered seriously. PMID:28875033

Exploring the salt-cocrystal continuum with solid-state NMR using natural-abundance samples: implications for crystal engineering.

PubMed

Rajput, Lalit; Banik, Manas; Yarava, Jayasubba Reddy; Joseph, Sumy; Pandey, Manoj Kumar; Nishiyama, Yusuke; Desiraju, Gautam R

2017-07-01

There has been significant recent interest in differentiating multicomponent solid forms, such as salts and cocrystals, and, where appropriate, in determining the position of the proton in the X -H⋯ A - Y X - ⋯H- A + - Y continuum in these systems, owing to the direct relationship of this property to the clinical, regulatory and legal requirements for an active pharmaceutical ingredient (API). In the present study, solid forms of simple cocrystals/salts were investigated by high-field (700 MHz) solid-state NMR (ssNMR) using samples with naturally abundant 15 N nuclei. Four model compounds in a series of prototypical salt/cocrystal/continuum systems exhibiting {PyN⋯H-O-}/{PyN + -H⋯O - } hydrogen bonds (Py is pyridine) were selected and prepared. The crystal structures were determined at both low and room temperature using X-ray diffraction. The H-atom positions were determined by measuring the 15 N- 1 H distances through 15 N- 1 H dipolar interactions using two-dimensional inversely proton-detected cross polarization with variable contact-time (invCP-VC) 1 H→ 15 N→ 1 H experiments at ultrafast (ν R ≥ 60-70 kHz) magic angle spinning (MAS) frequency. It is observed that this method is sensitive enough to determine the proton position even in a continuum where an ambiguity of terminology for the solid form often arises. This work, while carried out on simple systems, has implications in the pharmaceutical industry where the salt/cocrystal/continuum condition of APIs is considered seriously.

Pure detection of the acoustic spin pumping in Pt/YIG/PZT structures

NASA Astrophysics Data System (ADS)

Uchida, Ken-ichi; Qiu, Zhiyong; Kikkawa, Takashi; Saitoh, Eiji

2014-11-01

The acoustic spin pumping (ASP) stands for the generation of a spin voltage from sound waves in a ferromagnet/paramagnet junction. In this letter, we propose and demonstrate a method for pure detection of the ASP, which enables the separation of sound-wave-driven spin currents from the spin Seebeck effect due to the heating of a sample caused by a sound-wave injection. Our demonstration using a Pt/YIG/PZT sample shows that the ASP signal in this structure measured by a conventional method is considerably offset by the heating signal and that the pure ASP signal is one order of magnitude greater than that reported in the previous study.

1H magnetic resonance spectroscopy of invasive cervical cancer: an in vivo study with ex vivo corroboration.

PubMed

Mahon, Marrita M; Williams, Andreanna D; Soutter, W Patrick; Cox, I Jane; McIndoe, G Angus; Coutts, Glyn A; Dina, Roberto; deSouza, Nandita M

2004-02-01

The objective of this study was to establish in vivo (1)H-magnetic resonance (MR) spectroscopic appearances of cervical cancer using an endovaginal receiver coil and corroborate findings with magic angle spinning (MAS) MR spectroscopy of tissue samples. Fifty-three women (14 controls and 39 with cervical cancer) underwent endovaginal coil MR imaging at 1.5 T with T(1)- and T(2)-weighted scans sagittal and transverse to the cervix. Localized (1)H MR spectra (PRESS technique, TR 1600 ms, TE 135 ms) were accumulated in all controls and 29 cancer patients whose tumour filled > 50% of a single 3.4 cm(3) voxel. Peaks from triglyceride-CH(2) and -CH(3) were defined as present and in-phase (with the choline resonance), present but out-of-phase, or not present. Peak areas of choline-containing compounds were standardized to the area of unsuppressed tissue water resonance. Comparisons in observed resonances between groups were made using Fisher's exact test (qualitative data) and a t-test (quantitative data). Biopsies from these women analysed using MAS-MR spectroscopy and normalized to the intensity of an external standard of silicone rubber were similarly compared. Adequate water suppression permitted spectral analysis in 11 controls and 27 cancer patients. In-phase triglyceride-CH(2) resonances (1.3 ppm) were observed in 74% of tumours but in no control women (p < 0.001). No differences were observed in the presence of a 2 ppm resonance, choline-containing compounds or creatine in cancer compared with control women. However, ex vivo analysis showed significant differences not only in -CH(2), but also in -CH(3), a 2 ppm resonance, choline-containing compounds and creatine between tissues from control women and cancer tissue (p < 0.001, = 0.001, = 0.036, < 0.001 and = 0.004 respectively). On in vivo (1)H-MR spectroscopy, the presence of positive triglyceride-CH(2) resonances can be used to detect and confirm the presence of cervical cancer. However, technical improvements are required before routine clinical use. Copyright 2004 John Wiley & Sons, Ltd.

Effects of anthropogenic particles on the chemical and geophysical properties of urban soils, Detroit, Michigan

NASA Astrophysics Data System (ADS)

Orlicki, Katharine M.

There is a great need in many cities for a better quality of urban soil maps. This is due to the increasing interest in repurposing vacant land for urban redevelopment, agriculture, and green infrastructure. Mapping vacant urban land in Detroit can be very difficult because anthropogenic soils were often highly variable and frequently contained demolition debris (such as brick), making it difficult to use a hand auger. This study was undertaken in Detroit, MI to create a more efficient way to map urban soils based on their geophysical and chemical properties. This will make the mapping process faster, less labor intensive, and therefore more cost effective. Optical and chemical criteria for the identification and classification of microartifacts (MAs) were made from a set of reference artifacts of a known origin. These MAs were then observed and tested in urban topsoil samples from sites in Detroit, Michigan that represent three different land use types (residential demolition, fly ash-impacted, and industrial). Optical analyses, SEM, EDAX, and XRD showed that reference MAs may be classified into five basic compositional types (carbonaceous, calcareous, siliceous, ferruginous and miscellaneous). Reference MAs were generally distinguishable using optical microscopy by color, luster, fracture and microtexture. MAs that were more difficult to classify were further differentiable when using SEM, EDAX, and XRD. MAs were found in all of the anthropogenic soils studied, but were highly variable. All three study sites had concentrations coal-related wastes were the most common types of MAs observed and often included coal, ash (microspheres, microagglomerate), cinders, and burnt shale. MAs derived from waste building materials such as brick, mortar, and glass, were typically found on residential demolition sites. Manufacturing waste MAs, which included iron-making slag and coked coal were commonly observed on industrial sites. Fly ash-impacted sites were composed of only microspheres and microagglomerate that were concentrated within the soils by airborne deposition, making it widespread. These results support the hypothesis that MA assemblages of distinct composition vary with land use. Therefore, it seems likely that magnetic susceptibility surveying and other geophysical methods will prove effective for mapping anthropogenic soils on vacant urban land. Anthropogenic soils and MAs were assessed for pH, electrical conductivity (EC), and magnetic susceptibility (MS). The A horizons of urban soils at residential demolition, industrial-impacted, and fly ash-impacted sites were found to be distinguishable from those of native soils. Anthropogenic soils were higher by one pH unit or more than the background level, had an EC value two to three times the background level, and had MS measurements up to 20 times greater than the background level. The analysis of reference artifacts suggested that the elevated pH of anthropogenic soils was caused by calcareous building material wastes, the elevated EC were the result of both calcareous and ferruginous wastes, and elevated MS were attributable to ferromagnetic materials. Anthropogenic soils collected at residential demolition sites were differentiable by EC, whereas those at collected form industrial sites were distinguishable using MS. Therefore, anthropogenic soils and native soils have a unique chemical and geophysical signature which can be highly dependent on the concentration of MAs. This suggests that EC and MS surveying methods may be used to remotely sense and map urban soils more effectively than using traditional methods alone.

Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy.

PubMed

Shen, Ming; Trébosc, J; Lafon, O; Pourpoint, F; Hu, Bingwen; Chen, Qun; Amoureux, J-P

2014-08-01

Connectivities and proximities between protons and low-gamma nuclei can be probed in solid-state NMR spectroscopy using two-dimensional (2D) proton-detected heteronuclear correlation, through Heteronuclear Multiple Quantum Correlation (HMQC) pulse sequence. The indirect detection via protons dramatically enhances the sensitivity. However, the spectra are often broadened along the indirect F1 dimension by the decay of heteronuclear multiple-quantum coherences under the strong (1)H-(1)H dipolar couplings. This work presents a systematic comparison of the performances of various decoupling schemes during the indirect t1 evolution period of dipolar-mediated HMQC (D-HMQC) experiment. We demonstrate that (1)H-(1)H dipolar decoupling sequences during t1, such as symmetry-based schemes, phase-modulated Lee-Goldburg (PMLG) and Decoupling Using Mind-Boggling Optimization (DUMBO), provide better resolution than continuous wave (1)H irradiation. We also report that high resolution requires the preservation of (1)H isotropic chemical shifts during the decoupling sequences. When observing indirectly broad spectra presenting numerous spinning sidebands, the D-HMQC sequence must be fully rotor-synchronized owing to the rotor-synchronized indirect sampling and dipolar recoupling sequence employed. In this case, we propose a solution to reduce artefact sidebands caused by the modulation of window delays before and after the decoupling application during the t1 period. Moreover, we show that (1)H-(1)H dipolar decoupling sequence using Smooth Amplitude Modulation (SAM) minimizes the t1-noise. The performances of the various decoupling schemes are assessed via numerical simulations and compared to 2D (1)H-{(13)C} D-HMQC experiments on [U-(13)C]-L-histidine⋅HCl⋅H2O at various magnetic fields and Magic Angle spinning (MAS) frequencies. Great resolution and sensitivity enhancements resulting from decoupling during t1 period enable the detection of heteronuclear correlation between aliphatic protons and ammonium (14)N sites in L-histidine⋅HCl⋅H2O. Copyright © 2014 Elsevier Inc. All rights reserved.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

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

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

A Focus on L Dwarfs with Trigonometric Parallaxes

NASA Astrophysics Data System (ADS)

Wang, Y.; Smart, R. L.; Shao, Z.; Jones, H. R. A.; Marocco, F.; Luo, A.; Burgasser, A.; Zhong, J.; Du, B.

2018-06-01

We report new parallax measurements for 10 L- and early T-type dwarfs, five of which have no previous published values, using observations over 3 years at the robotic Liverpool Telescope. The resulting parallaxes and proper motions have median errors of 2 mas and 1.5 mas/year, respectively. Their space motions indicate they are all Galactic disk members. We combined this sample with other objects with astrometry from the Liverpool Telescope and with the published literature astrometry to construct a sample of 260 L- and early T type dwarfs with measured parallaxes, designated the Astrometry Sample. We study the kinematics of the Astrometry Sample, and derived a solar motion of (U, V, W)⊙ = (7.9 ± 1.7, 13.2 ± 1.2, 7.2 ± 1.0) km s‑1, with respect to the local standard of rest, in agreement with the recent literature. We derive a kinematic age of 1.5–1.7 Gyr for the Astrometry Sample assuming the age increases monotonically with the total velocity for a given disk sample. This kinematic age is less than half of the literature values for which used the same methods and similar but different low-mass dwarf samples. We believe this difference arises for two reasons: (1) the sample is mainly composed of mid to late L dwarfs, which are expected to be relatively young, and (2) the requirement that objects have a measured parallax biases the sample to the brighter examples, which tend to be younger.

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

Beltrán, J.J., E-mail: jjbj08@gmail.com; Grupo de Estado Sólido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia, UdeA, Calle 70 No 52-21, Medellín; Barrero, C.A.

We have carefully investigated the structural, optical and electronic properties and related them with changes in the magnetism of sol-gel synthesized Zn{sub 1−x}Co{sub x}O (0≤x≤0.10) nanoparticles. Samples with x≤0.05 were free of spurious phases. Samples with x≤0.03 were found to be with only high spin Co{sup 2+} ions into ZnO structure, whereas sample with x=0.05, exhibited the presence of high spin Co{sup 2+} and low spin Co{sup 3+}. We found that the intensity of the main EPR peak associated with Co{sup 2+} varies with the nominal Co content in a similar manner as the saturation magnetization and coercive field do.more » These results point out that the ferromagnetism in these samples should directly be correlated with the presence of divalent cobalt ions. Bound magnetic polaron (BMP) model and the charge transfer model are insufficient to explain the ferromagnetic properties of Zn{sub 1−x}Co{sub x}O nanoparticles. The room temperature ferromagnetism (RTFM) may be originated from a combination of several factors such as the interaction of high spin Co{sup 2+} ions, perturbation/alteration and/or changes in the electronic structure of ZnO close to the valence band edge and grain boundary effects. - Graphical abstract: The intensity of the main EPR peak associated with Co{sup 2+} varies with the nominal Co content in a similar manner as the saturation magnetization and coercive field do. These results point out that the ferromagnetism in these samples should directly be correlated with the presence of Co{sup 2+} ions. Display Omitted - Highlights: • Systematic and carefully study of physical-chemical properties of Zn{sub 1−x}Co{sub x}O nanoparticles. • Samples with x=0.01 and 0.03 were found to be with only high spin Co{sup 2+}. • Sample with x=0.05, exhibited the presence of high spin Co{sup 2+} and low spin Co{sup 3+}. • The BMP and charge transfer models seem not explain the ferromagnetic properties. • RTFM: high spin Co{sup 2+} ions, defects close to the valence band and grain boundary effects.« less

Medication adherence and symptom reduction in adults treated with mixed amphetamine salts in a randomized crossover study.

PubMed

Adler, Lenard A; Lynch, Lauren R; Shaw, David M; Wallace, Samantha P; Ciranni, Michael A; Briggie, Alexis M; Kulaga, Agatha; O'Donnell, Katherine E; Faraone, Stephen V

2011-09-01

The study objectives were to 1) evaluate medication adherence for adults with attention-deficit/hyperactivity disorder (ADHD) treated with 3 times daily (TID) mixed amphetamine salts immediate release (MAS IR) versus once-daily (qAM) MAS extended release (MAS XR) in a randomized, crossover study; and 2) to examine the associations between adherence and efficacy for MAS IR and MAS XR. Sixty-two adults with ADHD were enrolled and 49 completed the study. The treatment condition order (TID-qAM or qAM-TID) was counterbalanced across participants, with an intervening washout period of ≥ 7 days. Adherence was assessed via 3 measures: 1) self-report, 2) pill count, and 3) the Medication Event Monitoring System (MEMS(®)). The primary efficacy measure was the ADHD Rating Scale (ADHD-RS); secondary measures included the Time-Sensitive ADHD Symptom Scale (TASS) and Clinical Global Impressions-Severity of Illness (CGI-S) scale. Adherence to treatment as measured by self-report and pill count was not significantly different between MAS XR and MAS IR. Adherence was significantly better for MAS XR than MAS IR for all of the MEMS(®) measures. The mean change in ADHD-RS, TASS, and CGI-S scores at endpoint was significantly improved for both MAS IR and MAS XR and did not differ significantly between groups. There was not a significant adherence by efficacy interaction. Adults with ADHD adhered equally well with MAS IR as with MAS XR when assessed by pill count and self-report, but not by the MEMS(®) measures. Both treatments significantly reduced ADHD symptoms, and efficacy was not significantly different between groups. Adherence was not associated with treatment outcome.

Dynamic Behaviour of Tetramethylethylene Diamine (TMEDA) Ligands in Solid Organolithium Compounds: A Variable Temperature 13C and I5N CP/MAS NMR Study

NASA Astrophysics Data System (ADS)

Baumann, Wolfgang; Oprunenko, Yuri; Günther, Harald

1995-05-01

The dynamic behaviour of tetramethylethylene diamine (TMEDA) ligands in three organometallic complexes, dimeric phenyllithium, [Li(tmeda)μ-Ph]2 (1), lithium cyclopentadienide, [Li(tmeda)]C5H5 (2), and dilithium naphthalendiide, trans-[Li(tmeda)]2C10H8 (3), has been studied by CP/MAS 13C and 15N as well as 7Li MAS NMR spectroscopy of powdered samples. Two dynamic processes with free activation enthalpies of 40 and 68 kJ mol-1, respectively, were detected for 1. The first one can be assigned to ring inversion of the five-membered Li-TMEDA rings, while the second is caused by a complete rotation of the TMEDA ligands or a ring inversion of the central four-membered C-Li-C-Li metallacycle. Fast rotation of the ligands on the NMR time scale was found for 2, while 3 shows 180° ring flips of the Li-TMEDA groups, which are characterized by an energy barrier ΔG" (317) of 64 kJ mol-1

SUSANS With Polarized Neutrons.

PubMed

Wagh, Apoorva G; Rakhecha, Veer Chand; Strobl, Makus; Treimer, Wolfgang

2005-01-01

Super Ultra-Small Angle Neutron Scattering (SUSANS) studies over wave vector transfers of 10(-4) nm(-1) to 10(-3) nm(-1) afford information on micrometer-size agglomerates in samples. Using a right-angled magnetic air prism, we have achieved a separation of ≈10 arcsec between ≈2 arcsec wide up- and down-spin peaks of 0.54 nm neutrons. The SUSANS instrument has thus been equipped with the polarized neutron option. The samples are placed in a uniform vertical field of 8.8 × 10(4) A/m (1.1 kOe). Several magnetic alloy ribbon samples broaden the up-spin neutron peak significantly over the ±1.3 × 10(-3) nm(-1) range, while leaving the down-spin peak essentially unaltered. Fourier transforms of these SUSANS spectra corrected for the instrument resolution, yield micrometer-range pair distribution functions for up- and down-spin neutrons as well as the nuclear and magnetic scattering length density distributions in the samples.

Atypical Signaling and Functional Desensitization Response of MAS Receptor to Peptide Ligands

PubMed Central

Tirupula, Kalyan C.; Desnoyer, Russell; Speth, Robert C.; Karnik, Sadashiva S.

2014-01-01

MAS is a G protein-coupled receptor (GPCR) implicated in multiple physiological processes. Several physiological peptide ligands such as angiotensin-(1–7), angiotensin fragments and neuropeptide FF (NPFF) are reported to act on MAS. Studies of conventional G protein signaling and receptor desensitization upon stimulation of MAS with the peptide ligands are limited so far. Therefore, we systematically analyzed G protein signals activated by the peptide ligands. MAS-selective non-peptide ligands that were previously shown to activate G proteins were used as controls for comparison on a common cell based assay platform. Activation of MAS by the non-peptide agonist (1) increased intracellular calcium and D-myo-inositol-1-phosphate (IP1) levels which are indicative of the activation of classical Gαq-phospholipase C signaling pathways, (2) decreased Gαi mediated cAMP levels and (3) stimulated Gα12-dependent expression of luciferase reporter. In all these assays, MAS exhibited strong constitutive activity that was inhibited by the non-peptide inverse agonist. Further, in the calcium response assay, MAS was resistant to stimulation by a second dose of the non-peptide agonist after the first activation has waned suggesting functional desensitization. In contrast, activation of MAS by the peptide ligand NPFF initiated a rapid rise in intracellular calcium with very weak IP1 accumulation which is unlike classical Gαq-phospholipase C signaling pathway. NPFF only weakly stimulated MAS-mediated activation of Gα12 and Gαi signaling pathways. Furthermore, unlike non-peptide agonist-activated MAS, NPFF-activated MAS could be readily re-stimulated the second time by the agonists. Functional assays with key ligand binding MAS mutants suggest that NPFF and non-peptide ligands bind to overlapping regions. Angiotensin-(1–7) and other angiotensin fragments weakly potentiated an NPFF-like calcium response at non-physiological concentrations (≥100 µM). Overall, our data suggest that peptide ligands induce atypical signaling and functional desensitization of MAS. PMID:25068582

Method and sample spinning apparatus for measuring the NMR spectrum of an orientationally disordered sample

DOEpatents

Pines, Alexander; Samoson, Ago

1990-01-01

An improved NMR apparatus and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus spins the sample about an axis. The angle of the axis is mechanically varied such that the time average of two or more Legendre polynomials are zero.

Spin-analyzed SANS for soft matter applications

NASA Astrophysics Data System (ADS)

Chen, W. C.; Barker, J. G.; Jones, R.; Krycka, K. L.; Watson, S. M.; Gagnon, C.; Perevozchivoka, T.; Butler, P.; Gentile, T. R.

2017-06-01

The small angle neutron scattering (SANS) of nearly Q-independent nuclear spin-incoherent scattering from hydrogen present in most soft matter and biology samples may raise an issue in structure determination in certain soft matter applications. This is true at high wave vector transfer Q where coherent scattering is much weaker than the nearly Q-independent spin-incoherent scattering background. Polarization analysis is capable of separating coherent scattering from spin-incoherent scattering, hence potentially removing the nearly Q-independent background. Here we demonstrate SANS polarization analysis in conjunction with the time-of-flight technique for separation of coherent and nuclear spin-incoherent scattering for a sample of silver behenate back-filled with light water. We describe a complete procedure for SANS polarization analysis for separating coherent from incoherent scattering for soft matter samples that show inelastic scattering. Polarization efficiency correction and subsequent separation of the coherent and incoherent scattering have been done with and without a time-of-flight technique for direct comparisons. In addition, we have accounted for the effect of multiple scattering from light water to determine the contribution of nuclear spin-incoherent scattering in both the spin flip channel and non-spin flip channel when performing SANS polarization analysis. We discuss the possible gain in the signal-to-noise ratio for the measured coherent scattering signal using polarization analysis with the time-of-flight technique compared with routine unpolarized SANS measurements.

Overall properties of the Gaia DR1 reference frame

NASA Astrophysics Data System (ADS)

Liu, N.; Zhu, Z.; Liu, J.-C.; Ding, C.-Y.

2017-03-01

Aims: The first Gaia data release (Gaia DR1) provides 2191 ICRF2 sources with their positions in the auxiliary quasar solution and five astrometric parameters - positions, parallaxes, and proper motions - for stars in common between the Tycho-2 catalogue and Gaia in the joint Tycho-Gaia astrometric solution (TGAS). We aim to analyze the overall properties of Gaia DR1 reference frame. Methods: We compare quasar positions of the auxiliary quasar solution with ICRF2 sources using different samples and evaluate the influence on the Gaia DR1 reference frame owing to the Galactic aberration effect over the J2000.0-J2015.0 period. Then we estimate the global rotation between TGAS with Tycho-2 proper motion systems to investigate the property of the Gaia DR1 reference frame. Finally, the Galactic kinematics analysis using the K-M giant proper motions is performed to understand the property of Gaia DR1 reference frame. Results: The positional comparison between the auxiliary quasar solution and ICRF2 shows negligible orientation and validates the declination bias of -0.1mas in Gaia quasar positions with respect to ICRF2. Galactic aberration effect is thought to cause an offset 0.01mas of the Z axis direction of Gaia DR1 reference frame. The global rotation between TGAS and Tycho-2 proper motion systems, obtained by different samples, shows a much smaller value than the claimed value 0.24mas yr-1. For the Galactic kinematics analysis of the TGAS K-M giants, we find possible non-zero Galactic rotation components beyond the classical Oort constants: the rigid part ωYG = -0.38±0.15mas yr-1 and the differential part ω^primeYG = -0.29±0.19mas yr-1 around the YG axis of Galactic coordinates, which indicates possible residual rotation in Gaia DR1 reference frame or problems in the current Galactic kinematical model. Conclusions: The Gaia DR1 reference frame is well aligned to ICRF2, and the possible influence of the Galactic aberration effect should be taken into consideration for the future Gaia-ICRF link. The cause of the rather small global rotation between TGAS and Tycho-2 proper motion systems is unclear and needs further investigation. The possible residual rotation in Gaia DR1 reference frame inferred from the Galactic kinematic analysis should be noted and examined in future data release.

Retinal Microaneurysms Detection Using Gradient Vector Analysis and Class Imbalance Classification.

PubMed

Dai, Baisheng; Wu, Xiangqian; Bu, Wei

2016-01-01

Retinal microaneurysms (MAs) are the earliest clinically observable lesions of diabetic retinopathy. Reliable automated MAs detection is thus critical for early diagnosis of diabetic retinopathy. This paper proposes a novel method for the automated MAs detection in color fundus images based on gradient vector analysis and class imbalance classification, which is composed of two stages, i.e. candidate MAs extraction and classification. In the first stage, a candidate MAs extraction algorithm is devised by analyzing the gradient field of the image, in which a multi-scale log condition number map is computed based on the gradient vectors for vessel removal, and then the candidate MAs are localized according to the second order directional derivatives computed in different directions. Due to the complexity of fundus image, besides a small number of true MAs, there are also a large amount of non-MAs in the extracted candidates. Classifying the true MAs and the non-MAs is an extremely class imbalanced classification problem. Therefore, in the second stage, several types of features including geometry, contrast, intensity, edge, texture, region descriptors and other features are extracted from the candidate MAs and a class imbalance classifier, i.e., RUSBoost, is trained for the MAs classification. With the Retinopathy Online Challenge (ROC) criterion, the proposed method achieves an average sensitivity of 0.433 at 1/8, 1/4, 1/2, 1, 2, 4 and 8 false positives per image on the ROC database, which is comparable with the state-of-the-art approaches, and 0.321 on the DiaRetDB1 V2.1 database, which outperforms the state-of-the-art approaches.

The first observation of Carbon-13 spin noise spectra

PubMed Central

Schlagnitweit, Judith; Müller, Norbert

2012-01-01

We demonstrate the first 13C NMR spin noise spectra obtained without any pulse excitation by direct detection of the randomly fluctuating noise from samples in a cryogenically cooled probe. Noise power spectra were obtained from 13C enriched methanol and glycerol samples at 176 MHz without and with 1H decoupling, which increases the sensitivity without introducing radio frequency interference with the weak spin noise. The multiplet amplitude ratios in 1H coupled spectra indicate that, although pure spin noise prevails in these spectra, the influence of absorbed circuit noise is still significant at the high concentrations used. In accordance with the theory heteronuclear Overhauser enhancements are absent from the 1H-decoupled 13C spin noise spectra. PMID:23041799

Spin coherence and dephasing of localized electrons in monolayer MoS 2

DOE PAGES

Yang, Luyi; Chen, Weibing; McCreary, Kathleen M.; ...

2015-11-10

Here, we report a systematic study of coherent spin precession and spin dephasing in electron-doped monolayer MoS 2. Using time-resolved Kerr rotation spectroscopy and applied in-plane magnetic fields, a nanosecond time scale Larmor spin precession signal commensurate with g-factor |g 0| ≃ 1.86 is observed in several different MoS 2 samples grown by chemical vapor deposition. The dephasing rate of this oscillatory signal increases linearly with magnetic field, suggesting that the coherence arises from a subensemble of localized electron spins having an inhomogeneously broadened distribution of g-factors, g 0 + Δg. In contrast to g 0, Δg is sample-dependent andmore » ranges from 0.042 to 0.115.« less

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

Tani, Yasuo; Shikoh, Eiji, E-mail: shikoh@elec.eng.osaka-cu.ac.jp; Teki, Yoshio

We report the spin-pump-induced spin transport properties of a pentacene film prepared by thermal evaporation. In a palladium(Pd)/pentacene/Ni{sub 80}Fe{sub 20} tri-layer sample, a pure spin-current is generated in the pentacene layer by the spin-pumping of Ni{sub 80}Fe{sub 20}, which is independent of the conductance mismatch problem in spin injection. The spin current is absorbed into the Pd layer, converted into a charge current with the inverse spin-Hall effect in Pd, and detected as an electromotive force. This is clear evidence for the pure spin current at room temperature in pentacene films prepared by thermal evaporation.

Solid State NMR Characterization of Ibuprofen:Nicotinamide Cocrystals and New Idea for Controlling Release of Drugs Embedded into Mesoporous Silica Particles.

PubMed

Skorupska, Ewa; Kaźmierski, Sławomir; Potrzebowski, Marek J

2017-05-01

Grinding and melting methods were employed for synthesis of pharmaceutical cocrystals formed by racemic (R/S) and entiomeric (S) ibuprofen (IBU) and nicotinamide (NA) as coformer. Obtained (R/S)-IBU:NA and (S)-IBU:NA cocrystals were fully characterized by means of advanced one- and two-dimensional solid state nuclear magnetic resonance (SS NMR) techniques with very fast magic angle spinning (MAS) at 60 kHz. The distinction in molecular packing and specific hydrogen bonding pattern was clearly recognized by analysis of 1 H, 13 C, and 15 N spectra. It is concluded from these studies that both methods (grinding and melting) provide exactly the same, specific forms of cocrystals. Thermal solvent-free (TSF) approach was used for loading of (R/S)-IBU:NA and (S)-IBU:NA into the pores of MCM-41 mesoporous silica particle (MSP). The progress and efficiency of this process was analyzed by NMR spectroscopy. It has been confirmed that TSF method is an effective and safe technique of filling the MSP pores with active pharmaceutical ingredients (APIs). By analyzing the NMR results, it has been further proved that excess of IBU and NA components, which are not embedded into the pores during melting and cooling, crystallize on the MCM-41 walls preserving very specific arrangement, characteristic for crystalline samples. By investigating kinetic of release for (R/S)-IBU/MCM-41, (S)-IBU:NA/MCM-41, and (R/S)-IBU:NA/MCM-41 samples containing active components exclusively inside of the pores, it was revealed that release of IBU is much faster for the first of the samples compared to those containing IBU and NA inside the pores. The hypothesis that the rate of release of API can be controlled by specific composition of cocrystal embedded into the MSP pore was further supported by study of (R/S)-IBU:BA/MCM-41 sample with benzoic acid (BA) as coformer.

"Extracting" the key fragment in ETS-10 crystallization and its application in AM-6 assembly.

PubMed

Guo, Meiling; Feng, Zhaochi; Li, Guanna; Hofmann, Jan P; Pidko, Evgeny A; Magusin, Pieter C M M; Guo, Qiang; Weckhuysen, Bert M; Hensen, Emiel J M; Fan, Fengtao; Li, Can

2012-09-17

The mechanism of crystallization of microporous titanosilicate ETS-10 was investigated by Raman spectroscopy combined with (29)Si magic-angle spinning (MAS) NMR spectroscopy, DFT calculations, and SEM imaging. The formation of three-membered ring species is shown to be the key step in the hydrothermal synthesis of ETS-10. They are formed by means of a complex process that involves the interaction of silicate species in the reaction mixture, which promotes the dissolution of TiO(2) particles. These insights into the mechanism of ETS-10 growth led to the successful development of a new synthesis route to the vanadosilicate AM-6 that involves the use of intermediates that contain three-membered ring species as an initiator. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of spin polarization in FM/Al/FM trilayer film at low temperature

NASA Astrophysics Data System (ADS)

Lu, Ning; Webb, Richard

2014-03-01

Measurements of electronic transport in diffusive FM/normal metal/FM trilayer film are performed at temperature ranging from 2K to 300K to determine the behavior of the spin polarized current in normal metal under the influence of quantum phase coherence and spin-orbital interaction. Ten samples of Hall bar with length of 200 micron and width of 20 micron are fabricated through e-beam lithography followed by e-gun evaporation of Ni0.8Fe0.2, aluminum and Ni0.8Fe0.2 with different thickness (5nm to 45nm) in vacuum. At low temperature of 4.2K, coherent backscattering, Rashba spin-orbital interaction and spin flip scattering of conduction electrons contribute to magnetoresistance at low field. Quantitative analysis of magnetoresistance shows transition between weak localization and weak anti-localization for samples with different thickness ratio, which indicates the spin polarization actually affects the phase coherence length and spin-orbital scattering length. However, at temperature between 50K and 300K, only the spin polarization dominates the magnetoresistance.

Polarisation in spin-echo experiments: Multi-point and lock-in measurements

NASA Astrophysics Data System (ADS)

Tamtögl, Anton; Davey, Benjamin; Ward, David J.; Jardine, Andrew P.; Ellis, John; Allison, William

2018-02-01

Spin-echo instruments are typically used to measure diffusive processes and the dynamics and motion in samples on ps and ns time scales. A key aspect of the spin-echo technique is to determine the polarisation of a particle beam. We present two methods for measuring the spin polarisation in spin-echo experiments. The current method in use is based on taking a number of discrete readings. The implementation of a new method involves continuously rotating the spin and measuring its polarisation after being scattered from the sample. A control system running on a microcontroller is used to perform the spin rotation and to calculate the polarisation of the scattered beam based on a lock-in amplifier. First experimental tests of the method on a helium spin-echo spectrometer show that it is clearly working and that it has advantages over the discrete approach, i.e., it can track changes of the beam properties throughout the experiment. Moreover, we show that real-time numerical simulations can perfectly describe a complex experiment and can be easily used to develop improved experimental methods prior to a first hardware implementation.

Room-temperature in situ nuclear spin hyperpolarization from optically pumped nitrogen vacancy centres in diamond

DOE PAGES

King, Jonathan P.; Jeong, Keunhong; Vassiliou, Christophoros C.; ...

2015-12-07

Low detection sensitivity stemming from the weak polarization of nuclear spins is a primary limitation of magnetic resonance spectroscopy and imaging. Methods have been developed to enhance nuclear spin polarization but they typically require high magnetic fields, cryogenic temperatures or sample transfer between magnets. Here we report bulk, room-temperature hyperpolarization of 13C nuclear spins observed via high-field magnetic resonance. The technique harnesses the high optically induced spin polarization of diamond nitrogen vacancy centres at room temperature in combination with dynamic nuclear polarization. We observe bulk nuclear spin polarization of 6%, an enhancement of ~170,000 over thermal equilibrium. The signal ofmore » the hyperpolarized spins was detected in situ with a standard nuclear magnetic resonance probe without the need for sample shuttling or precise crystal orientation. In conclusion, hyperpolarization via optical pumping/dynamic nuclear polarization should function at arbitrary magnetic fields enabling orders of magnitude sensitivity enhancement for nuclear magnetic resonance of solids and liquids under ambient conditions.« less

Structure and properties of novel fibers spun from cellulose in NaOH/thiourea aqueous solution.

PubMed

Ruan, Dong; Zhang, Lina; Zhou, Jinping; Jin, Huiming; Chen, Hui

2004-12-15

Cellulose was dissolved rapidly in a NaOH/thiourea aqueous solution (9.5:4.5 in wt.-%) to prepare a transparent cellulose solution, which was employed, for the first time, to spin a new class of regenerated cellulose fibers by wet spinning. The structure and mechanical properties of the resulting cellulose fibers were characterized, and compared with those of commercially available viscose rayon, cuprammonium rayon and Lyocell fibers. The results from wide angle X-ray diffraction and CP/MAS 13C NMR indicated that the novel cellulose fibers have a structure typical for a family II cellulose and possessed relatively high degrees of crystallinity. Scanning electron microscopy (SEM) and optical microscopy images revealed that the cross-section of the fibers is circular, similar to natural silk. The new fibers have higher molecular weights and better mechanical properties than those of viscose rayon. This low-cost technology is simple, different from the polluting viscose process. The dissolution and regeneration of the cellulose in the NaOH/thiourea aqueous solutions were a physical process and a sol-gel transition rather than a chemical reaction, leading to the smoothness and luster of the fibers. This work provides a potential application in the field of functional fiber manufacturing.

Automatic detection of micro-aneurysms in retinal images based on curvelet transform and morphological operations

NASA Astrophysics Data System (ADS)

Mohammad Alipour, Shirin Hajeb; Rabbani, Hossein

2013-09-01

Diabetic retinopathy (DR) is one of the major complications of diabetes that changes the blood vessels of the retina and distorts patient vision that finally in high stages can lead to blindness. Micro-aneurysms (MAs) are one of the first pathologies associated with DR. The number and the location of MAs are very important in grading of DR. Early diagnosis of micro-aneurysms (MAs) can reduce the incidence of blindness. As MAs are tiny area of blood protruding from vessels in the retina and their size is about 25 to 100 microns, automatic detection of these tiny lesions is still challenging. MAs occurring in the macula can lead to visual loss. Also the position of a lesion such as MAs relative to the macula is a useful feature for analysis and classification of different stages of DR. Because MAs are more distinguishable in fundus fluorescin angiography (FFA) compared to color fundus images, we introduce a new method based on curvelet transform and morphological operations for MAs detection in FFA images. As vessels and MAs are the bright parts of FFA image, firstly extracted vessels by curvelet transform are removed from image. Then morphological operations are applied on resulted image for detecting MAs.

Depressed perivascular sensory innervation of mouse mesenteric arteries with advanced age.

PubMed

Boerman, Erika M; Segal, Steven S

2016-04-15

The dilatory role for sensory innervation of mesenteric arteries (MAs) is impaired in Old (∼24 months) versus Young (∼4 months) mice. We investigated the nature of this impairment in isolated pressurized MAs. With perivascular sensory nerve stimulation, dilatation and inhibition of sympathetic vasoconstriction observed in Young MAs were lost in Old MAs along with impaired dilatation to calcitonin gene-related peptide (CGRP). Inhibiting NO and prostaglandin synthesis increased CGRP EC50 in Young and Old MAs. Endothelial denudation attenuated dilatation to CGRP in Old MAs yet enhanced dilatation to CGRP in Young MAs while abolishing all dilatations to ACh. In Old MAs, sensory nerve density was reduced and RAMP1 (CGRP receptor component) associated with nuclear regions of endothelial cells in a manner not seen in Young MAs or in smooth muscle cells of either age. With advanced age, loss of dilatory signalling mediated through perivascular sensory nerves may compromise perfusion of visceral organs. Vascular dysfunction and sympathetic nerve activity increase with advancing age. In the gut, blood flow is governed by perivascular sensory and sympathetic nerves but little is known of how their functional role is affected by advanced age. We tested the hypothesis that functional sensory innervation of mesenteric arteries (MAs) is impaired for Old (24 months) versus Young (4 months) C57BL/6 male mice. In cannulated pressurized MAs preconstricted 50% with noradrenaline and treated with guanethidine (to inhibit sympathetic neurotransmission), perivascular nerve stimulation (PNS) evoked dilatation in Young but not Old MAs while dilatations to ACh were not different between age groups. In Young MAs, capsaicin (to inhibit sensory neurotransmission) blocked dilatation and increased constriction during PNS. With no difference in efficacy, the EC50 of CGRP as a vasodilator was ∼6-fold greater in Old versus Young MAs. Inhibiting nitric oxide (l-NAME) and prostaglandin (indomethacin) synthesis increased CGRP EC50 in both age groups. Endothelial denudation reduced the efficacy of dilatation to CGRP by ∼30% in Old MAs yet increased this efficacy ∼15% in Young MAs while all dilatations to ACh were abolished. Immunolabelling revealed reduced density of sensory (CGRP) but not sympathetic (tyrosine hydroxylase) innervation for Old versus Young MAs. Whereas the distribution of CGRP receptor proteins was similar in SMCs, RAMP1 associated with nuclear regions of endothelial cells of Old but not Young MAs. With advanced age, the loss of sensory nerve function and diminished effectiveness of CGRP as a vasodilator is multifaceted and may adversely affect splanchnic perfusion. © 2015 The Authors. The Journal of Physiology © 2015 The Physiological Society.

AFRRI (Armed Forces Radiobiology Research Institute) Reports, October, November, December 1986

DTIC Science & Technology

1986-12-01

Acta Chemica Scandinavica, 20, 494-504. RUPPRECHT, A., 1970a, A wet spinning apparatus and auxiliary equipment suitable for preparing samples of...Acta Chemica Scandinavica, B33, 779-780. SEVILLA, M. D., FAILOR, R., CLARK, C, HOLROYD, R. A., and PETTEI, M., 1976, Electron transfer in dinucleoside...spinning. Acta Chemica Scandinavica, 20, 494-504. RUPPRECHT, A., 1970a, A wet spinning apparatus and auxiliary equipment suitable for preparing samples

Magnetic, ferroelectric, and spin phonon coupling studies of Sr{sub 3}Co{sub 2}Fe{sub 24}O{sub 41} multiferroic Z-type hexaferrite

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

Raju, N.; Shravan Kumar Reddy, S.; Ramesh, J.

2016-08-07

The magnetic, Raman, ferroelectric, and in-field {sup 57}Fe Mössbauer studies of polycrystalline multiferroic Sr{sub 3}Co{sub 2}Fe{sub 24}O{sub 41} are reported in this paper. From the magnetization studies, it is observed that the sample is soft magnetic in nature with low temperature magnetic spin transitions like longitudinal to transverse conical structure around 130 K and change in magnetic crystalline anisotropy from conical to planar structure at 250 K. Ferroelectric studies of the sample exhibit the spontaneous polarization at low temperature. Strong spin phonon and spin lattice coupling is observed through low temperature Raman spectroscopy. From the in-field {sup 57}Fe Mössbauer spectroscopy, spin upmore » and spin down site occupations of Fe ions are calculated in the unit cell.« less

Minimal Access Surgery Educational Needs of Trainees from Africa: Perspectives from an Asian Training Institution.

PubMed

Ahmad, J I; Mishra, R K

2015-01-01

The establishment of minimal access surgery (MAS) in the last three decades brought new dimensions to surgical training. The sole role of traditional apprenticeship training model was challenged and adjunctive surgical simulation models were introduced. Knowledge of the trainees' educational needs is important in designing MAS training curriculum. To study the MAS educational needs of trainees from Africa, review MAS training models and offer recommendations for MAS training. Data was obtained from questionnaires filled by trainees from Africa who attended the monthly MAS training at the World Laparoscopy Hospital, India from October 2013 to May 2014 about their MAS educational needs. There were 38 trainees from different parts of Africa (Central, East, North, South and West Africa) with average age of 41.92 ± 8.67 years (minimum-28 years and maximum 63 years) and majority were males (92%). General surgeons constituted 57% while Gynaecologists were 41%. Only a quarter have MAS training integrated in their training curriculum. Box trainers, Animal models, live human surgeries and virtual reality simulation were the commonest models used in previous trainings and favoured in the educational needs for MAS training. Using cadaveric models and self sponsorship were deemphasised. Widespread application of MAS, globalisation and trainees educational needs call for establishing training programmes. Box trainers, animal models, live human surgeries and virtual reality simulators should be adopted and a synergy between Postgraduate surgical programmes, biomedical industry, universities and trainees will facilitate the setting of MAS skills laboratories and programmes.

Angiotensin-(1-7)/Mas axis modulates fear memory and extinction in mice.

PubMed

Lazaroni, Thiago Luiz do Nascimento; Bastos, Cristiane Perácio; Moraes, Márcio Flávio Dutra; Santos, Robson Souza; Pereira, Grace Schenatto

2016-01-01

Inappropriate defense-alerting reaction to fear is a common feature of neuropsychiatric diseases. Therefore, impairments in brain circuits, as well as in molecular pathways underlying the neurovegetative adjustments to fear may play an essential role on developing neuropsychiatric disorders. Here we tested the hypothesis that interfering with angiotensin-(1-7) [Ang-(1-7)]/Mas receptor axis homeostasis, which appears to be essential to arterial pressure control, would affect fear memory and extinction. Mas knockout (MasKO) mice, in FVB/N background, showed normal cued fear memory and extinction, but increased freezing in response to context. Next, as FVB/N has poor performance in contextual fear memory, we tested MasKO in mixed 129xC57BL/6 background. MasKO mice behaved similarly to wild-type (WT), but memory extinction was slower in contextual fear conditioning to a weak protocol (1CS/US). In addition, delayed extinction in MasKO mice was even more pronounced after a stronger protocol (3CS/US). We showed previously that Angiotensin II receptor AT1 antagonist, losantan, rescued object recognition memory deficit in MasKO mice. Here, losartan was also effective. Memory extinction was accelerated in MasKO mice after treatment with losartan. In conclusion, we showed for the first time that Ang-(1-7)/Mas axis may modulate fear memory extinction. Furthermore, we suggest MasKO mice as an animal model to study post-traumatic stress disorder (PTSD). Copyright © 2015 Elsevier Inc. All rights reserved.

The Solar Neighborhood XLIV: RECONS Discoveries within 10 parsecs

NASA Astrophysics Data System (ADS)

Henry, Todd J.; Jao, Wei-Chun; Winters, Jennifer G.; Dieterich, Sergio B.; Finch, Charlie T.; Ianna, Philip A.; Riedel, Adric R.; Silverstein, Michele L.; Subasavage, John P.; Halley Vrijmoet, Eliot

2018-06-01

We describe the 44 systems discovered to be within 10 pc of the Sun by the RECONS team, primarily via the long-term astrometry program at the CTIO/SMARTS 0.9 m that began in 1999. The systems—including 41 with red dwarf primaries, 2 white dwarfs, and 1 brown dwarf—have trigonometric parallaxes greater than 100 mas, with errors of 0.4–2.4 mas in all but one case. We provide updated astrometric, photometric (VRIJHK magnitudes), spectral type, and multiplicity information here. Among these are 14 systems that are new entries to the 10 pc sample, including the first parallaxes for 9 systems and new values for 5 systems that had previous parallaxes with errors greater than 10 mas or values placing them beyond 10 pc. We also provide new data for 22 systems known to lie within 10 pc and 9 systems reported to be closer than that horizon but for which new parallaxes place them further away, bringing the total to 75 systems. The 44 systems added by RECONS comprise one of every 7 systems known within 10 pc. We illustrate the evolution of the 10 pc sample from the 191 systems known when the final Yale Parallax Catalog was published in 1995 to the 317 systems known today. Even so close to the Sun, additional discoveries of white, red, and brown dwarfs are possible, both as primaries and secondaries, although we estimate that at least 90% of the stellar systems closer than 10 pc have now been identified.

FIRE_AX_ER2_MAS

Atmospheric Science Data Center

2015-11-24

... Transition Experiment (ASTEX) ER-2 MODIS Airborne Simulator (MAS) Data Project Title:  MAS ... Temporal Resolution:  Each granule contains one flight track File Format:  HDF Tools:  ... Additional Info:  NASA ER-2 MODIS Airborne Simulator (MAS) SCAR-B Block:  SCAR-B ...

Classification of Human Retinal Microaneurysms Using Adaptive Optics Scanning Light Ophthalmoscope Fluorescein Angiography

PubMed Central

Dubow, Michael; Pinhas, Alexander; Shah, Nishit; Cooper, Robert F.; Gan, Alexander; Gentile, Ronald C.; Hendrix, Vernon; Sulai, Yusufu N.; Carroll, Joseph; Chui, Toco Y. P.; Walsh, Joseph B.; Weitz, Rishard; Dubra, Alfredo; Rosen, Richard B.

2014-01-01

Purpose. Microaneurysms (MAs) are considered a hallmark of retinal vascular disease, yet what little is known about them is mostly based upon histology, not clinical observation. Here, we use the recently developed adaptive optics scanning light ophthalmoscope (AOSLO) fluorescein angiography (FA) to image human MAs in vivo and to expand on previously described MA morphologic classification schemes. Methods. Patients with vascular retinopathies (diabetic, hypertensive, and branch and central retinal vein occlusion) were imaged with reflectance AOSLO and AOSLO FA. Ninety-three MAs, from 14 eyes, were imaged and classified according to appearance into six morphologic groups: focal bulge, saccular, fusiform, mixed, pedunculated, and irregular. The MA perimeter, area, and feret maximum and minimum were correlated to morphology and retinal pathology. Select MAs were imaged longitudinally in two eyes. Results. Adaptive optics scanning light ophthalmoscope fluorescein angiography imaging revealed microscopic features of MAs not appreciated on conventional images. Saccular MAs were most prevalent (47%). No association was found between the type of retinal pathology and MA morphology (P = 0.44). Pedunculated and irregular MAs were among the largest MAs with average areas of 4188 and 4116 μm2, respectively. Focal hypofluorescent regions were noted in 30% of MAs and were more likely to be associated with larger MAs (3086 vs. 1448 μm2, P = 0.0001). Conclusions. Retinal MAs can be classified in vivo into six different morphologic types, according to the geometry of their two-dimensional (2D) en face view. Adaptive optics scanning light ophthalmoscope fluorescein angiography imaging of MAs offers the possibility of studying microvascular change on a histologic scale, which may help our understanding of disease progression and treatment response. PMID:24425852

Double stabilization of nanocrystalline silicon: a bonus from solvent

NASA Astrophysics Data System (ADS)

Kolyagin, Y. G.; Zakharov, V. N.; Yatsenko, A. V.; Paseshnichenko, K. A.; Savilov, S. V.; Aslanov, L. A.

2016-01-01

Double stabilization of the silicon nanocrystals was observed for the first time by 29Si and 13C MAS NMR spectroscopy. The role of solvent, 1,2-dimethoxyethane (glyme), in formation and stabilization of silicon nanocrystals as well as mechanism of modification of the surface of silicon nanocrystals by nitrogen-heterocyclic carbene (NHC) was studied in this research. It was shown that silicon nanocrystals were stabilized by the products of cleavage of the C-O bonds in ethers and similar compounds. The fact of stabilization of silicon nanoparticles with NHC ligands in glyme was experimentally detected. It was demonstrated that MAS NMR spectroscopy is rather informative for study of the surface of silicon nanoparticles but it needs very pure samples.

Neuroglial metabolic compartmentation underlying leptin deficiency in the obese ob/ob mice as detected by magnetic resonance imaging and spectroscopy methods

PubMed Central

Delgado, Teresa C; Violante, Inês R; Nieto-Charques, Laura; Cerdán, Sebastián

2011-01-01

Manganese-Enhanced Magnetic Resonance Imaging (MEMRI), 1H and 13C High-Resolution-Magic Angle Spinning (HR-MAS) Spectroscopy, and genomic approaches were used to compare cerebral activation and neuronal and glial oxidative metabolism in ad libitum fed C57BL6/J leptin-deficient, genetically obese ob/ob mice. T1-weighted Magnetic Resonance Images across the hypothalamic Arcuate and the Ventromedial nuclei were acquired kinetically after manganese infusion. Neuroglial compartmentation was investigated in hypothalamic biopsies after intraperitoneal injections of [1-13C]glucose or [2-13C]acetate. Total RNA was extracted to determine the effects of leptin deficiency in the expression of representative genes coding for regulatory enzymes of hypothalamic energy pathways and glutamatergic neurotransmission. Manganese-Enhanced Magnetic Resonance Imaging revealed enhanced cerebral activation in the hypothalamic Arcuate and Ventromedial nuclei of the ob/ob mice. 13C HR-MAS analysis showed increased 13C accumulation in the hypothalamic glutamate and glutamine carbons of ob/ob mice after the administration of [1-13C]glucose, a primarily neuronal substrate. Hypothalamic expression of the genes coding for glucokinase, phosphofructokinase, pyruvate dehydrogenase, and glutamine synthase was not significantly altered while pyruvate kinase expression was slightly upregulated. In conclusion, leptin deficiency associated with obesity led to increased cerebral activation in the hypothalamic Arcuate and Ventromedial nuclei, concomitant with significant increases in neuronal oxidative metabolism and glutamatergic neurotransmission. PMID:21971349

Further conventions for NMR shielding and chemical shifts IUPAC recommendations 2008.

PubMed

Harris, Robin K; Becker, Edwin D; Cabral De Menezes, Sonia M; Granger, Pierre; Hoffman, Roy E; Zilm, Kurt W

2008-03-01

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the (1)H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating (13)C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice.

Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008).

PubMed

Harris, Robin K; Becker, Edwin D; De Menezes, Sonia M Cabral; Granger, Pierre; Hoffman, Roy E; Zilm, Kurt W

2008-06-01

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the (1)H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating (13)C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice. Copyright (c) 2008 John Wiley & Sons, Ltd

Adsorption and decomposition of dimethyl methylphosphonate (DMMP) on expanded graphite/metal oxides

NASA Astrophysics Data System (ADS)

Hung, Wei-Che; Wang, Je-Chuang; Wu, Kuo-Hui

2018-06-01

Composites based on expanded graphite (EG) and metal oxides (MOs) were prepared by an explosive combustion and blending method. A metal oxide (Ag2O, CuO or ZnO)-containing phase was employed as a component with reactive functionality, which was supported on EG as a component with adsorptive functionality. The physical properties of the EG/MO composites were examined using SEM and FTIR spectroscopy, the results of which indicated that the MOs were incorporated in the EG matrix after impregnation. Solid state magic angle spinning (MAS) 1H, 31P and cross polarization (CP) MAS 13C NMR studies of the EG/MO composites were performed after adsorption of dimethyl methylphosphonate (DMMP). The FTIR and NMR data showed that the initial uptake occurred through both molecular and reactive adsorption. Molecular adsorption occurred by van der Waals interaction of M(Zn, Cu, Ag)⋯Odbnd P and hydrogen-bond formation to isolated hydroxyl groups. Reactive chemisorption appeared to occur through interaction with both Lewis acid sites and active oxygen species present on the MO surface. The FTIR and NMR results exhibited a trend of reactivity towards DMMP in the order Ag2O > ZnO > CuO, which indicated stronger interaction between the Lewis acid sites and the phosphoryl O atom of DMMP for Ag2O as compared with ZnO and CuO, with concomitant formation of surface-coordinated DMMP and bridge-bonded Osbnd Psbnd O phosphorus oxide species.

Topological Magnonics: A Paradigm for Spin-Wave Manipulation and Device Design

NASA Astrophysics Data System (ADS)

Wang, X. S.; Zhang, H. W.; Wang, X. R.

2018-02-01

Conventional magnonic devices use magnetostatic waves whose properties are sensitive to device geometry and the details of magnetization structure, so the design and the scalability of the device or circuitry are difficult. We propose topological magnonics, in which topological exchange spin waves are used as information carriers, that do not suffer from conventional problems of magnonic devices with additional nice features of nanoscale wavelength and high frequency. We show that a perpendicularly magnetized ferromagnet on a honeycomb lattice is generically a topological magnetic material in the sense that topologically protected chiral edge spin waves exist in the band gap as long as a spin-orbit-induced nearest-neighbor pseudodipolar interaction (and/or a next-nearest-neighbor Dzyaloshinskii-Moriya interaction) is present. The edge spin waves propagate unidirectionally along sample edges and domain walls regardless of the system geometry and defects. As a proof of concept, spin-wave diodes, spin-wave beam splitters, and spin-wave interferometers are designed by using sample edges and domain walls to manipulate the propagation of topologically protected chiral spin waves. Since magnetic domain walls can be controlled by magnetic fields or electric current or fields, one can essentially draw, erase, and redraw different spin-wave devices and circuitry on the same magnetic plate so that the proposed devices are reconfigurable and tunable. The topological magnonics opens up an alternative direction towards a robust, reconfigurable and scalable spin-wave circuitry.

Nondestructive tissue analysis for ex vivo and in vivo cancer diagnosis using a handheld mass spectrometry system

PubMed Central

Zhang, Jialing; Rector, John; Lin, John Q.; Young, Jonathan H.; Sans, Marta; Katta, Nitesh; Giese, Noah; Yu, Wendong; Nagi, Chandandeep; Suliburk, James; Liu, Jinsong; Bensussan, Alena; DeHoog, Rachel J.; Garza, Kyana Y.; Ludolph, Benjamin; Sorace, Anna G.; Syed, Anum; Zahedivash, Aydin; Milner, Thomas E.; Eberlin, Livia S.

2018-01-01

Conventional methods for histopathologic tissue diagnosis are labor- and time-intensive and can delay decision-making during diagnostic and therapeutic procedures. We report the development of an automated and biocompatible handheld mass spectrometry device for rapid and nondestructive diagnosis of human cancer tissues. The device, named MasSpec Pen, enables controlled and automated delivery of a discrete water droplet to a tissue surface for efficient extraction of biomolecules. We used the MasSpec Pen for ex vivo molecular analysis of 20 human cancer thin tissue sections and 253 human patient tissue samples including normal and cancerous tissues from breast, lung, thyroid, and ovary. The mass spectra obtained presented rich molecular profiles characterized by a variety of potential cancer biomarkers identified as metabolites, lipids, and proteins. Statistical classifiers built from the histologically validated molecular database allowed cancer prediction with high sensitivity (96.4%), specificity (96.2%), and overall accuracy (96.3%), as well as prediction of benign and malignant thyroid tumors and different histologic subtypes of lung cancer. Notably, our classifier allowed accurate diagnosis of cancer in marginal tumor regions presenting mixed histologic composition. Last, we demonstrate that the MasSpec Pen is suited for in vivo cancer diagnosis during surgery performed in tumor-bearing mouse models, without causing any observable tissue harm or stress to the animal. Our results provide evidence that the MasSpec Pen could potentially be used as a clinical and intraoperative technology for ex vivo and in vivo cancer diagnosis. PMID:28878011

Quality of Kelantan drinking water and knowledge, attitude and practice among the population of Pasir Mas, Malaysia.

PubMed

Ab Razak, N H; Praveena, S M; Aris, A Z; Hashim, Z

2016-02-01

Information about the quality of drinking water, together with analysis of knowledge, attitude and practice (KAP) analysis and health risk assessment (HRA) remain limited. The aims of this study were: (1) to ascertain the level of KAP regarding heavy metal contamination of drinking water in Pasir Mas; (2) to determine the concentration of heavy metals (Al, Cr, Cu, Fe, Ni, Pb, Zn and Cd) in drinking water in Pasir Mas; and (3) to estimate the health risks (non-carcinogenic and carcinogenic) caused by heavy metal exposure through drinking water using hazard quotient and lifetime cancer risk. Information on KAP was collected using a standardized questionnaire. Heavy metal analysis of drinking water samples was performed using graphite furnace atomic absorption spectrophotometry. The population of Pasir Mas has good knowledge (80%), a less positive attitude (93%) and good practice (81%) towards heavy metal contamination of drinking water. The concentrations of heavy metals analysed in this study were found to be below the permissible limits for drinking water set by the Malaysian Ministry of Health and the World Health Organization. The HRA showed no potential non-carcinogenic and carcinogenic risks from the intake of heavy metal through drinking water. By investigating the quality of drinking water, KAP and HRA, the results of this study will provide authorities with the knowledge and resources to improve the management of drinking water quality in the future. Copyright © 2015 The Royal Society for Public Health. Published by Elsevier Ltd. All rights reserved.

Mandibular Advancement Splint as Short-Term Alternative Treatment in Patients with Obstructive Sleep Apnea Already Effectively Treated with Continuous Positive Airway Pressure

PubMed Central

Almeida, Fernanda R.; Mulgrew, Alan; Ayas, Najib; Tsuda, Hiroko; Lowe, Alan A.; Fox, Nurit; Harrison, Sandra; Fleetham, John A.

2013-01-01

Study Objectives: CPAP is used as the first-line treatment for patients with severe OSA, but this machine is not always feasible to use on the long term. We performed a clinical trial to determine whether patients with OSA could use a mandibular advancement splint (MAS) as a short-term treatment alternative to CPAP. Methods: Twenty-two patients adherent with CPAP therapy were recruited to the study. Each patient used the MAS for approximately 4 months. The transition between CPAP to MAS was gradual, and patients were asked to start using MAS together with CPAP during the MAS titration until subjective improvement or maximum mandibular advancement was achieved. Sleepiness (ESS), quality of life (SAQLI), and polysomnography were recorded prior to and after MAS titration. Patients recorded CPAP or MAS usage for the following 3 months. Results: Seven women and 12 men with a mean age of 53.8 (± 12.1) years and mean body mass index of 28.1 (± 4.8) kg/m2 completed the clinical trial. Prior to MAS, CPAP adherence was 5.8 h/night. AHI decreased significantly with MAS use compared to baseline (30.7 ± 23.1 vs 13.2 ± 11; p < 0.01). Fourteen patients (74%) had > 50% decrease in their AHI, while 2 patients had an increase in their AHI. There were no significant differences in SAQLI between MAS and CPAP treatment, while ESS decreased significantly on MAS. MAS self-reported usage was correlated with treatment efficacy (r = 0.52; p < 0.05). Seventy-five percent of the patients reported being sufficiently satisfied with MAS to continue to use it as an alternative short-term therapy. Conclusions: MAS partially or completely reduced sleep disordered breathing in the majority of selected, successfully CPAP-treated severe OSA patients. Many patients can probably effectively use MAS as a short-term treatment alternative to CPAP. Clinical Trial Registration: ClinicalTrials.gov registration number NCT00358605. Commentary: A commentary on this article appears in this issue on page 325. Citation: Almeida FR; Mulgrew A; Ayas N; Tsuda H; Lowe AA; Fox N; Harrison S; Fleetham JA. Mandibular advancement splint as short-term alternative treatment in patients with obstructive sleep apnea already effectively treated with continuous positive airway pressure. J Clin Sleep Med 2013;9(4):319-324. PMID:23585745

A randomized, double-blind study of SHP465 mixed amphetamine salts extended-release in adults with ADHD using a simulated adult workplace design.

PubMed

Wigal, Timothy; Brams, Matthew; Frick, Glen; Yan, Brian; Madhoo, Manisha

2018-06-18

The objective of this paper was to evaluate the efficacy, duration of effect, and tolerability of SHP465 mixed amphetamine salts (MAS) extended-release versus placebo and immediate-release MAS (MAS IR) in adults with attention-deficit/hyperactivity disorder (ADHD). Adults with ADHD Rating Scale, Version IV (ADHD-RS-IV) scores ≥24 were randomized to SHP465 MAS (50 or 75 mg), placebo, or 25 mg MAS IR in a double-blind, three-period, crossover study using a simulated adult workplace environment. On the final day of each 7-day treatment period, efficacy was assessed for 16 h postdose. Primary efficacy analyses for Permanent Product Measure of Performance (PERMP) total score averaged across all postdose assessments and each postdose time point were conducted in the intent-to-treat population using a mixed linear model. Secondary end-points included PERMP problems attempted and answered correctly and ADHD-RS-IV scores based on clinician ratings of counselor observations using the Time Segment Rating System and participant self-report. Tolerability assessments included treatment-emergent adverse events (TEAEs) and vital signs. Least squares mean (95% CI) treatment differences (combined 50/75 mg SHP465 MAS-placebo) significantly favored SHP465 MAS over placebo for PERMP total score averaged across all postdose assessments (18.38 [11.28, 25.47]; P < .0001) and at each postdose assessment (all P < .02). Nominal superiority of MAS IR over placebo for PERMP total score averaged across all postdose assessments was observed (nominal P = .0001); treatment differences between SHP465 MAS and MAS IR were not significant (nominal P = .2443). The two most frequently reported TEAEs associated with SHP465 MAS were insomnia (36.5%) and anorexia (21.2%). Mean increases in pulse and blood pressure with SHP465 MAS exceeded those of placebo. SHP465 MAS (combined 50/75 mg) significantly improved PERMP total score versus placebo, with superiority observed from 2 to 16 h postdose. The tolerability profile of SHP465 MAS was similar to previous reports of SHP465 MAS in adults with ADHD. https://clinicaltrials.gov/ct2/show/NCT00928148 identifier is NCT00928148.

MODIS airborne simulator visible and near-infrared calibration, 1991 FIRE-Cirrus field experiment. Calibration version: FIRE King 1.1

NASA Technical Reports Server (NTRS)

Arnold, G. Thomas; Fitzgerald, Michael; Grant, Patrick S.; King, Michael D.

1994-01-01

Calibration of the visible and near-infrared channels of the MODIS Airborne Simulator (MAS) is derived from observations of a calibrated light source. For the 1991 FIRE-Cirrus field experiment, the calibrated light source was the NASA Goddard 48-inch integrating hemisphere. Laboratory tests during the FIRE Cirrus field experiment were conducted to calibrate the hemisphere and from the hemisphere to the MAS. The purpose of this report is to summarize the FIRE-Cirrus hemisphere calibration, and then describe how the MAS was calibrated from observations of the hemisphere data. All MAS calibration measurements are presented, and determination of the MAS calibration coefficients (raw counts to radiance conversion) is discussed. Thermal sensitivity of the MAS visible and near-infrared calibration is also discussed. Typically, the MAS in-flight is 30 to 60 degrees C colder than the room temperature laboratory calibration. Results from in-flight temperature measurements and tests of the MAS in a cold chamber are given, and from these, equations are derived to adjust the MAS in-flight data to what the value would be at laboratory conditions. For FIRE-Cirrus data, only channels 3 through 6 were found to be temperature sensitive. The final section of this report describes comparisons to an independent MAS (room temperature) calibration by Ames personnel using their 30-inch integrating sphere.

Hyperspectral Microwave Atmospheric Sounder (HyMAS) Architecture and Design Accommodations

NASA Technical Reports Server (NTRS)

Hilliard, Lawrence; Racette, Paul; Blackwell, William; Galbraith, Christopher; Thompson, Erik

2013-01-01

The Hyperspectral Microwave Atmospheric Sounder (HyMAS) is being developed at Lincoln Laboratories and accommodated by the Goddard Space Flight Center for a flight opportunity on a NASA research aircraft. The term "hyperspectral microwave" is used to indicate an all-weather sounding that performs equivalent to hyperspectral infrared sounders in clear air with vertical resolution of approximately 1 km. Deploying the HyMAS equipped scanhead with the existing Conical Scanning Microwave Imaging Radiometer (CoSMIR) shortens the path to a flight demonstration. Hyperspectral microwave is achieved through the use of independent RF antennas that sample the volume of the Earth s atmosphere through various levels of frequencies, thereby producing a set of dense, spaced vertical weighting functions. The simulations proposed for HyMAS 118/183-GHz system should yield surface precipitation rate and water path retrievals for small hail, soft hail, or snow pellets, snow, rainwater, etc. with accuracies comparable to those of the Advanced Technology Microwave Sounder. Further improvements in retrieval methodology (for example, polarization exploitation) are expected. The CoSMIR instrument is a packaging concept re-used on HyMAS to ease the integration features of the scanhead. The HyMAS scanhead will include an ultra-compact Intermediate Frequency Processor (IFP) module that is mounted inside the door to improve thermal management. The IFP is fabricated with materials made of Low-Temperature Co-fired Ceramic (LTCC) technology integrated with detectors, amplifiers, A/D conversion and data aggregation. The IFP will put out 52 channels of 16 bit data comprised of 4-9 channel data streams for temperature profiles and 2-8 channel streams for water vapor. With the limited volume of the existing CoSMIR scanhead and new HyMAS front end components, the HyMAS team at Goddard began preliminary layout work inside the new drum. Importing and re-using models of the shell, the scan head computer, and the slip rings developed for CoSMIR was the starting point. The next step was to modify the antenna faceplate to accommodate the dimensions of the three dual polarization Gaussian Optics Antenna (GOA) assemblies. Two mechanical concepts for the core technology, the hyperspectral IFP, were captured in a design tradeoff. Connector models considered minimum bend radii for the IFP analog connectors. Hyperspectral imaging is accomplished by strategically using a short wavelength intermediate frequency of 18-29 GHz, and thus reducing the size of components in the connection of the front end to the IFP. The SMK (2.92mm) Series connector will lay near the hinge line to minimize its flexing. The digital output of the IFP will use a Serial Peripheral Interface (SPI) that must be accommodated by the scan head computer. To make that computer more reliable, maintainable, and forward compatible with the 52 HyMAS channels, a testbed of the scan head, calibration, and archive computers and the PIC24 microprocessor that resides on the IFP is in development. The computers will be programmed using a new framework application called Interoperable Remote Component (IRC). This software allows flexibility to program computers that communicate with each other and can adapt easily to the emerging HyMAS requirements for data format, algorithms, and graphical user interface (GUI). It is expected that the CoSMIR instrument will cut over to the IRC after it is adapted on an updated CoSMIR testbed.

Hyperspectral Microwave Atmospheric Sounder (HyMAS) architecture and design accommodations

NASA Astrophysics Data System (ADS)

Hilliard, L.; Racette, P.; Blackwell, W.; Galbraith, C.; Thompson, E.

The Hyperspectral Microwave Atmospheric Sounder (HyMAS) is being developed at Lincoln Laboratories and accommodated by the Goddard Space Flight Center for a flight opportunity on a NASA research aircraft. The term “ hyperspectral microwave” is used to indicate an all-weather sounding that performs equivalent to hyperspectral infrared sounders in clear air with vertical resolution of approximately 1 km. Deploying the HyMAS equipped scanhead with the existing Conical Scanning Microwave Imaging Radiometer (CoSMIR) shortens the path to a flight demonstration. Hyperspectral microwave is achieved through the use of independent RF antennas that sample the volume of the Earth's atmosphere through various levels of frequencies, thereby producing a set of dense, spaced vertical weighting functions. The simulations proposed for HyMAS 118/183-GHz system should yield surface precipitation rate and water path retrievals for small hail, soft hail, or snow pellets, snow, rainwater, etc. with accuracies comparable to those of the Advanced Technology Microwave Sounder. Further improvements in retrieval methodology (for example, polarization exploitation) are expected. The CoSMIR instrument is a packaging concept re-used on HyMAS to ease the integration features of the scanhead. The HyMAS scanhead will include an ultra-compact Intermediate Frequency Processor (IFP) module that is mounted inside the door to improve thermal management. The IFP is fabricated with materials made of Low-Temperature Co-fired Ceramic (LTCC) technology integrated with detectors, amplifiers, A/D conversion and data aggregation. The IFP will put out 52 channels of 16 bit data comprised of 4 - 9 channel data streams for temperature profiles and 2-8 channel streams for water vapor. With the limited volume of the existing CoSMIR scanhead and new HyMAS front end components, the HyMAS team at Goddard began preliminary layout work inside the new drum. Importing and re-using models of the shell, the s- an head computer, and the slip rings developed for CoSMIR was the starting point. The next step was to modify the antenna faceplate to accommodate the dimensions of the three dual polarization Gaussian Optics Antenna (GOA) assemblies. Two mechanical concepts for the core technology, the hyperspectral IFP, were captured in a design tradeoff. Connector models considered minimum bend radii for the IFP analog connectors. Hyperspectral imaging is accomplished by strategically using a short wavelength intermediate frequency of 18-29 GHz, and thus reducing the size of components in the connection of the front end to the IFP. The SMK (2.92mm) Series connector will lay near the hinge line to minimize its' flexing. The digital output of the IFP will use a Serial Peripheral Interface (SPI) that must be accommodated by the scan head computer. To make that computer more reliable, maintainable, and forward compatible with the 52 HyMAS channels, a testbed of the scan head, calibration, and archive computers and the PIC24 microprocessor that resides on the IFP is in development. The computers will be programmed using a new framework application called Interoperable Remote Component (IRC). This software allows flexibility to program computers that communicate with each other and can adapt easily to the emerging HyMAS requirements for data format, algorithms, and graphical user interface (GUI). It is expected that the CoSMIR instrument will cut over to the IRC after it is adapted on an updated CoSMIR testbed.

Undergraduate Electron-Spin-Resonance Experiment.

ERIC Educational Resources Information Center

Willis, James S.

1980-01-01

Describes the basic procedures for use of an electron-spin resonance spectrometer and potassium azide (KN3) in an experiment which extends from the phase of sample preparation (crystal growth, sample mounting, and orientation) through data taking to the stages of calculation and theoretical explanation. (Author/DS)

SUSANS With Polarized Neutrons

PubMed Central

Wagh, Apoorva G.; Rakhecha, Veer Chand; Strobl, Makus; Treimer, Wolfgang

2005-01-01

Super Ultra-Small Angle Neutron Scattering (SUSANS) studies over wave vector transfers of 10–4 nm–1 to 10–3 nm–1 afford information on micrometer-size agglomerates in samples. Using a right-angled magnetic air prism, we have achieved a separation of ≈10 arcsec between ≈2 arcsec wide up- and down-spin peaks of 0.54 nm neutrons. The SUSANS instrument has thus been equipped with the polarized neutron option. The samples are placed in a uniform vertical field of 8.8 × 104 A/m (1.1 kOe). Several magnetic alloy ribbon samples broaden the up-spin neutron peak significantly over the ±1.3 × 10–3 nm–1 range, while leaving the down-spin peak essentially unaltered. Fourier transforms of these SUSANS spectra corrected for the instrument resolution, yield micrometer-range pair distribution functions for up- and down-spin neutrons as well as the nuclear and magnetic scattering length density distributions in the samples. PMID:27308127

Quantitative characterization of spin-orbit torques in Pt/Co/Pt/Co/Ta/BTO heterostructures due to the magnetization azimuthal angle dependence

NASA Astrophysics Data System (ADS)

Engel, Christian; Goolaup, Sarjoosing; Luo, Feilong; Lew, Wen Siang

2017-08-01

Substantial understanding of spin-orbit interactions in heavy-metal (HM)/ferromagnet (FM) heterostructures is crucial in developing spin-orbit torque (SOT) spintronics devices utilizing spin Hall and Rashba effects. Though the study of SOT effective field dependence on the out-of-plane magnetization angle has been relatively extensive, the understanding of in-plane magnetization angle dependence remains unknown. Here, we analytically propose a method to compute the SOT effective fields as a function of the in-plane magnetization angle using the harmonic Hall technique in perpendicular magnetic anisotropy (PMA) structures. Two different samples with PMA, a Pt /Co /Pt /Co /Ta /BaTi O3 (BTO) test sample and a Pt/Co/Pt/Co/Ta reference sample, are studied using the derived formula. Our measurements reveal that only the dampinglike field of the test sample with a BTO capping layer exhibits an in-plane magnetization angle dependence, while no angular dependence is found in the reference sample. The presence of the BTO layer in the test sample, which gives rise to a Rashba effect at the interface, is ascribed as the source of the angular dependence of the dampinglike field.

Scaling Behavior of the Spin Pumping Effect in Ferromagnet-Platinum Bilayers

NASA Astrophysics Data System (ADS)

Czeschka, F. D.; Dreher, L.; Brandt, M. S.; Weiler, M.; Althammer, M.; Imort, I.-M.; Reiss, G.; Thomas, A.; Schoch, W.; Limmer, W.; Huebl, H.; Gross, R.; Goennenwein, S. T. B.

2011-07-01

We systematically measured the dc voltage VISH induced by spin pumping together with the inverse spin Hall effect in ferromagnet-platinum bilayer films. In all our samples, comprising ferromagnetic 3d transition metals, Heusler compounds, ferrite spinel oxides, and magnetic semiconductors, VISH invariably has the same polarity, and scales with the magnetization precession cone angle. These findings, together with the spin mixing conductance derived from the experimental data, quantitatively corroborate the present theoretical understanding of spin pumping in combination with the inverse spin Hall effect.

Cavity Mediated Manipulation of Distant Spin Currents Using a Cavity-Magnon-Polariton.

PubMed

Bai, Lihui; Harder, Michael; Hyde, Paul; Zhang, Zhaohui; Hu, Can-Ming; Chen, Y P; Xiao, John Q

2017-05-26

Using electrical detection of a strongly coupled spin-photon system comprised of a microwave cavity mode and two magnetic samples, we demonstrate the long distance manipulation of spin currents. This distant control is not limited by the spin diffusion length, instead depending on the interplay between the local and global properties of the coupled system, enabling systematic spin current control over large distance scales (several centimeters in this work). This flexibility opens the door to improved spin current generation and manipulation for cavity spintronic devices.

Scanned-probe detection of electron spin resonance from a nitroxide spin probe

PubMed Central

Moore, Eric W.; Lee, SangGap; Hickman, Steven A.; Wright, Sarah J.; Harrell, Lee E.; Borbat, Peter P.; Freed, Jack H.; Marohn, John A.

2009-01-01

We report an approach that extends the applicability of ultrasensitive force-gradient detection of magnetic resonance to samples with spin-lattice relaxation times (T 1) as short as a single cantilever period. To demonstrate the generality of the approach, which relies on detecting either cantilever frequency or phase, we used it to detect electron spin resonance from a T 1 = 1 ms nitroxide spin probe in a thin film at 4.2 K and 0.6 T. By using a custom-fabricated cantilever with a 4 μm-diameter nickel tip, we achieve a magnetic resonance sensitivity of 400 Bohr magnetons in a 1 Hz bandwidth. A theory is presented that quantitatively predicts both the lineshape and the magnitude of the observed cantilever frequency shift as a function of field and cantilever-sample separation. Good agreement was found between nitroxide T 1 's measured mechanically and inductively, indicating that the cantilever magnet is not an appreciable source of spin-lattice relaxation here. We suggest that the new approach has a number of advantages that make it well suited to push magnetic resonance detection and imaging of nitroxide spin labels in an individual macromolecule to single-spin sensitivity. PMID:20018707

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS IN AN ATMOSPHERIC PRESSURE ETHYLENE DIFFUSION FLAME. (R825412)

EPA Science Inventory

Abstract

The microstructure of an atmospheric pressure, counterflow, sooting, flat, laminar ethylene diffusion flame has been studied experimentally by withdrawing samples from within the flame using a heated quartz microprobe coupled to an online gas chromatograph/mas...

Nuclear spin polarized H and D by means of spin-exchange optical pumping

NASA Astrophysics Data System (ADS)

Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

1998-01-01

Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

Quasiparticle spin resonance and coherence in superconducting aluminium

NASA Astrophysics Data System (ADS)

Quay, C. H. L.; Weideneder, M.; Chiffaudel, Y.; Strunk, C.; Aprili, M.

2015-10-01

Conventional superconductors were long thought to be spin inert; however, there is now increasing interest in both (the manipulation of) the internal spin structure of the ground-state condensate, as well as recently observed long-lived, spin-polarized excitations (quasiparticles). We demonstrate spin resonance in the quasiparticle population of a mesoscopic superconductor (aluminium) using novel on-chip microwave detection techniques. The spin decoherence time obtained (~100 ps), and its dependence on the sample thickness are consistent with Elliott-Yafet spin-orbit scattering as the main decoherence mechanism. The striking divergence between the spin coherence time and the previously measured spin imbalance relaxation time (~10 ns) suggests that the latter is limited instead by inelastic processes. This work stakes out new ground for the nascent field of spin-based electronics with superconductors or superconducting spintronics.

Hydronephrosis alters cardiac ACE2 and Mas receptor expression in mice.

PubMed

Zhang, Yanling; Ma, Lulu; Wu, Junyan; Chen, Tingting

2015-06-01

Hydronephrosis is characterized by substantial loss of tubules and affects renin secretion in the kidney. However, whether alterations of angiotensin-converting enzyme (ACE), ACE2 and Mas receptor in the heart are observed in hydronephrosis is unknown. Thus, we assessed these components in hydronephrotic mice treated with AT1 receptor blockade and ACE inhibitor. Hydronephrosis was induced by left ureteral ligation in Balb/C mice except sham-operated animals. The levels of cardiac ACE, ACE2 and Mas receptor were measured after treatment of losartan or enalapril. Hydronephrosis led to an increase of ACE level and a decrease of ACE2 and Mas receptor in the heart. Losartan decreased cardiac ACE level, but ACE2 and Mas receptor levels significantly increased in hydronephrotic mice (p < 0.01). Enalapril increased ACE2 levels (p < 0.01), but did not affect Mas receptor in the heart. Plasma renin activity (PRA) and Ang II decreased in hydronephrotic mice, but significantly increased after treatment with losartan or enalapril. Hydronephrosis increased cardiac ACE and suppressed ACE2 and Mas receptor levels. AT1 blockade caused sustained activation of cardiac ACE2 and Mas receptor, but ACE inhibitor had the limitation of such activation of Mas receptor in hydronephrotic animals. © The Author(s) 2015.

Nitrogen-vacancy-assisted magnetometry of paramagnetic centers in an individual diamond nanocrystal.

PubMed

Laraoui, Abdelghani; Hodges, Jonathan S; Meriles, Carlos A

2012-07-11

Semiconductor nanoparticles host a number of paramagnetic point defects and impurities, many of them adjacent to the surface, whose response to external stimuli could help probe the complex dynamics of the particle and its local, nanoscale environment. Here, we use optically detected magnetic resonance in a nitrogen-vacancy (NV) center within an individual diamond nanocrystal to investigate the composition and spin dynamics of the particle-hosted spin bath. For the present sample, a ∼45 nm diamond crystal, NV-assisted dark-spin spectroscopy reveals the presence of nitrogen donors and a second, yet-unidentified class of paramagnetic centers. Both groups share a common spin lifetime considerably shorter than that observed for the NV spin, suggesting some form of spatial clustering, possibly on the nanoparticle surface. Using double spin resonance and dynamical decoupling, we also demonstrate control of the combined NV center-spin bath dynamics and attain NV coherence lifetimes comparable to those reported for bulk, Type Ib samples. Extensions based on the experiments presented herein hold promise for applications in nanoscale magnetic sensing, biomedical labeling, and imaging.

Optimizing a dynamical decoupling protocol for solid-state electronic spin ensembles in diamond

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

Farfurnik, D.; Jarmola, A.; Pham, L. M.

2015-08-24

In this study, we demonstrate significant improvements of the spin coherence time of a dense ensemble of nitrogen-vacancy (NV) centers in diamond through optimized dynamical decoupling (DD). Cooling the sample down to 77 K suppresses longitudinal spin relaxation T 1 effects and DD microwave pulses are used to increase the transverse coherence time T 2 from ~0.7ms up to ~30ms. Furthermore, we extend previous work of single-axis (Carr-Purcell-Meiboom-Gill) DD towards the preservation of arbitrary spin states. Following a theoretical and experimental characterization of pulse and detuning errors, we compare the performance of various DD protocols. We also identify that themore » optimal control scheme for preserving an arbitrary spin state is a recursive protocol, the concatenated version of the XY8 pulse sequence. The improved spin coherence might have an immediate impact on improvements of the sensitivities of ac magnetometry. Moreover, the protocol can be used on denser diamond samples to increase coherence times up to NV-NV interaction time scales, a major step towards the creation of quantum collective NV spin states.« less

Effects of Continuous and Interval Training on Running Economy, Maximal Aerobic Speed and Gait Kinematics in Recreational Runners.

PubMed

González-Mohíno, Fernando; González-Ravé, José M; Juárez, Daniel; Fernández, Francisco A; Barragán Castellanos, Rubén; Newton, Robert U

2016-04-01

The purpose of this study was to evaluate the effects on running economy (RE), V[Combining Dot Above]O2max, maximal aerobic speed (MAS), and gait kinematics (step length [SL] and frequency, flight and contact time [CT]) in recreational athletes, with 2 different training methods, Interval and Continuous (CON). Eleven participants were randomly distributed in an interval training group (INT; n = 6) or CON training group (CON; n = 5). Interval training and CON performed 2 different training programs (95-110% and 70-75% of MAS, respectively), which consisted of 3 sessions per week during 6 weeks with the same external workload (%MAS × duration). An incremental test to exhaustion was performed to obtain V[Combining Dot Above]O2max, MAS, RE, and gait variables (high speed camera) before and after the training intervention. There was a significant improvement (p ≤ 0.05) in RE at 60 and 90% of MAS by the CON group; without changes in gait. The INT group significantly increased MAS and higher stride length at 80, 90, and 100% of MAS and lower CT at 100% of MAS. As expected, training adaptations are highly specific to the overload applied with CON producing improvements in RE at lower percentage of MAS whereas INT produces improvements in MAS. The significantly increased stride length and decreased CT for the INT group are an important outcome of favorable changes in running gait.

Epidemiological characteristics and methodological quality of meta-analyses on diabetes mellitus treatment: a systematic review.

PubMed

Wu, Xin Yin; Lam, Victor C K; Yu, Yue Feng; Ho, Robin S T; Feng, Ye; Wong, Charlene H L; Yip, Benjamin H K; Tsoi, Kelvin K F; Wong, Samuel Y S; Chung, Vincent C H

2016-11-01

Well-conducted meta-analyses (MAs) are considered as one of the best sources of clinical evidence for treatment decision. MA with methodological flaws may introduce bias and mislead evidence users. The aim of this study is to investigate the characteristics and methodological quality of MAs on diabetes mellitus (DM) treatments. Systematic review. Cochrane Database of Systematic Review and Database of Abstract of Reviews of Effects were searched for relevant MAs. Assessing methodological quality of systematic reviews (AMSTAR) tool was used to evaluate the methodological quality of included MAs. Logistic regression analysis was used to identify association between characteristics of MA and AMSTAR results. A total of 252 MAs including 4999 primary studies and 13,577,025 patients were included. Over half of the MAs (65.1%) only included type 2 DM patients and 160 MAs (63.5%) focused on pharmacological treatments. About 89.7% MAs performed comprehensive literature search and 89.3% provided characteristics of included studies. Included MAs generally had poor performance on the remaining AMSTAR items, especially in assessing publication bias (39.3%), providing lists of studies (19.0%) and declaring source of support comprehensively (7.5%). Only 62.7% MAs mentioned about harm of interventions. MAs with corresponding author from Asia performed less well in providing MA protocol than those from Europe. Methodological quality of MA on DM treatments was unsatisfactory. There is considerable room for improvement, especially in assessing publication bias, providing lists of studies and declaring source of support comprehensively. Also, there is an urgent need for MA authors to report treatment harm comprehensively. © 2016 European Society of Endocrinology.

The Mini-Social Phobia Inventory: psychometric properties in an adolescent general population sample.

PubMed

Ranta, Klaus; Kaltiala-Heino, Riittakerttu; Rantanen, Päivi; Marttunen, Mauri

2012-07-01

Onset of social phobia (SP) typically occurs in adolescence. Short screening instruments for its assessment are needed for use in primary health and school settings. The 3-item Mini-Social Phobia Inventory (SPIN) has demonstrated effectiveness in screening for generalized SP (GSP) in adults. This study examined the psychometrics of the Mini-SPIN in an adolescent general population sample. Three hundred fifty adolescents aged 12 to 17 years were clinically interviewed using the Schedule for Affective Disorders and Schizophrenia for School-Age Children-Present and Lifetime Version for identification of SP and other Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, Axis I disorders, blind to their Mini-SPIN status. Associations between SP; subclinical SP; other anxiety, depressive, and disruptive disorders; and Mini-SPIN scores were examined, and diagnostic efficiency statistics were calculated. The association between Mini-SPIN scores and the generalized subtype of SP was also examined. As in adults, the Mini-SPIN items differentiated subjects with SP from those without. A score of 6 points or greater was found optimal in predicting SP with a sensitivity of 86%, specificity of 84%, and positive and negative predictive values of 26% and 99%. The Mini-SPIN also possessed discriminative validity, as scores were higher for adolescents with SP than they were for those with depressive, disruptive, and other anxiety disorders. The Mini-SPIN was also able to differentiate adolescents with GSP from the rest of the sample. The Mini-SPIN has good psychometrics for screening SP in adolescents from general population and may have value in screening for GSP. Copyright © 2012 Elsevier Inc. All rights reserved.

2016 Classification Criteria for Macrophage Activation Syndrome Complicating Systemic Juvenile Idiopathic Arthritis: A European League Against Rheumatism/American College of Rheumatology/Paediatric Rheumatology International Trials Organisation Collaborative Initiative.

PubMed

Ravelli, Angelo; Minoia, Francesca; Davì, Sergio; Horne, AnnaCarin; Bovis, Francesca; Pistorio, Angela; Aricò, Maurizio; Avcin, Tadej; Behrens, Edward M; De Benedetti, Fabrizio; Filipovic, Lisa; Grom, Alexei A; Henter, Jan-Inge; Ilowite, Norman T; Jordan, Michael B; Khubchandani, Raju; Kitoh, Toshiyuki; Lehmberg, Kai; Lovell, Daniel J; Miettunen, Paivi; Nichols, Kim E; Ozen, Seza; Pachlopnik Schmid, Jana; Ramanan, Athimalaipet V; Russo, Ricardo; Schneider, Rayfel; Sterba, Gary; Uziel, Yosef; Wallace, Carol; Wouters, Carine; Wulffraat, Nico; Demirkaya, Erkan; Brunner, Hermine I; Martini, Alberto; Ruperto, Nicolino; Cron, Randy Q

2016-03-01

To develop criteria for the classification of macrophage activation syndrome (MAS) in patients with systemic juvenile idiopathic arthritis (JIA). A multistep process, based on a combination of expert consensus and analysis of real patient data, was conducted. A panel of 28 experts was first asked to classify 428 patient profiles as having or not having MAS, based on clinical and laboratory features at the time of disease onset. The 428 profiles comprised 161 patients with systemic JIA-associated MAS and 267 patients with a condition that could potentially be confused with MAS (active systemic JIA without evidence of MAS, or systemic infection). Next, the ability of candidate criteria to classify individual patients as having MAS or not having MAS was assessed by evaluating the agreement between the classification yielded using the criteria and the consensus classification of the experts. The final criteria were selected in a consensus conference. Experts achieved consensus on the classification of 391 of the 428 patient profiles (91.4%). A total of 982 candidate criteria were tested statistically. The 37 best-performing criteria and 8 criteria obtained from the literature were evaluated at the consensus conference. During the conference, 82% consensus among experts was reached on the final MAS classification criteria. In validation analyses, these criteria had a sensitivity of 0.73 and a specificity of 0.99. Agreement between the classification (MAS or not MAS) obtained using the criteria and the original diagnosis made by the treating physician was high (κ = 0.76). We have developed a set of classification criteria for MAS complicating systemic JIA and provided preliminary evidence of its validity. Use of these criteria will potentially improve understanding of MAS in systemic JIA and enhance efforts to discover effective therapies, by ensuring appropriate patient enrollment in studies. © 2015, American College of Rheumatology.

Macrophage activation syndrome in children with systemic juvenile idiopathic arthritis and systemic lupus erythematosus.

PubMed

Aytaç, Selin; Batu, Ezgi Deniz; Ünal, Şule; Bilginer, Yelda; Çetin, Mualla; Tuncer, Murat; Gümrük, Fatma; Özen, Seza

2016-10-01

Macrophage activation syndrome (MAS) is a hyper-inflammatory disorder secondary to a rheumatic disease such as systemic juvenile idiopathic arthritis (SJIA) and systemic lupus erythematosus (SLE). We aimed to present the characteristics of our pediatric MAS patients. Clinical features, laboratory parameters, treatment, and outcome of 34 patients (28 SJIA; six SLE; 37 MAS episodes) followed at a tertiary health center between 2009 and 2015 were retrospectively reviewed. The median age at MAS onset was 11 years. More SJIA patients had MAS at disease onset than SLE patients (53.6 vs. 16.7 %). Fever, high C-reactive protein and hyperferritinemia were present in all MAS episodes. Rash was less (p = 0.03), and fatigue was more frequent (p = 0.042) in SLE than SJIA patients. All received corticosteroids. Cyclosporine was given in 74.2 % of SJIA-MAS; 66.7 % of SLE-MAS episodes. Intravenous immunoglobulin, anakinra, or etoposide was administered during 67.7; 41.9; 32.3 % of SJIA-MAS and 33.3; 33.3; 50 % of SLE-MAS episodes, respectively. Plasmapheresis was performed during 41.9 % of SJIA-MAS and 33.3 % of SLE-MAS episodes. The mortality rate was 11.8 % (n = 4;3 SJIA, 1 SLE). Hepatosplenomegaly was more frequent (p = 0.005), and plasmapheresis was performed more frequently (p = 0.021) in the patients who died compared to the cured patients. The median duration between symptom onset and admission to our hospital was longer among the patients who died (16.5 vs. 7 days; p = 0.049). Our patients' characteristics were similar to the reported cases, but our mortality rate is slightly higher probably due to late referral to our center. Early diagnosis and effective treatment are crucial to prevent mortality.

Low dose dynamic myocardial CT perfusion using advanced iterative reconstruction

NASA Astrophysics Data System (ADS)

Eck, Brendan L.; Fahmi, Rachid; Fuqua, Christopher; Vembar, Mani; Dhanantwari, Amar; Bezerra, Hiram G.; Wilson, David L.

2015-03-01

Dynamic myocardial CT perfusion (CTP) can provide quantitative functional information for the assessment of coronary artery disease. However, x-ray dose in dynamic CTP is high, typically from 10mSv to >20mSv. We compared the dose reduction potential of advanced iterative reconstruction, Iterative Model Reconstruction (IMR, Philips Healthcare, Cleveland, Ohio) to hybrid iterative reconstruction (iDose4) and filtered back projection (FBP). Dynamic CTP scans were obtained using a porcine model with balloon-induced ischemia in the left anterior descending coronary artery to prescribed fractional flow reserve values. High dose dynamic CTP scans were acquired at 100kVp/100mAs with effective dose of 23mSv. Low dose scans at 75mAs, 50mAs, and 25mAs were simulated by adding x-ray quantum noise and detector electronic noise to the projection space data. Images were reconstructed with FBP, iDose4, and IMR at each dose level. Image quality in static CTP images was assessed by SNR and CNR. Blood flow was obtained using a dynamic CTP analysis pipeline and blood flow image quality was assessed using flow-SNR and flow-CNR. IMR showed highest static image quality according to SNR and CNR. Blood flow in FBP was increasingly over-estimated at reduced dose. Flow was more consistent for iDose4 from 100mAs to 50mAs, but was over-estimated at 25mAs. IMR was most consistent from 100mAs to 25mAs. Static images and flow maps for 100mAs FBP, 50mAs iDose4, and 25mAs IMR showed comparable, clear ischemia, CNR, and flow-CNR values. These results suggest that IMR can enable dynamic CTP at significantly reduced dose, at 5.8mSv or 25% of the comparable 23mSv FBP protocol.

The CTFA Evaluation of Alternatives Program: an evaluation of in vitro alternatives to the Draize primary eye irritation test. (Phase III) surfactant-based formulations.

PubMed

Gettings, S D; Lordo, R A; Hintze, K L; Bagley, D M; Casterton, P L; Chudkowski, M; Curren, R D; Demetrulias, J L; Dipasquale, L C; Earl, L K; Feder, P I; Galli, C L; Glaza, S M; Gordon, V C; Janus, J; Kurtz, P J; Marenus, K D; Moral, J; Pape, W J; Renskers, K J; Rheins, L A; Roddy, M T; Rozen, M G; Tedeschi, J P; Zyracki, J

1996-01-01

The CTFA Evaluation of Alternatives Program is an evaluation of the relationship between data from the Draize primary eye irritation test and comparable data from a selection of promising in vitro eye irritation tests. In Phase III, data from the Draize test and 41 in vitro endpoints on 25 representative surfactant-based personal care formulations were compared. As in Phase I and Phase II, regression modelling of the relationship between maximum average Draize score (MAS) and in vitro endpoint was the primary approach adopted for evaluating in vitro assay performance. The degree of confidence in prediction of MAS for a given in vitro endpoint is quantified in terms of the relative widths of prediction intervals constructed about the fitted regression curve. Prediction intervals reflect not only the error attributed to the model but also the material-specific components of variation in both the Draize and the in vitro assays. Among the in vitro assays selected for regression modeling in Phase III, the relationship between MAS and in vitro score was relatively well defined. The prediction bounds on MAS were most narrow for materials at the lower or upper end of the effective irritation range (MAS = 0-45), where variability in MAS was smallest. This, the confidence with which the MAS of surfactant-based formulations is predicted is greatest when MAS approaches zero or when MAS approaches 45 (no comment is made on prediction of MAS > 45 since extrapolation beyond the range of observed data is not possible). No single in vitro endpoint was found to exhibit relative superiority with regard to prediction of MAS. Variability associated with Draize test outcome (e.g. in MAS values) must be considered in any future comparisons of in vivo and in vitro test results if the purpose is to predict in vivo response using in vitro data.

Radiation dose reduction in soft tissue neck CT using adaptive statistical iterative reconstruction (ASIR).

PubMed

Vachha, Behroze; Brodoefel, Harald; Wilcox, Carol; Hackney, David B; Moonis, Gul

2013-12-01

To compare objective and subjective image quality in neck CT images acquired at different tube current-time products (275 mAs and 340 mAs) and reconstructed with filtered-back-projection (FBP) and adaptive statistical iterative reconstruction (ASIR). HIPAA-compliant study with IRB approval and waiver of informed consent. 66 consecutive patients were randomly assigned to undergo contrast-enhanced neck CT at a standard tube-current-time-product (340 mAs; n = 33) or reduced tube-current-time-product (275 mAs, n = 33). Data sets were reconstructed with FBP and 2 levels (30%, 40%) of ASIR-FBP blending at 340 mAs and 275 mAs. Two neuroradiologists assessed subjective image quality in a blinded and randomized manner. Volume CT dose index (CTDIvol), dose-length-product (DLP), effective dose, and objective image noise were recorded. Signal-to-noise ratio (SNR) was computed as mean attenuation in a region of interest in the sternocleidomastoid muscle divided by image noise. Compared with FBP, ASIR resulted in a reduction of image noise at both 340 mAs and 275 mAs. Reduction of tube current from 340 mAs to 275 mAs resulted in an increase in mean objective image noise (p=0.02) and a decrease in SNR (p = 0.03) when images were reconstructed with FBP. However, when the 275 mAs images were reconstructed using ASIR, the mean objective image noise and SNR were similar to those of the standard 340 mAs CT images reconstructed with FBP (p>0.05). Subjective image noise was ranked by both raters as either average or less-than-average irrespective of the tube current and iterative reconstruction technique. Adapting ASIR into neck CT protocols reduced effective dose by 17% without compromising image quality. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Role of the antiferromagnetic pinning layer on spin wave properties in IrMn/NiFe based spin-valves

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

Gubbiotti, G., E-mail: gubbiotti@fisica.unipg.it; Tacchi, S.; Del Bianco, L.

2015-05-07

Brillouin light scattering (BLS) was exploited to study the spin wave properties of spin-valve (SV) type samples basically consisting of two 5 nm-thick NiFe layers (separated by a Cu spacer of 5 nm), differently biased through the interface exchange coupling with an antiferromagnetic IrMn layer. Three samples were investigated: a reference SV sample, without IrMn (reference); one sample with an IrMn underlayer (10 nm thick) coupled to the bottom NiFe film; one sample with IrMn underlayer and overlayer of different thickness (10 nm and 6 nm), coupled to the bottom and top NiFe film, respectively. The exchange coupling with the IrMn, causing the insurgence ofmore » the exchange bias effect, allowed the relative orientation of the NiFe magnetization vectors to be controlled by an external magnetic field, as assessed through hysteresis loop measurements by magneto-optic magnetometry. Thus, BLS spectra were acquired by sweeping the magnetic field so as to encompass both the parallel and antiparallel alignment of the NiFe layers. The BLS results, well reproduced by the presented theoretical model, clearly revealed the combined effects on the spin dynamic properties of the dipolar interaction between the two NiFe films and of the interface IrMn/NiFe exchange coupling.« less

New Roles for Medical Assistants in Innovative Primary Care Practices.

PubMed

Chapman, Susan A; Blash, Lisel K

2017-02-01

To identify and describe new roles for medical assistants (MAs) in innovative care models that improve care while providing training and career advancement opportunities for MAs. Primary data collected at 15 case study sites; 173 key informant interviews and de-identified secondary data on staffing, wages, patient satisfaction, and health outcomes. Researchers used snowball sampling and screening calls to identify 15 organizations using MAs in new roles. Conducted site visits from 2010 to 2012 and updated information in 2014. Thematic analysis explored key topics: factors driving MA role innovation, role description, training required, and wage gains. Categorized outcome data in patient and staff satisfaction, quality of care, and efficiency. New MA roles included health coach, medical scribe, dual role translator, health navigator, panel manager, cross-trained flexible role, and supervisor. Implementation of new roles required extensive training. MA incentives and enhanced compensation varied by role type. New MA roles are part of a larger attempt to reform workflow and relieve primary care providers. Despite some evidence of success, spread has been limited. Key challenges to adoption included leadership and provider resistance to change, cost of additional MA training, and lack of reimbursement for nonbillable services. © Health Research and Educational Trust.

Probing atomic scale transformation of fossil dental enamel using Fourier transform infrared and nuclear magnetic resonance spectroscopy: a case study from the Tugen Hills (Rift Gregory, Kenya).

PubMed

Yi, Haohao; Balan, Etienne; Gervais, Christel; Ségalen, Loïc; Roche, Damien; Person, Alain; Fayon, Franck; Morin, Guillaume; Babonneau, Florence

2014-09-01

A series of fossil tooth enamel samples was investigated by Fourier transform infrared (FTIR) spectroscopy, (13)C and (19)F magic-angle spinning nuclear magnetic resonance (MAS NMR) and scanning electron microscopy (SEM). Tooth remains were collected in Mio-Pliocene deposits of the Tugen Hills in Kenya. Significant transformations were observed in fossil enamel as a function of increasing fluorine content (up to 2.8wt.%). FTIR spectroscopy revealed a shift of the ν1 PO4 stretching band to higher frequency. The ν2 CO3 vibrational band showed a decrease in the intensity of the primary B-type carbonate signal, which was replaced by a specific band at 864cm(-1). This last band was ascribed to a specific carbonate environment in which the carbonate group is closely associated to a fluoride ion. The occurrence of this carbonate defect was consistently attested by the observation of two different fluoride signals in the (19)F NMR spectra. One main signal, at ∼-100ppm, is related to structural F ions in the apatite channel and the other, at -88ppm, corresponds to the composite defect. These spectroscopic observations can be understood as resulting from the mixture of two phases: biogenic hydroxylapatite (bioapatite) and secondary fluorapatite. SEM observations of the most altered sample confirmed the extensive replacement of the bioapatite by fluorapatite, resulting from the dissolution of the primary bioapatite followed by the precipitation of carbonate-fluorapatite. The ν2 CO3 IR bands can be efficiently used to monitor the extent of this type of bioapatite transformation during fossilization. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02709a Click here for additional data file.

PubMed Central

Märker, Katharina; Paul, Subhradip; Fernández-de-Alba, Carlos; Lee, Daniel; Mouesca, Jean-Marie; Hediger, Sabine

2017-01-01

The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13C at its natural isotopic abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to ∼7 Å, allowing us to observe π-stacking through 13C–13C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra- and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR. PMID:28451235

Antisite disorder induced spin glass and exchange bias effect in Nd2NiMnO6 epitaxial thin film

NASA Astrophysics Data System (ADS)

Singh, Amit Kumar; Chauhan, Samta; Chandra, Ramesh

2017-03-01

We report the observation of the exchange bias effect and spin glass behaviour at low temperature in a ferromagnetic Nd2NiMnO6 epitaxial thin film. Along with the ferromagnetic transition at ˜194 K, an additional transition is observed at lower temperature (˜55 K) as seen from M-T curves of the sample. A shift in the ac susceptibility peak with frequency has been observed at low temperature, which is a signature of a glassy phase within the sample. The detailed investigation of the memory effect and time dependent magnetic relaxation measurements reveals the presence of a spin glass phase in the Nd2NiMnO6 thin film. The exchange bias effect observed at low temperature in the sample has been associated with an antisite disorder induced spin glass phase, which results in a ferromagnetic/spin glass interface at low temperature. The exchange bias behaviour has been further confirmed by performing cooling field and temperature dependence of exchange bias along with training effect measurements.

Quantum memory enhanced nuclear magnetic resonance of nanometer-scale samples with a single spin in diamond

NASA Astrophysics Data System (ADS)

Aslam, Nabeel; Pfender, Matthias; Zaiser, Sebastian; Favaro de Oliveira, Felipe; Momenzadeh, S. Ali; Denisenko, Andrej; Isoya, Junichi; Neumann, Philipp; Wrachtrup, Joerg

Recently nuclear magnetic resonance (NMR) of nanoscale samples at ambient conditions has been achieved with nitrogen-vacancy (NV) centers in diamond. So far the spectral resolution in the NV NMR experiments was limited by the sensor's coherence time, which in turn prohibited revealing the chemical composition and dynamics of the system under investigation. By entangling the NV electron spin sensor with a long-lived memory spin qubit we increase the spectral resolution of NMR measurement sequences for the detection of external nuclear spins. Applying the latter sensor-memory-couple it is particularly easy to track diffusion processes, to identify the molecules under study and to deduce the actual NV center depth inside the diamond. We performed nanoscale NMR on several liquid and solid samples exhibiting unique NMR response. Our method paves the way for nanoscale identification of molecule and protein structures and dynamics of conformational changes.

Spin-wave resonances and surface spin pinning in Ga1-xMnxAs thin films

NASA Astrophysics Data System (ADS)

Bihler, C.; Schoch, W.; Limmer, W.; Goennenwein, S. T. B.; Brandt, M. S.

2009-01-01

We investigate the dependence of the spin-wave resonance (SWR) spectra of Ga0.95Mn0.05As thin films on the sample treatment. We find that for the external magnetic field perpendicular to the film plane, the SWR spectrum of the as-grown thin films and the changes upon etching and short-term hydrogenation can be quantitatively explained via a linear gradient in the uniaxial magnetic anisotropy field in growth direction. The model also qualitatively explains the SWR spectra observed for the in-plane easy-axis orientation of the external magnetic field. Furthermore, we observe a change in the effective surface spin pinning of the partially hydrogenated sample, which results from the tail in the hydrogen-diffusion profile. The latter leads to a rapidly changing hole concentration/magnetic anisotropy profile acting as a barrier for the spin-wave excitations. Therefore, short-term hydrogenation constitutes a simple method to efficiently manipulate the surface spin pinning.

A Magic-Angle Spinning NMR Method for the Site-Specific Measurement of Proton Chemical-Shift Anisotropy in Biological and Organic Solids.

PubMed

Hou, Guangjin; Gupta, Rupal; Polenova, Tatyana; Vega, Alexander J

2014-02-01

Proton chemical shifts are a rich probe of structure and hydrogen bonding environments in organic and biological molecules. Until recently, measurements of 1 H chemical shift tensors have been restricted to either solid systems with sparse proton sites or were based on the indirect determination of anisotropic tensor components from cross-relaxation and liquid-crystal experiments. We have introduced an MAS approach that permits site-resolved determination of CSA tensors of protons forming chemical bonds with labeled spin-1/2 nuclei in fully protonated solids with multiple sites, including organic molecules and proteins. This approach, originally introduced for the measurements of chemical shift tensors of amide protons, is based on three RN -symmetry based experiments, from which the principal components of the 1 H CS tensor can be reliably extracted by simultaneous triple fit of the data. In this article, we expand our approach to a much more challenging system involving aliphatic and aromatic protons. We start with a review of the prior work on experimental-NMR and computational-quantum-chemical approaches for the measurements of 1 H chemical shift tensors and for relating these to the electronic structures. We then present our experimental results on U- 13 C, 15 N-labeled histdine demonstrating that 1 H chemical shift tensors can be reliably determined for the 1 H 15 N and 1 H 13 C spin pairs in cationic and neutral forms of histidine. Finally, we demonstrate that the experimental 1 H(C) and 1 H(N) chemical shift tensors are in agreement with Density Functional Theory calculations, therefore establishing the usefulness of our method for characterization of structure and hydrogen bonding environment in organic and biological solids.

Structural changes of TasA in biofilm formation of Bacillus subtilis.

PubMed

Diehl, Anne; Roske, Yvette; Ball, Linda; Chowdhury, Anup; Hiller, Matthias; Molière, Noel; Kramer, Regina; Stöppler, Daniel; Worth, Catherine L; Schlegel, Brigitte; Leidert, Martina; Cremer, Nils; Erdmann, Natalja; Lopez, Daniel; Stephanowitz, Heike; Krause, Eberhard; van Rossum, Barth-Jan; Schmieder, Peter; Heinemann, Udo; Turgay, Kürşad; Akbey, Ümit; Oschkinat, Hartmut

2018-03-27

Microorganisms form surface-attached communities, termed biofilms, which can serve as protection against host immune reactions or antibiotics. Bacillus subtilis biofilms contain TasA as major proteinaceous component in addition to exopolysaccharides. In stark contrast to the initially unfolded biofilm proteins of other bacteria, TasA is a soluble, stably folded monomer, whose structure we have determined by X-ray crystallography. Subsequently, we characterized in vitro different oligomeric forms of TasA by NMR, EM, X-ray diffraction, and analytical ultracentrifugation (AUC) experiments. However, by magic-angle spinning (MAS) NMR on live biofilms, a swift structural change toward only one of these forms, consisting of homogeneous and protease-resistant, β-sheet-rich fibrils, was observed in vivo. Thereby, we characterize a structural change from a globular state to a fibrillar form in a functional prokaryotic system on the molecular level. Copyright © 2018 the Author(s). Published by PNAS.

Structural changes of TasA in biofilm formation of Bacillus subtilis

PubMed Central

Diehl, Anne; Roske, Yvette; Ball, Linda; Chowdhury, Anup; Hiller, Matthias; Molière, Noel; Kramer, Regina; Stöppler, Daniel; Worth, Catherine L.; Schlegel, Brigitte; Leidert, Martina; Cremer, Nils; Erdmann, Natalja; Lopez, Daniel; Stephanowitz, Heike; Krause, Eberhard; Schmieder, Peter; Akbey, Ümit; Oschkinat, Hartmut

2018-01-01

Microorganisms form surface-attached communities, termed biofilms, which can serve as protection against host immune reactions or antibiotics. Bacillus subtilis biofilms contain TasA as major proteinaceous component in addition to exopolysaccharides. In stark contrast to the initially unfolded biofilm proteins of other bacteria, TasA is a soluble, stably folded monomer, whose structure we have determined by X-ray crystallography. Subsequently, we characterized in vitro different oligomeric forms of TasA by NMR, EM, X-ray diffraction, and analytical ultracentrifugation (AUC) experiments. However, by magic-angle spinning (MAS) NMR on live biofilms, a swift structural change toward only one of these forms, consisting of homogeneous and protease-resistant, β-sheet–rich fibrils, was observed in vivo. Thereby, we characterize a structural change from a globular state to a fibrillar form in a functional prokaryotic system on the molecular level. PMID:29531041

Supramolecular Amino Acid Based Hydrogels: Probing the Contribution of Additive Molecules using NMR Spectroscopy

PubMed Central

Ramalhete, Susana M.; Nartowski, Karol P.; Sarathchandra, Nichola; Foster, Jamie S.; Round, Andrew N.; Angulo, Jesús

2017-01-01

Abstract Supramolecular hydrogels are composed of self‐assembled solid networks that restrict the flow of water. l‐Phenylalanine is the smallest molecule reported to date to form gel networks in water, and it is of particular interest due to its crystalline gel state. Single and multi‐component hydrogels of l‐phenylalanine are used herein as model materials to develop an NMR‐based analytical approach to gain insight into the mechanisms of supramolecular gelation. Structure and composition of the gel fibres were probed using PXRD, solid‐state NMR experiments and microscopic techniques. Solution‐state NMR studies probed the properties of free gelator molecules in an equilibrium with bound molecules. The dynamics of exchange at the gel/solution interfaces was investigated further using high‐resolution magic angle spinning (HR‐MAS) and saturation transfer difference (STD) NMR experiments. This approach allowed the identification of which additive molecules contributed in modifying the material properties. PMID:28401991

Sodium Copper Chlorophyllin Immobilization onto Hippospongia communis Marine Demosponge Skeleton and Its Antibacterial Activity

PubMed Central

Norman, Małgorzata; Bartczak, Przemysław; Zdarta, Jakub; Tomala, Wiktor; Żurańska, Barbara; Dobrowolska, Anna; Piasecki, Adam; Czaczyk, Katarzyna; Ehrlich, Hermann; Jesionowski, Teofil

2016-01-01

In this study, Hippospongia communis marine demosponge skeleton was used as an adsorbent for sodium copper chlorophyllin (SCC). Obtained results indicate the high sorption capacity of this biomaterial with respect to SCC. Batch experiments were performed under different conditions and kinetic and isotherms properties were investigated. Acidic pH and the addition of sodium chloride increased SCC adsorption. The experimental data were well described by a pseudo-second order kinetic model. Equilibrium adsorption isotherms were determined and the experimental data were analyzed using both Langmuir and Freundlich isotherms. The effectiveness of the process was confirmed by 13C Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (13C CP/MAS NMR), Fourier transform infrared spectroscopy (FTIR), energy-dispersive X-ray spectroscopy (EDS) and thermogravimetric analysis (TG). This novel SCC-sponge-based functional hybrid material was found to exhibit antimicrobial activity against the gram-positive bacterium Staphylococcus aureus. PMID:27690001

NMR Based Cerebrum Metabonomic Analysis Reveals Simultaneous Interconnected Changes during Chick Embryo Incubation.

PubMed

Feng, Yue; Zhu, Hang; Zhang, Xu; Wang, Xuxia; Xu, Fuqiang; Tang, Huiru; Ye, Chaohui; Liu, Maili

2015-01-01

To find out if content changes of the major functional cerebrum metabolites are interconnected and formed a network during the brain development, we obtained high-resolution magic-angle-spinning (HR-MAS) 1H NMR spectra of cerebrum tissues of chick embryo aged from incubation day 10 to 20, and postnatal day 1, and analyzed the data with principal component analysis (PCA). Within the examined time window, 26 biological important molecules were identified and 12 of them changed their relative concentration significantly in a time-dependent manner. These metabolites are generally belonged to three categories, neurotransmitters, nutrition sources, and neuronal or glial markers. The relative concentration changes of the metabolites were interconnected among/between the categories, and, more interestingly, associated with the number and size of Nissl-positive neurons. These results provided valuable biochemical and neurochemical information to understand the development of the embryonic brain.

NMR Based Cerebrum Metabonomic Analysis Reveals Simultaneous Interconnected Changes during Chick Embryo Incubation

PubMed Central

Feng, Yue; Zhu, Hang; Zhang, Xu; Wang, Xuxia; Xu, Fuqiang; Tang, Huiru; Ye, Chaohui; Liu, Maili

2015-01-01

To find out if content changes of the major functional cerebrum metabolites are interconnected and formed a network during the brain development, we obtained high-resolution magic-angle-spinning (HR-MAS) 1H NMR spectra of cerebrum tissues of chick embryo aged from incubation day 10 to 20, and postnatal day 1, and analyzed the data with principal component analysis (PCA). Within the examined time window, 26 biological important molecules were identified and 12 of them changed their relative concentration significantly in a time-dependent manner. These metabolites are generally belonged to three categories, neurotransmitters, nutrition sources, and neuronal or glial markers. The relative concentration changes of the metabolites were interconnected among/between the categories, and, more interestingly, associated with the number and size of Nissl-positive neurons. These results provided valuable biochemical and neurochemical information to understand the development of the embryonic brain. PMID:26485040

Competing exchange interactions in multiferroic and ferrimagnetic CaBaCo 4 O 7

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

Fishman, Randy Scott; Bordacs, S.; Kocsis, Vilmos

Competing exchange interactions can produce complex magnetic states together with spin-induced electric polarizations. With competing interactions on alternating triangular and kagome layers, the swedenborgite CaBaCo 4O 7 may have one of the largest measured spin-induced polarizations of ~1700 nC/cm 2 below its ferrimagnetic transition temperature at 70 K. Upon rotating our sample about c = [0,0,1] while the magnetic field is fixed along [1,0,0], the threefold splitting of the spin-wave frequencies indicates that our sample is hexagonally twinned. In addition, magnetization measurements then suggest that roughly 20% of the sample is in a domain with the a axis along [1,0,0]more » and that 80% of the sample is in one of two other domains with the a axis along either [-1/2,√3/2, 0] or [-1/2, -√3/2, 0] . Powder neutron-diffraction data, magnetization measurements, and terahertz (THz) absorption spectroscopy reveal that the complex spin order in each domain can be described as a triangular array of bitetrahedral c-axis chains ferrimagnetically coupled to each other in the ab plane. In conclusion, the electric-field dependence of bonds coupling those chains produces the large spin-induced polarization of CaBaCo 4O 7 .« less

Competing exchange interactions in multiferroic and ferrimagnetic CaBaCo 4 O 7

DOE PAGES

Fishman, Randy Scott; Bordacs, S.; Kocsis, Vilmos; ...

2017-01-23

Competing exchange interactions can produce complex magnetic states together with spin-induced electric polarizations. With competing interactions on alternating triangular and kagome layers, the swedenborgite CaBaCo 4O 7 may have one of the largest measured spin-induced polarizations of ~1700 nC/cm 2 below its ferrimagnetic transition temperature at 70 K. Upon rotating our sample about c = [0,0,1] while the magnetic field is fixed along [1,0,0], the threefold splitting of the spin-wave frequencies indicates that our sample is hexagonally twinned. In addition, magnetization measurements then suggest that roughly 20% of the sample is in a domain with the a axis along [1,0,0]more » and that 80% of the sample is in one of two other domains with the a axis along either [-1/2,√3/2, 0] or [-1/2, -√3/2, 0] . Powder neutron-diffraction data, magnetization measurements, and terahertz (THz) absorption spectroscopy reveal that the complex spin order in each domain can be described as a triangular array of bitetrahedral c-axis chains ferrimagnetically coupled to each other in the ab plane. In conclusion, the electric-field dependence of bonds coupling those chains produces the large spin-induced polarization of CaBaCo 4O 7 .« less

Combined use of EPR and 23Na MAS NMR spectroscopy for assessing the properties of the mixed cobalt-nickel-manganese layers of P3-NayCo1-2xNixMnxO2.

PubMed

Kalapsazova, M; Ivanova, S; Kukeva, R; Simova, S; Wegner, S; Zhecheva, E; Stoyanova, R

2017-10-11

Knowledge on the formation of mixed transition metal layers on lithium and sodium transition metal oxides, Li/Na(Co,Ni,Mn,)O 2 , determines the ability to control their electrochemical properties as electrode materials in alkaline ion batteries. Taking this into account, herein we combine the EPR and 23 Na MAS NMR spectroscopic techniques to gain insights into the structural peculiarities of the mixed cobalt-nickel-manganese layers of Na y Co 1-2x Ni x Mn x O 2 with a three-layer stacking (P3-type) structure. Two types of compositions are examined where diamagnetic Co 3+ and paramagnetic Ni 3+ and Mn 4+ are stabilized: Na 2/3 Co 1/3 Ni 1/3 Mn 1/3 O 2 and Na 1/2 Ni 1/2 Mn 1/2 O 2 . EPR spectroscopy operating in the X- and Q-band region is applied with an aim to improve the spectra resolution and, on the other hand, to provide straightforward information on the coordination of the transition metal ions inside the layers. The analysis of EPR spectra is based on the reference for the Mn 4+ and Ni 2+ ions occurring simultaneously in oxides with two layer stacking, P2-Na 2/3 Ni 1/3 Mn 2/3 O 2 . Complementary to EPR, 23 Na MAS NMR spectroscopy at high spinning rates is undertaken to assess the local structure of the Na nucleus in the layered P3-Na y Co 1-2x Ni x Mn x O 2 oxides. All results are discussed taking into account the EPR and NMR data for the well-known lithium analogues O3-LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and O3-LiNi 1/2 Mn 1/2 O 2 . Finally, the structure peculiarities of the transition metal layers extracted from the EPR and NMR methods are demonstrated by electrochemical intercalation of Li + ions into P3-Na y Co 1-2x Ni x Mn x O 2 .

CP/MAS 13C NMR characterization of the isomeric states and intermolecular packing in tris(8-hydroxyquinoline) aluminum(III) (Alq3).

PubMed

Kaji, Hironori; Kusaka, Yasunari; Onoyama, Goro; Horii, Fumitaka

2006-04-05

The isomeric states and intermolecular packing of tris(8-hydroxyquinoline) aluminum(III) (Alq(3)) in the alpha-, gamma-, and delta-crystalline forms and in the amorphous state, which are important for understanding the light-emitting and electron-transport properties, have been analyzed by CP/MAS (13)C NMR. This simple NMR experiment shows that the isomeric state of alpha- and amorphous Alq(3) is meridional, whereas that of gamma- and delta-Alq(3) is facial. In the amorphous Alq(3), the inclusion of facial isomers has been under debate. Our experiments show that meridional isomers are dominant in the amorphous Alq(3), although the existence of facial isomers cannot be completely denied. The local structure of amorphous Alq(3) is similar to that of alpha-Alq(3) and is significantly different from those of gamma- and delta-Alq(3). Among these Alq(3) samples, the effect of intermolecular interaction is not found only for gamma-Alq(3). This finding can explain the good solvent solubility of gamma-Alq(3), compared with the other crystalline forms. It is also shown that the structures are locally disordered not only for amorphous Alq(3) but also for alpha-Alq(3), although clear X-ray diffraction peaks are observed for alpha-Alq(3). In contrast, the local structures of gamma- and delta-Alq(3) are well defined. A clear relation is found between the spectral patterns of CP/MAS (13)C NMR and the fluorescence wavelengths; the samples, which consist of facial isomers, show blue-shifted fluorescence compared with those of meridionals.

Quasiparticle spin resonance and coherence in superconducting aluminium.

PubMed

Quay, C H L; Weideneder, M; Chiffaudel, Y; Strunk, C; Aprili, M

2015-10-26

Conventional superconductors were long thought to be spin inert; however, there is now increasing interest in both (the manipulation of) the internal spin structure of the ground-state condensate, as well as recently observed long-lived, spin-polarized excitations (quasiparticles). We demonstrate spin resonance in the quasiparticle population of a mesoscopic superconductor (aluminium) using novel on-chip microwave detection techniques. The spin decoherence time obtained (∼100 ps), and its dependence on the sample thickness are consistent with Elliott-Yafet spin-orbit scattering as the main decoherence mechanism. The striking divergence between the spin coherence time and the previously measured spin imbalance relaxation time (∼10 ns) suggests that the latter is limited instead by inelastic processes. This work stakes out new ground for the nascent field of spin-based electronics with superconductors or superconducting spintronics.

Spin-current probe for phase transition in an insulator

DOE PAGES

Qiu, Zhiyong; Li, Jia; Hou, Dazhi; ...

2016-08-30

Spin fluctuation and transition have always been one of the central topics of magnetism and condensed matter science. Experimentally, the spin fluctuation is found transcribed onto scattering intensity in the neutron-scattering process, which is represented by dynamical magnetic susceptibility and maximized at phase transitions. Importantly, a neutron carries spin without electric charge, and therefore it can bring spin into a sample without being disturbed by electric energy. However, large facilities such as a nuclear reactor are necessary. Here we present that spin pumping, frequently used in nanoscale spintronic devices, provides a desktop microprobe for spin transition; spin current is amore » flux of spin without an electric charge and its transport reflects spin excitation. Additionally, we demonstrate detection of antiferromagnetic transition in ultra-thin CoO films via frequency-dependent spin-current transmission measurements, which provides a versatile probe for phase transition in an electric manner in minute devices.« less

Examining brain structures associated with the motive to achieve success and the motive to avoid failure: A voxel-based morphometry study.

PubMed

Ming, Dan; Chen, Qunlin; Yang, Wenjing; Chen, Rui; Wei, Dongtao; Li, Wenfu; Qiu, Jiang; Xu, Zhan; Zhang, Qinglin

2016-01-01

The motive to achieve success (MAS) and motive to avoid failure (MAF) are two different but classical kinds of achievement motivation. Though many functional magnetic resonance imaging studies have explored functional activation in motivation-related conditions, research has been silent as to the brain structures associated with individual differences in achievement motivation, especially with respect to MAS and MAF. In this study, the voxel-based morphometry method was used to uncover focal differences in brain structures related to MAS and MAF measured by the Mehrabian Achieving Tendency Scale in 353 healthy young Chinese adults. The results showed that the brain structures associated with individual differences in MAS and MAF were distinct. MAS was negatively correlated with regional gray matter volume (rGMV) in the medial prefrontal cortex (mPFC)/orbitofrontal cortex while MAF was negatively correlated with rGMV in the mPFC/subgenual cingulate gyrus. After controlling for mutual influences of MAS and MAF scores, MAS scores were found to be related to rGMV in the mPFC/orbitofrontal cortex and another cluster containing the parahippocampal gyrus and precuneus. These results may predict that compared with MAF, the generation process of MAS may be more complex and rational, thus in the real world, perhaps MAS is more beneficial to personal growth and guaranteeing the quality of task performance.

Spin Hall effects in metallic antiferromagnets – perspectives for future spin-orbitronics

DOE PAGES

Sklenar, Joseph; Zhang, Wei; Jungfleisch, Matthias B.; ...

2016-03-07

In this paper, we investigate angular dependent spin-orbit torques from the spin Hall effect in a metallic antiferromagnet using the spin-torque ferromagnetic resonance technique. The large spin Hall effect exists in PtMn, a prototypical CuAu-I-type metallic antiferromagnet. By applying epitaxial growth, we previously reported an appreciable difference in spin-orbit torques for c- and a-axis orientated samples, implying anisotropic effects in magnetically ordered materials. In this work we demonstrate through bipolar-magnetic-field experiments a small but noticeable asymmetric behavior in the spin-transfer-torque that appears as a hysteresis effect. Finally, we also suggest that metallic antiferromagnets may be good candidates for the investigationmore » of various unidirectional effects related to novel spin-orbitronics phenomena.« less

The Gα o Activator Mastoparan-7 Promotes Dendritic Spine Formation in Hippocampal Neurons

PubMed Central

Ramírez, Valerie T.; Ramos-Fernández, Eva; Inestrosa, Nibaldo C.

2016-01-01

Mastoparan-7 (Mas-7), an analogue of the peptide mastoparan, which is derived from wasp venom, is a direct activator of Pertussis toxin- (PTX-) sensitive G proteins. Mas-7 produces several biological effects in different cell types; however, little is known about how Mas-7 influences mature hippocampal neurons. We examined the specific role of Mas-7 in the development of dendritic spines, the sites of excitatory synaptic contact that are crucial for synaptic plasticity. We report here that exposure of hippocampal neurons to a low dose of Mas-7 increases dendritic spine density and spine head width in a time-dependent manner. Additionally, Mas-7 enhances postsynaptic density protein-95 (PSD-95) clustering in neurites and activates Gα o signaling, increasing the intracellular Ca2+ concentration. To define the role of signaling intermediates, we measured the levels of phosphorylated protein kinase C (PKC), c-Jun N-terminal kinase (JNK), and calcium-calmodulin dependent protein kinase IIα (CaMKIIα) after Mas-7 treatment and determined that CaMKII activation is necessary for the Mas-7-dependent increase in dendritic spine density. Our results demonstrate a critical role for Gα o subunit signaling in the regulation of synapse formation. PMID:26881110

Measurements of eight early-type stars angular diameters using VEGA/CHARA interferometer

NASA Astrophysics Data System (ADS)

Challouf, M.; Nardetto, N.; Mourard, D.; Aroui, H.; Delaa, O.

2014-12-01

The surface brightness color (SBC) relation is an important tool to derive the distance of extragalatic eclipsing binaries. We determined the uniform disc angular diameter of the eight following early-type stars using VEGA/CHARA interferometric observations: θ_{UD}[δ Cyg] = 0.766 ± 0.047 mas, θ_{UD}[γ Lyr] = 0.742& ± 0.010 mas, θ_{UD}[γ Ori] = 0.701 ± 0.005 mas, θ_{UD}[ζ Peg] = 0.539 ± 0.009 mas, θ_{UD}[λ Aql] = 0.529 ± 0.003 mas, θ_{UD}[ζ Per] = 0.531 ± 0.007 mas, θ_{UD}[ι Her] = 0.304 ± 0.010 mas and θ_{UD}[8 Cyg] = 0.229 ± 0.011 mas (by extending V-K range from -0.76 to 0.02) with typical precision of about 1.5%. By combining these data with previous angular diameter determinations available in the literature, Challouf et al. (2014) provide for the very first time a SBC relation for early-type stars (-1≤V-K≤0) with a precision of about 0.16 magnitude or 7% in term of angular diameter (when using this SBC relation to derive the angular diameter of early-type stars).

The Gαo Activator Mastoparan-7 Promotes Dendritic Spine Formation in Hippocampal Neurons.

PubMed

Ramírez, Valerie T; Ramos-Fernández, Eva; Inestrosa, Nibaldo C

2016-01-01

Mastoparan-7 (Mas-7), an analogue of the peptide mastoparan, which is derived from wasp venom, is a direct activator of Pertussis toxin- (PTX-) sensitive G proteins. Mas-7 produces several biological effects in different cell types; however, little is known about how Mas-7 influences mature hippocampal neurons. We examined the specific role of Mas-7 in the development of dendritic spines, the sites of excitatory synaptic contact that are crucial for synaptic plasticity. We report here that exposure of hippocampal neurons to a low dose of Mas-7 increases dendritic spine density and spine head width in a time-dependent manner. Additionally, Mas-7 enhances postsynaptic density protein-95 (PSD-95) clustering in neurites and activates Gα(o) signaling, increasing the intracellular Ca(2+) concentration. To define the role of signaling intermediates, we measured the levels of phosphorylated protein kinase C (PKC), c-Jun N-terminal kinase (JNK), and calcium-calmodulin dependent protein kinase IIα (CaMKIIα) after Mas-7 treatment and determined that CaMKII activation is necessary for the Mas-7-dependent increase in dendritic spine density. Our results demonstrate a critical role for Gα(o) subunit signaling in the regulation of synapse formation.

Radio Measurements of the Stellar Proper Motions in the Core of the Orion Nebula Cluster

NASA Astrophysics Data System (ADS)

Dzib, Sergio A.; Loinard, Laurent; Rodríguez, Luis F.; Gómez, Laura; Forbrich, Jan; Menten, Karl M.; Kounkel, Marina A.; Mioduszewski, Amy J.; Hartmann, Lee; Tobin, John J.; Rivera, Juana L.

2017-01-01

Using multi-epoch Very Large Array observations, covering a time baseline of 29.1 years, we have measured the proper motions of 88 young stars with compact radio emission in the core of the Orion Nebula Cluster (ONC) and the neighboring BN/KL region. Our work increases the number of young stars with measured proper motion at radio frequencies by a factor of 2.5 and enables us to perform a better statistical analysis of the kinematics of the region than was previously possible. Most stars (79 out of 88) have proper motions consistent with a Gaussian distribution centered on \\overline{{μ }α \\cos δ }=1.07+/- 0.09 mas yr-1, and \\overline{{μ }δ }=-0.84+/- 0.16 mas yr-1, with velocity dispersions of {σ }α =1.08+/- 0.07 mas yr-1, {σ }δ =1.27+/- 0.15 mas yr-1. We looked for organized movements of these stars but found no clear indication of radial expansion/contraction or rotation. The remaining nine stars in our sample show peculiar proper motions that differ from the mean proper motions of the ONC by more than 3σ. One of these stars, V 1326 Ori, could have been expelled from the Orion Trapezium 7000 years ago. Two could be related to the multi-stellar disintegration in the BN/KL region, in addition to the previously known sources BN, I and n. The others either have high uncertainties (so their anomalous proper motions are not firmly established) or could be foreground objects.

Positive Effects of Extracorporeal Shock Wave Therapy on Spasticity in Poststroke Patients: A Meta-Analysis.

PubMed

Guo, Peipei; Gao, Fuqiang; Zhao, Tingting; Sun, Wei; Wang, Bailiang; Li, Zirong

2017-11-01

Spasticity is a common and serious complication following a stroke, and many clinical research have been conducted to evaluate the effect of extracorporeal shock wave therapy (ESWT) on muscle spasticity in poststroke patients. This meta-analysis aimed to evaluate the therapeutic effect on decreasing spasticity caused by a stroke immediately and 4 weeks after the application of shock wave therapy. We searched PubMed, Embase, Web of Science, and Cochrane Library databases for relevant studies through November 2016 using the following item: (Hypertonia OR Spasticity) and (Shock Wave or ESWT) and (Stroke). The outcomes were evaluated by Modified Ashworth Scale (MAS) grades and pooled by Stata 12.0 (Stata Corp, College Station, TX, USA). Six studies consisting of 9 groups were included in this meta-analysis. The MAS grades immediately after ESWT were significantly improved compared with the baseline values (standardized mean difference [SMD], -1.57; 95% confidence intervals [CIs], -2.20, -.94). Similarly, the MAS grades judged at 4 weeks after ESWT were also showed to be significantly lower than the baseline values (SMD, -1.93; 95% CIs, -2.71, -1.15). ESWT for the spasticity of patients after a stroke is effective, as measured by MAS grades. Moreover, no serious side effects were observed in any patients after shock wave therapy. Nevertheless, our current study with some limitations such as the limited sample size only provided limited quality of evidence; confirmation from a further systematic review or meta-analysis with large-scale, well-designed randomized control trials is required. Copyright © 2017. Published by Elsevier Inc.

The relative importance of physicochemical factors to stream biological condition in urbanizing basins: Evidence from multimodel inference

USGS Publications Warehouse

Carlisle, Daren M.; Bryant, Wade L.

2011-01-01

Many physicochemical factors potentially impair stream ecosystems in urbanizing basins, but few studies have evaluated their relative importance simultaneously, especially in different environmental settings. We used data collected in 25 to 30 streams along a gradient of urbanization in each of 6 metropolitan areas (MAs) to evaluate the relative importance of 11 physicochemical factors on the condition of algal, macroinvertebrate, and fish assemblages. For each assemblage, biological condition was quantified using 2 separate metrics, nonmetric multidimensional scaling ordination site scores and the ratio of observed/expected taxa, both derived in previous studies. Separate linear regression models with 1 or 2 factors as predictors were developed for each MA and assemblage metric. Model parsimony was evaluated based on Akaike’s Information Criterion for small sample size (AICc) and Akaike weights, and variable importance was estimated by summing the Akaike weights across models containing each stressor variable. Few of the factors were strongly correlated (Pearson |r| > 0.7) within MAs. Physicochemical factors explained 17 to 81% of variance in biological condition. Most (92 of 118) of the most plausible models contained 2 predictors, and generally more variance could be explained by the additive effects of 2 factors than by any single factor alone. None of the factors evaluated was universally important for all MAs or biological assemblages. The relative importance of factors varied for different measures of biological condition, biological assemblages, and MA. Our results suggest that the suite of physicochemical factors affecting urban stream ecosystems varies across broad geographic areas, along gradients of urban intensity, and among basins within single MAs.

Edge-directed inference for microaneurysms detection in digital fundus images

NASA Astrophysics Data System (ADS)

Huang, Ke; Yan, Michelle; Aviyente, Selin

2007-03-01

Microaneurysms (MAs) detection is a critical step in diabetic retinopathy screening, since MAs are the earliest visible warning of potential future problems. A variety of algorithms have been proposed for MAs detection in mass screening. Different methods have been proposed for MAs detection. The core technology for most of existing methods is based on a directional mathematical morphological operation called "Top-Hat" filter that requires multiple filtering operations at each pixel. Background structure, uneven illumination and noise often cause confusion between MAs and some non-MA structures and limits the applicability of the filter. In this paper, a novel detection framework based on edge directed inference is proposed for MAs detection. The candidate MA regions are first delineated from the edge map of a fundus image. Features measuring shape, brightness and contrast are extracted for each candidate MA region to better exclude false detection from true MAs. Algorithmic analysis and empirical evaluation reveal that the proposed edge directed inference outperforms the "Top-Hat" based algorithm in both detection accuracy and computational speed.

Hospital acquisitions, parenting styles and management accounting change: An institutional perspective.

PubMed

Dossi, Andrea; Lecci, Francesca; Longo, Francesco; Morelli, Marco

2017-02-01

Many healthcare scholars have applied institutional theories to the study of management accounting systems (MAS) change. However, little attention has been devoted to MAS change within groups. Kostova et al. highlight the limitations of traditional institutional frameworks in studying groups since they are characterised not only by the existence of external institutional environments but also by intra-organisational (meso-level) ones. Given this background, the research question is: how does the meso-level institutional environment affect MAS change in healthcare groups? We use a longitudinal multiple-case study design to understand the role of headquarters in shaping local MAS change. We would expect companies to adopt similar MAS. However, we argue that the relationship between external institutions and MAS change cannot be wholly understood without taking into consideration the role of headquarters. Our analysis shows how hospitals facing the same external institutional environment implement different MAS as a consequence of different parenting styles. From a scientific perspective, our article contributes to broaden traditional institutional theoretical frameworks.

Separating inverse spin Hall voltage and spin rectification voltage by inverting spin injection direction

NASA Astrophysics Data System (ADS)

Zhang, Wenxu; Peng, Bin; Han, Fangbin; Wang, Qiuru; Soh, Wee Tee; Ong, Chong Kim; Zhang, Wanli

2016-03-01

We develop a method for universally resolving the important issue of separating the inverse spin Hall effect (ISHE) from the spin rectification effect (SRE) signal. This method is based on the consideration that the two effects depend on the spin injection direction: The ISHE is an odd function of the spin injection direction while the SRE is independent on it. Thus, the inversion of the spin injection direction changes the ISHE voltage signal, while the SRE voltage remains. It applies generally to analyzing the different voltage contributions without fitting them to special line shapes. This fast and simple method can be used in a wide frequency range and has the flexibility of sample preparation.