A high-resolution (13)C 3D CSA-CSA-CSA correlation experiment by means of magic angle turning.

PubMed

Hu, J Z; Ye, C; Pugmire, R J; Grant, D M

2000-08-01

It is shown in this paper that a previously reported 90 degrees sample flipping (13)C 2D CSA-CSA correlation experiment may be carried out alternatively by employing constant slow sample rotation about the magic angle axis and by synchronizing the read pulse to 13 of the rotor cycle. A high-resolution 3D CSA-CSA-CSA correlation experiment based on the magic angle turning technique is reported in which the conventional 90 degrees 2D CSA-CSA powder pattern for each carbon in a system containing a number of inequivalent carbons may be separated according to the isotropic chemical shift value. The technique is demonstrated on 1,2,3-trimethoxybenzene in which all of the overlapping powder patterns that cannot be segregated by the 2D CSA-CSA experiment are resolved successfully by the 3D CSA-CSA-CSA experiment, including even the two methoxy groups (M(1) and M(3)) whose isotropic shifts, confirmed by high-speed MAS, are separated by only 1 ppm. A difference of 4 ppm in the principal value component (delta(33)) between M(1) and M(3) is readily obtained. Copyright 2000 Academic Press.

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.

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

Controlling soliton excitations in Heisenberg spin chains through the magic angle.

PubMed

Lu, Jing; Zhou, Lan; Kuang, Le-Man; Sun, C P

2009-01-01

We study the nonlinear dynamics of collective excitation in an N -site XXZ quantum spin chain, which is manipulated by an oblique magnetic field. We show that, when the tilted field is applied along the magic angle, theta_{0}=+/-arccossqrt[13] , the anisotropic Heisenberg spin chain becomes isotropic and thus an freely propagating spin wave is stimulated. Also, in the regime of tilted angles larger and smaller than the magic angle, two types of nonlinear excitations appear: bright and dark solitons.

Screening molecular associations with lipid membranes using natural abundance 13C cross-polarization magic-angle spinning NMR and principal component analysis.

PubMed

Middleton, David A; Hughes, Eleri; Madine, Jillian

2004-08-11

We describe an NMR approach for detecting the interactions between phospholipid membranes and proteins, peptides, or small molecules. First, 1H-13C dipolar coupling profiles are obtained from hydrated lipid samples at natural isotope abundance using cross-polarization magic-angle spinning NMR methods. Principal component analysis of dipolar coupling profiles for synthetic lipid membranes in the presence of a range of biologically active additives reveals clusters that relate to different modes of interaction of the additives with the lipid bilayer. Finally, by representing profiles from multiple samples in the form of contour plots, it is possible to reveal statistically significant changes in dipolar couplings, which reflect perturbations in the lipid molecules at the membrane surface or within the hydrophobic interior.

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.

Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder

PubMed Central

Thurber, Kent R.; Tycko, Robert

2009-01-01

Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of 79Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the 79Br NMR frequency to that of 13C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions. PMID:18930418

Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder.

PubMed

Thurber, Kent R; Tycko, Robert

2009-01-01

Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of (79)Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the (79)Br NMR frequency to that of (13)C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions.

Towards real-time metabolic profiling of a biopsy specimen during a surgical operation by 1H high resolution magic angle spinning nuclear magnetic resonance: a case report.

PubMed

Piotto, Martial; Moussallieh, François-Marie; Neuville, Agnès; Bellocq, Jean-Pierre; Elbayed, Karim; Namer, Izzie Jacques

2012-01-18

Providing information on cancerous tissue samples during a surgical operation can help surgeons delineate the limits of a tumoral invasion more reliably. Here, we describe the use of metabolic profiling of a colon biopsy specimen by high resolution magic angle spinning nuclear magnetic resonance spectroscopy to evaluate tumoral invasion during a simulated surgical operation. Biopsy specimens (n = 9) originating from the excised right colon of a 66-year-old Caucasian women with an adenocarcinoma were automatically analyzed using a previously built statistical model. Metabolic profiling results were in full agreement with those of a histopathological analysis. The time-response of the technique is sufficiently fast for it to be used effectively during a real operation (17 min/sample). Metabolic profiling has the potential to become a method to rapidly characterize cancerous biopsies in the operation theater.

Biomolecular solid state NMR with magic-angle spinning at 25K.

PubMed

Thurber, Kent R; Tycko, Robert

2008-12-01

A magic-angle spinning (MAS) probe has been constructed which allows the sample to be cooled with helium, while the MAS bearing and drive gases are nitrogen. The sample can be cooled to 25K using roughly 3 L/h of liquid helium, while the 4-mm diameter rotor spins at 6.7 kHz with good stability (+/-5 Hz) for many hours. Proton decoupling fields up to at least 130 kHz can be applied. This helium-cooled MAS probe enables a variety of one-dimensional and two-dimensional NMR experiments on biomolecular solids and other materials at low temperatures, with signal-to-noise proportional to 1/T. We show examples of low-temperature (13)C NMR data for two biomolecular samples, namely the peptide Abeta(14-23) in the form of amyloid fibrils and the protein HP35 in frozen glycerol/water solution. Issues related to temperature calibration, spin-lattice relaxation at low temperatures, paramagnetic doping of frozen solutions, and (13)C MAS NMR linewidths are discussed.

Studies of an Isolated 15N- 15N Spin Pair. Off-Angle Fast-Sample-Spinning NMR and Self-Consistent-Field Calculations for Diazo Systems

NASA Astrophysics Data System (ADS)

Challoner, Robin; Harris, Robin K.; Tossell, John A.

1997-05-01

An off-magic-angle spinning study of the nonassociated molecular solid, doubly15N-labeled 5-methyl-2-diazobenzenesulphonic acid hydrochloride (I) is reported. The validity of the off-magic-angle spinning approach under fast-spinning conditions is verified by average Hamiltonian theory. Ab initio SCF calculations were performed on the simpler molecule, C6H5N2+, to provide the shielding parameters, the dipolar coupling between the two nitrogen nuclei, and the electric field gradient existing at both the α-nitrogen and β-nitrogen sites. The calculated values are in good agreement with the shielding and effective dipolar coupling data elucidated in the present investigation, and with a previous study of the two singly15N-labeled isotopomers in which information concerning the electric field gradient at the α and β sites was deduced.

Magic-Angle-Spinning NMR Magnet Development: Field Analysis and Prototypes

PubMed Central

Voccio, John; Hahn, Seungyong; Park, Dong Keun; Ling, Jiayin; Kim, Youngjae; Bascuñán, Juan; Iwasa, Yukikazu

2013-01-01

We are currently working on a program to complete a 1.5 T/75 mm RT bore magic-angle-spinning nuclear magnetic resonance magnet. The magic-angle-spinning magnet comprises a z-axis 0.866-T solenoid and an x-axis 1.225-T dipole, each to be wound with NbTi wire and operated at 4.2 K in persistent mode. A combination of the fields creates a 1.5-T field pointed at 54.74 degrees (magic angle) from the rotation (z) axis. In the first year of this 3-year program, we have completed magnetic analysis and design of both coils. Also, using a winding machine of our own design and fabrication, we have wound several prototype dipole coils with NbTi wire. As part of this development, we have repeatedly made successful persistent NbTi-NbTi joints with this multifilamentary NbTi wire. PMID:24058275

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.

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.

Nuclear Magnetic Resonance Spectroscopy Applications: Proton NMR In Biological Objects Subjected To Magic Angle Spinning

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

Wind, Robert A.; Hu, Jian Zhi

2005-01-01

Proton NMR in Biological Objects Submitted to Magic Angle Spinning, In Encyclopedia of Analytical Science, Second Edition (Paul J. Worsfold, Alan Townshend and Colin F. Poole, eds.), Elsevier, Oxford 6:333-342. Published January 1, 2005. Proposal Number 10896.

Towards real-time metabolic profiling of a biopsy specimen during a surgical operation by 1H high resolution magic angle spinning nuclear magnetic resonance: a case report

PubMed Central

2012-01-01

Introduction Providing information on cancerous tissue samples during a surgical operation can help surgeons delineate the limits of a tumoral invasion more reliably. Here, we describe the use of metabolic profiling of a colon biopsy specimen by high resolution magic angle spinning nuclear magnetic resonance spectroscopy to evaluate tumoral invasion during a simulated surgical operation. Case presentation Biopsy specimens (n = 9) originating from the excised right colon of a 66-year-old Caucasian women with an adenocarcinoma were automatically analyzed using a previously built statistical model. Conclusions Metabolic profiling results were in full agreement with those of a histopathological analysis. The time-response of the technique is sufficiently fast for it to be used effectively during a real operation (17 min/sample). Metabolic profiling has the potential to become a method to rapidly characterize cancerous biopsies in the operation theater. PMID:22257563

Solid state nuclear magnetic resonance with magic-angle spinning and dynamic nuclear polarization below 25 K

PubMed Central

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

2012-01-01

We describe an apparatus for solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS) at 20–25 K and 9.4 Tesla. The MAS NMR probe uses helium to cool the sample space and nitrogen gas for MAS drive and bearings, as described earlier (Thurber et al., J. Magn. Reson. 2008) [1], but also includes a corrugated waveguide for transmission of microwaves from below the probe to the sample. With a 30 mW circularly polarized microwave source at 264 GHz, MAS at 6.8 kHz, and 21 K sample temperature, greater than 25-fold enhancements of cross-polarized 13C NMR signals are observed in spectra of frozen glycerol/water solutions containing the triradical dopant DOTOPA-TEMPO when microwaves are applied. As demonstrations, we present DNP-enhanced one-dimensional and two-dimensional 13C MAS NMR spectra of frozen solutions of uniformly 13C-labeled L-alanine and melittin, a 26-residue helical peptide that we have synthesized with four uniformly 13C-labeled amino acids. PMID:23238592

Solid state nuclear magnetic resonance with magic-angle spinning and dynamic nuclear polarization below 25 K.

PubMed

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

2013-01-01

We describe an apparatus for solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS) at 20-25 K and 9.4 Tesla. The MAS NMR probe uses helium to cool the sample space and nitrogen gas for MAS drive and bearings, as described earlier, but also includes a corrugated waveguide for transmission of microwaves from below the probe to the sample. With a 30 mW circularly polarized microwave source at 264 GHz, MAS at 6.8 kHz, and 21 K sample temperature, greater than 25-fold enhancements of cross-polarized (13)C NMR signals are observed in spectra of frozen glycerol/water solutions containing the triradical dopant DOTOPA-TEMPO when microwaves are applied. As demonstrations, we present DNP-enhanced one-dimensional and two-dimensional (13)C MAS NMR spectra of frozen solutions of uniformly (13)C-labeled l-alanine and melittin, a 26-residue helical peptide that we have synthesized with four uniformly (13)C-labeled amino acids. 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.

A Simple Approach for Obtaining High Resolution, High Sensitivity ¹H NMR Metabolite Spectra of Biofluids with Limited Mass Supply

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

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

2006-11-01

A simple approach is reported that yields high resolution, high sensitivity ¹H NMR spectra of biofluids with limited mass supply. This is achieved by spinning a capillary sample tube containing a biofluid at the magic angle at a frequency of about 80Hz. A 2D pulse sequence called ¹H PASS is then used to produce a high-resolution ¹H NMR spectrum that is free from magnetic susceptibility induced line broadening. With this new approach a high resolution ¹H NMR spectrum of biofluids with a volume less than 1.0 µl can be easily achieved at a magnetic field strength as low as 7.05T.more » Furthermore, the methodology facilitates easy sample handling, i.e., the samples can be directly collected into inexpensive and disposable capillary tubes at the site of collection and subsequently used for NMR measurements. In addition, slow magic angle spinning improves magnetic field shimming and is especially suitable for high throughput investigations. In this paper first results are shown obtained in a magnetic field of 7.05T on urine samples collected from mice using a modified commercial NMR probe.« less

Method for high resolution magnetic resonance analysis using magic angle technique

DOEpatents

Wind, Robert A.; Hu, Jian Zhi

2003-12-30

A method of performing a magnetic resonance analysis of a biological object that includes placing the object in a main magnetic field (that has a static field direction) and in a radio frequency field; rotating the object at a frequency of less than about 100 Hz around an axis positioned at an angle of about 54.degree.44' relative to the main magnetic static field direction; pulsing the radio frequency to provide a sequence that includes a phase-corrected magic angle turning pulse segment; and collecting data generated by the pulsed radio frequency. The object may be reoriented about the magic angle axis between three predetermined positions that are related to each other by 120.degree.. The main magnetic field may be rotated mechanically or electronically. Methods for magnetic resonance imaging of the object are also described.

Method for high resolution magnetic resonance analysis using magic angle technique

DOEpatents

Wind, Robert A.; Hu, Jian Zhi

2004-12-28

A method of performing a magnetic resonance analysis of a biological object that includes placing the object in a main magnetic field (that has a static field direction) and in a radio frequency field; rotating the object at a frequency of less than about 100 Hz around an axis positioned at an angle of about 54.degree.44' relative to the main magnetic static field direction; pulsing the radio frequency to provide a sequence that includes a phase-corrected magic angle turning pulse segment; and collecting data generated by the pulsed radio frequency. The object may be reoriented about the magic angle axis between three predetermined positions that are related to each other by 120.degree.. The main magnetic field may be rotated mechanically or electronically. Methods for magnetic resonance imaging of the object are also described.

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.

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

A highly ordered mesostructured material containing regularly distributed phenols: preparation and characterization at a molecular level through ultra-fast magic angle spinning proton NMR spectroscopy.

PubMed

Roussey, Arthur; Gajan, David; Maishal, Tarun K; Mukerjee, Anhurada; Veyre, Laurent; Lesage, Anne; Emsley, Lyndon; Copéret, Christophe; Thieuleux, Chloé

2011-03-14

Highly ordered organic-inorganic mesostructured material containing regularly distributed phenols is synthesized by combining a direct synthesis of the functional material and a protection-deprotection strategy and characterized at a molecular level through ultra-fast magic angle spinning proton NMR spectroscopy.

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

Multidimensional High-Resolution Magic Angle Spinning and Solution-State NMR Characterization of 13C-labeled Plant Metabolites and Lignocellulose

PubMed Central

Mori, Tetsuya; Tsuboi, Yuuri; Ishida, Nobuhiro; Nishikubo, Nobuyuki; Demura, Taku; Kikuchi, Jun

2015-01-01

Lignocellulose, which includes mainly cellulose, hemicellulose, and lignin, is a potential resource for the production of chemicals and for other applications. For effective production of materials derived from biomass, it is important to characterize the metabolites and polymeric components of the biomass. Nuclear magnetic resonance (NMR) spectroscopy has been used to identify biomass components; however, the NMR spectra of metabolites and lignocellulose components are ambiguously assigned in many cases due to overlapping chemical shift peaks. Using our 13C-labeling technique in higher plants such as poplar samples, we demonstrated that overlapping peaks could be resolved by three-dimensional NMR experiments to more accurately assign chemical shifts compared with two-dimensional NMR measurements. Metabolites of the 13C-poplar were measured by high-resolution magic angle spinning NMR spectroscopy, which allows sample analysis without solvent extraction, while lignocellulose components of the 13C-poplar dissolved in dimethylsulfoxide/pyridine solvent were analyzed by solution-state NMR techniques. Using these methods, we were able to unambiguously assign chemical shifts of small and macromolecular components in 13C-poplar samples. Furthermore, using samples of less than 5 mg, we could differentiate between two kinds of genes that were overexpressed in poplar samples, which produced clearly modified plant cell wall components. PMID:26143886

Magic-angle spinning NMR of intact bacteriophages: Insights into the capsid, DNA and their interface

NASA Astrophysics Data System (ADS)

Abramov, Gili; Morag, Omry; Goldbourt, Amir

2015-04-01

Bacteriophages are viruses that infect bacteria. They are complex macromolecular assemblies, which are composed of multiple protein subunits that protect genomic material and deliver it to specific hosts. Various biophysical techniques have been used to characterize their structure in order to unravel phage morphogenesis. Yet, most bacteriophages are non-crystalline and have very high molecular weights, in the order of tens of MegaDaltons. Therefore, complete atomic-resolution characterization on such systems that encompass both capsid and DNA is scarce. In this perspective article we demonstrate how magic-angle spinning solid-state NMR has and is used to characterize in detail bacteriophage viruses, including filamentous and icosahedral phage. We discuss the process of sample preparation, spectral assignment of both capsid and DNA and the use of chemical shifts and dipolar couplings to probe the capsid-DNA interface, describe capsid structure and dynamics and extract structural differences between viruses.

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.

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.

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.

Investigation of Regional Influence of Magic-Angle Effect on T2 in Human Articular Cartilage with Osteoarthritis at 3 T

PubMed Central

Wang, Ligong; Regatte, Ravinder R.

2014-01-01

Rationale and Objectives The objectives of this research study were to determine the magic-angle effect on different subregions of in vivo human femoral cartilage through the quantitative assessment of the effect of static magnetic field orientation (B0) on transverse (T2) relaxation time at 3.0 T. Materials and Methods Healthy volunteers (n = 5l; mean age, 36.4 years) and clinical patients (n = 5; mean age, 64 years) with early osteoarthritis (OA) were scanned at 3.0-T magnetic resonance using an 8-channel phased-array knee coil (transmit-receive). Results The T2 maps revealed significantly greater values in ventral than in dorsal regions. When the cartilage regions were oriented at 55° to B0 (magic angle), the longest T2 values were detected in comparison with the neighboring regions oriented 90° and 180° (0°) to B0. The subregions oriented 180° (0°) to B0 showed the lowest T2 values. Conclusions The differences in T2 values of different subregions suggest that magic-angle effect needs to be considered when interpreting cartilage abnormalities in OA patients. PMID:25481517

Metabolomics by Proton High-Resolution Magic-Angle-Spinning Nuclear Magnetic Resonance of Tomato Plants Treated with Two Secondary Metabolites Isolated from Trichoderma.

PubMed

Mazzei, Pierluigi; Vinale, Francesco; Woo, Sheridan Lois; Pascale, Alberto; Lorito, Matteo; Piccolo, Alessandro

2016-05-11

Trichoderma fungi release 6-pentyl-2H-pyran-2-one (1) and harzianic acid (2) secondary metabolites to improve plant growth and health protection. We isolated metabolites 1 and 2 from Trichoderma strains, whose different concentrations were used to treat seeds of Solanum lycopersicum. The metabolic profile in the resulting 15 day old tomato leaves was studied by high-resolution magic-angle-spinning nuclear magnetic resonance (HRMAS NMR) spectroscopy directly on the whole samples without any preliminary extraction. Principal component analysis (PCA) of HRMAS NMR showed significantly enhanced acetylcholine and γ-aminobutyric acid (GABA) content accompanied by variable amount of amino acids in samples treated with both Trichoderma secondary metabolites. Seed germination rates, seedling fresh weight, and the metabolome of tomato leaves were also dependent upon doses of metabolites 1 and 2 treatments. HRMAS NMR spectroscopy was proven to represent a rapid and reliable technique for evaluating specific changes in the metabolome of plant leaves and calibrating the best concentration of bioactive compounds required to stimulate plant growth.

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.

Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves.

PubMed

Thurber, Kent R; Tycko, Robert

2014-05-14

We report solid state (13)C and (1)H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, (1)H and cross-polarized (13)C NMR signals from (15)N,(13)C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations.

Magic-angle spinning NMR of intact bacteriophages: insights into the capsid, DNA and their interface.

PubMed

Abramov, Gili; Morag, Omry; Goldbourt, Amir

2015-04-01

Bacteriophages are viruses that infect bacteria. They are complex macromolecular assemblies, which are composed of multiple protein subunits that protect genomic material and deliver it to specific hosts. Various biophysical techniques have been used to characterize their structure in order to unravel phage morphogenesis. Yet, most bacteriophages are non-crystalline and have very high molecular weights, in the order of tens of MegaDaltons. Therefore, complete atomic-resolution characterization on such systems that encompass both capsid and DNA is scarce. In this perspective article we demonstrate how magic-angle spinning solid-state NMR has and is used to characterize in detail bacteriophage viruses, including filamentous and icosahedral phage. We discuss the process of sample preparation, spectral assignment of both capsid and DNA and the use of chemical shifts and dipolar couplings to probe the capsid-DNA interface, describe capsid structure and dynamics and extract structural differences between viruses. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

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.

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.

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

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.

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

NASA Astrophysics Data System (ADS)

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

2008-08-01

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

Chemical and carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance characterization of logyard fines from British Columbia.

PubMed

Preston, C M; Forrester, P D

2004-01-01

Phasing out beehive burners and rising costs for landfilling have increased the need to widen options for utilization of the smaller size fractions of woody wastes generated during log handling and sawmilling in British Columbia. We characterized several size classes of logyard fines up to 16 mm sampled from coastal and interior operations. Total C, total N, ash, and condensed tannin concentrations were consistent with properties derived largely from wood, with varying proportions of bark and mixing with mineral soil. Especially for < 3-mm fractions, the latter resulted in high ash contents that would make them unsuitable for fuel. Solid-state 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectra were consistent with the chemical data, with high O-alkyl intensity and similarity to naturally occurring woody forest floor; no samples were high in aromatic or phenolic C. Aqueous extracts of two < 16-mm fines, which accounted for only a small proportion of the total C, were enriched in alkyl C and had low or undetectable tannins. Application to forest sites might cause short-term immobilization of N, but also might include possible longer-term benefits from reduction of N loss after harvesting and restoration of soil organic matter in degraded sites.

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

Double cross polarization for the indirect detection of nitrogen-14 nuclei in magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Carnevale, Diego; Ji, Xiao; Bodenhausen, Geoffrey

2017-11-01

Nitrogen-14 NMR spectra at fast magic-angle spinning rates can be acquired indirectly by means of two-dimensional techniques based on double cross polarization transfer 1H → 14N →1H. Experimental evidence is given for polycrystalline samples of glycine, l-histidine, and the dipeptide Ala-Gly. Either one-bond or long-range correlations can be favored by choosing the length of the cross polarization contact pulses. Longer contact pulses allow the detection of unprotonated nitrogen sites. In contrast to earlier methods that exploited second-order quadrupolar/dipolar cross-terms, cross polarization operates in the manner of the method of Hartmann and Hahn, even for 14N quadrupolar couplings up to 4 MHz. Simulations explain why amorphous samples tend to give rise to featureless spectra because the 14N quadrupolar interactions may vary dramatically with the lattice environment. The experiments are straightforward to set up and are shown to be effective for different nitrogen environments and robust with respect to the rf-field strengths and to the 14N carrier frequency during cross polarization. The efficiency of indirect detection of 14N nuclei by double cross polarization is shown to be similar to that of isotopically enriched 13C nuclei.

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.

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.

Multiple scattering calculations of relativistic electron energy loss spectra

NASA Astrophysics Data System (ADS)

Jorissen, K.; Rehr, J. J.; Verbeeck, J.

2010-04-01

A generalization of the real-space Green’s-function approach is presented for ab initio calculations of relativistic electron energy loss spectra (EELS) which are particularly important in anisotropic materials. The approach incorporates relativistic effects in terms of the transition tensor within the dipole-selection rule. In particular, the method accounts for relativistic corrections to the magic angle in orientation resolved EELS experiments. The approach is validated by a study of the graphite CK edge, for which we present an accurate magic angle measurement consistent with the predicted value.

Spin-locking and cross-polarization under magic-angle spinning of uniformly labeled solids.

PubMed

Hung, Ivan; Gan, Zhehong

2015-07-01

Spin-locking and cross-polarization under magic-angle spinning are investigated for uniformly (13)C and (15)N labeled solids. In particular, the interferences from chemical shift anisotropy, and (1)H heteronuclear and (13)C homonuclear dipolar couplings are identified. The physical origin of these interferences provides guidelines for selecting the best (13)C and (15)N polarization transfer rf fields. Optimal settings for both the zero- and double-quantum cross-polarization transfer mechanisms are recommended. Copyright © 2015 Elsevier Inc. All rights reserved.

Magic Angle Spinning NMR Metabolomics

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

Zhi Hu, Jian

Nuclear Magnetic Resonance (NMR) spectroscopy is a non-destructive, quantitative, reproducible, untargeted and unbiased method that requires no or minimal sample preparation, and is one of the leading analytical tools for metabonomics research [1-3]. The easy quantification and the no need of prior knowledge about compounds present in a sample associated with NMR are advantageous over other techniques [1,4]. 1H NMR is especially attractive because protons are present in virtually all metabolites and its NMR sensitivity is high, enabling the simultaneous identification and monitoring of a wide range of low molecular weight metabolites.

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.

Magic angle for barrier-controlled double quantum dots

NASA Astrophysics Data System (ADS)

Yang, Xu-Chen; Wang, Xin

2018-01-01

We show that the exchange interaction of a singlet-triplet spin qubit confined in double quantum dots, when being controlled by the barrier method, is insensitive to a charged impurity lying along certain directions away from the center of the double-dot system. These directions differ from the polar axis of the double dots by the magic angle, equaling arccos(1 /√{3 })≈54 .7∘ , a value previously found in atomic physics and nuclear magnetic resonance. This phenomenon can be understood from an expansion of the additional Coulomb interaction created by the impurity, but also relies on the fact that the exchange interaction solely depends on the tunnel coupling in the barrier-control scheme. Our results suggest that for a scaled-up qubit array, when all pairs of double dots rotate their respective polar axes from the same reference line by the magic angle, crosstalk between qubits can be eliminated, allowing clean single-qubit operations. While our model is a rather simplified version of actual experiments, our results suggest that it is possible to minimize unwanted couplings by judiciously designing the layout of the qubits.

Floquet-Magnus expansion for general N-coupled spins systems in magic-angle spinning nuclear magnetic resonance spectra

NASA Astrophysics Data System (ADS)

Mananga, Eugene Stephane; Charpentier, Thibault

2015-04-01

In this paper we present a theoretical perturbative approach for describing the NMR spectrum of strongly dipolar-coupled spin systems under fast magic-angle spinning. Our treatment is based on two approaches: the Floquet approach and the Floquet-Magnus expansion. The Floquet approach is well known in the NMR community as a perturbative approach to get analytical approximations. Numerical procedures are based on step-by-step numerical integration of the corresponding differential equations. The Floquet-Magnus expansion is a perturbative approach of the Floquet theory. Furthermore, we address the " γ -encoding" effect using the Floquet-Magnus expansion approach. We show that the average over " γ " angle can be performed for any Hamiltonian with γ symmetry.

Method for high resolution magnetic resonance analysis using magic angle technique

DOEpatents

Wind, Robert A.; Hu, Jian Zhi

2003-11-25

A method of performing a magnetic resonance analysis of a biological object that includes placing the biological object in a main magnetic field and in a radio frequency field, the main magnetic field having a static field direction; rotating the biological object at a rotational frequency of less than about 100 Hz around an axis positioned at an angle of about 54.degree.44' relative to the main magnetic static field direction; pulsing the radio frequency to provide a sequence that includes a magic angle turning pulse segment; and collecting data generated by the pulsed radio frequency. According to another embodiment, the radio frequency is pulsed to provide a sequence capable of producing a spectrum that is substantially free of spinning sideband peaks.

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).

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.

Magic angle spinning NMR with metallized rotors as cylindrical microwave resonators.

PubMed

Scott, Faith J; Sesti, Erika L; Choi, Eric J; Laut, Alexander J; Sirigiri, Jagadishwar R; Barnes, Alexander B

2018-04-19

We introduce a novel design for millimeter wave electromagnetic structures within magic angle spinning (MAS) rotors. In this demonstration, a copper coating is vacuum deposited onto the outside surface of a sapphire rotor at a thickness of 50 nm. This thickness is sufficient to reflect 197-GHz microwaves, yet not too thick as to interfere with radiofrequency fields at 300 MHz or prevent sample spinning due to eddy currents. Electromagnetic simulations of an idealized rotor geometry show a microwave quality factor of 148. MAS experiments with sample rotation frequencies of ω r /2π = 5.4 kHz demonstrate that the drag force due to eddy currents within the copper does not prevent sample spinning. Spectra of sodium acetate show resolved 13 C J-couplings of 60 Hz and no appreciable broadening between coated and uncoated sapphire rotors, demonstrating that the copper coating does not prevent shimming and high-resolution nuclear magnetic resonance spectroscopy. Additionally, 13 C Rabi nutation curves of ω 1 /2π = 103 kHz for both coated and uncoated rotors indicate no detrimental impact of the copper coating on radio frequency coupling of the nuclear spins to the sample coil. We present this metal coated rotor as a first step towards an MAS resonator. MAS resonators are expected to have a significant impact on developments in electron decoupling, pulsed dynamic nuclear polarization (DNP), room temperature DNP, DNP with low-power microwave sources, and electron paramagnetic resonance detection. Copyright © 2018 John Wiley & Sons, Ltd.

NMR of samples containing metal foils.

PubMed

Xiong, J; Lock, H; Tao, T; Keeler, C; Maciel, G E

1999-07-01

By using spool configurations of a sample containing aluminum foil, in which the axis of the spool is collinear with the RF coil axis, one can obtain high-quality 13C NMR spectra of static samples of organic material attached to the aluminum foil. By combining such a spool configuration (or, alternatively, analogous samples containing equivalent amounts of fine aluminum powder) with the magic-angle hopping (MAH) technique, one can achieve a high degree of isotropic averaging of the 13C spectrum. This opens to NMR techniques the study of a variety of samples containing macroscopic pieces of metal foils, e.g., thin films deposited on metal foils and electrochemical systems with species adsorbed on metal-foil electrodes.

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.

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.

Magic tilt angle for stabilizing two-dimensional solitons by dipole-dipole interactions

NASA Astrophysics Data System (ADS)

Chen, Xing-You; Chuang, You-Lin; Lin, Chun-Yan; Wu, Chien-Ming; Li, Yongyao; Malomed, Boris A.; Lee, Ray-Kuang

2017-10-01

In the framework of the Gross-Pitaevskii equation, we study the formation and stability of effectively two-dimensional solitons in dipolar Bose-Einstein condensates (BECs), with dipole moments polarized at an arbitrary angle θ relative to the direction normal to the system's plane. Using numerical methods and the variational approximation, we demonstrate that unstable Townes solitons, created by the contact attractive interaction, may be completely stabilized (with an anisotropic shape) by the dipole-dipole interaction (DDI), in the interval θcr<θ ≤π /2 . The stability boundary θcr weakly depends on the relative strength of the DDI, remaining close to the magic angle θm=arccos(1 /√{3 }) . The results suggest that DDIs provide a generic mechanism for the creation of stable BEC solitons in higher dimensions.

A permanent MRI magnet for magic angle imaging having its field parallel to the poles.

PubMed

McGinley, John V M; Ristic, Mihailo; Young, Ian R

2016-10-01

A novel design of open permanent magnet is presented, in which the magnetic field is oriented parallel to the planes of its poles. The paper describes the methods whereby such a magnet can be designed with a field homogeneity suitable for Magnetic Resonance Imaging (MRI). Its primary purpose is to take advantage of the Magic Angle effect in MRI of human extremities, particularly the knee joint, by being capable of rotating the direction of the main magnetic field B0 about two orthogonal axes around a stationary subject and achieve all possible angulations. The magnet comprises a parallel pair of identical profiled arrays of permanent magnets backed by a flat steel yoke such that access in lateral directions is practical. The paper describes the detailed optimization procedure from a target 150mm DSV to the achievement of a measured uniform field over a 130mm DSV. Actual performance data of the manufactured magnet, including shimming and a sample image, is presented. The overall magnet system mounting mechanism is presented, including two orthogonal axes of rotation of the magnet about its isocentre. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Simultaneous acquisition of 2D and 3D solid-state NMR experiments for sequential assignment of oriented membrane protein samples.

PubMed

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

2015-05-01

We present a new method called DAISY (Dual Acquisition orIented ssNMR spectroScopY) for the simultaneous acquisition of 2D and 3D oriented solid-state NMR experiments for membrane proteins reconstituted in mechanically or magnetically aligned lipid bilayers. DAISY utilizes dual acquisition of sine and cosine dipolar or chemical shift coherences and long living (15)N longitudinal polarization to obtain two multi-dimensional spectra, simultaneously. In these new experiments, the first acquisition gives the polarization inversion spin exchange at the magic angle (PISEMA) or heteronuclear correlation (HETCOR) spectra, the second acquisition gives PISEMA-mixing or HETCOR-mixing spectra, where the mixing element enables inter-residue correlations through (15)N-(15)N homonuclear polarization transfer. The analysis of the two 2D spectra (first and second acquisitions) enables one to distinguish (15)N-(15)N inter-residue correlations for sequential assignment of membrane proteins. DAISY can be implemented in 3D experiments that include the polarization inversion spin exchange at magic angle via I spin coherence (PISEMAI) sequence, as we show for the simultaneous acquisition of 3D PISEMAI-HETCOR and 3D PISEMAI-HETCOR-mixing experiments.

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.

Relationships between magical thinking, obsessive-compulsiveness and other forms of anxiety in a sample of non-clinical children.

PubMed

Simonds, Laura M; Demetre, James D; Read, Cristina

2009-06-01

Despite the obvious phenomenological similarities between magical thinking and obsessive-compulsiveness, the relationship between them has been the subject of few empirical investigations in samples of children. The present study aimed to examine the relationship between a general epistemic stance towards magical causation and tendencies towards obsessive-compulsiveness in a non-clinical sample of schoolchildren. One-hundred and two children, aged between 5 and 10 years (48 boys and 54 girls), completed questionnaire measures designed to assess magical thinking, obsessive-compulsiveness, and other forms of anxiety. School teachers completed a measure of strengths and difficulties for each child. General belief in magical causation was correlated with all types of anxiety, not just obsessive-compulsiveness, with significant correlations shown for boys in the sample, but not girls. General belief in magical causation contributed little to the prediction of obsessive-compulsiveness beyond general anxiety. In this study, a general epistemic stance towards magical causation did not differentiate obsessive-compulsiveness from other anxiety dimensions. The findings are considered in the context of developmental theories of magical and scientific causal reasoning.

High-resolution molecular structure of a peptide in an amyloid fibril determined by magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Macphee, Cait E.; Bajaj, Vikram S.; McMahon, Michael T.; Dobson, Christopher M.; Griffin, Robert G.

2004-01-01

Amyloid fibrils are self-assembled filamentous structures associated with protein deposition conditions including Alzheimer's disease and the transmissible spongiform encephalopathies. Despite the immense medical importance of amyloid fibrils, no atomic-resolution structures are available for these materials, because the intact fibrils are insoluble and do not form diffraction-quality 3D crystals. Here we report the high-resolution structure of a peptide fragment of the amyloidogenic protein transthyretin, TTR(105-115), in its fibrillar form, determined by magic angle spinning NMR spectroscopy. The structure resolves not only the backbone fold but also the precise conformation of the side chains. Nearly complete 13C and 15N resonance assignments for TTR(105-115) formed the basis for the extraction of a set of distance and dihedral angle restraints. A total of 76 self-consistent experimental measurements, including 41 restraints on 19 backbone dihedral angles and 35 13C-15N distances between 3 and 6 Å were obtained from 2D and 3D NMR spectra recorded on three fibril samples uniformly 13C, 15N-labeled in consecutive stretches of four amino acids and used to calculate an ensemble of peptide structures. Our results indicate that TTR(105-115) adopts an extended -strand conformation in the amyloid fibrils such that both the main- and side-chain torsion angles are close to their optimal values. Moreover, the structure of this peptide in the fibrillar form has a degree of long-range order that is generally associated only with crystalline materials. These findings provide an explanation of the unusual stability and characteristic properties of this form of polypeptide assembly.

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).

Magic Angle Spinning NMR of Viruses

PubMed Central

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

2015-01-01

Viruses, relatively simple pathogens, are able to replicate in many living organisms and to adapt to various environments. Conventional atomic-resolution structural biology techniques, X-ray crystallography and solution NMR spectroscopy provided abundant information on the structures of individual proteins and nucleic acids comprising viruses; however, viral assemblies are not amenable to analysis by these techniques because of their large size, insolubility, and inherent lack of long-range order. In this article, we review the recent advances in magic angle spinning NMR spectroscopy that enabled atomic-resolution analysis of structure and dynamics of large viral systems and give examples of several exciting case studies. PMID:25919197

UTE bi-component analysis of T2* relaxation in articular cartilage

PubMed Central

Shao, H.; Chang, E.Y.; Pauli, C.; Zanganeh, S.; Bae, W.; Chung, C.B.; Tang, G.; Du, J.

2015-01-01

SUMMARY Objectives To determine T2* relaxation in articular cartilage using ultrashort echo time (UTE) imaging and bi-component analysis, with an emphasis on the deep radial and calcified cartilage. Methods Ten patellar samples were imaged using two-dimensional (2D) UTE and Car-Purcell-Meiboom-Gill (CPMG) sequences. UTE images were fitted with a bi-component model to calculate T2* and relative fractions. CPMG images were fitted with a single-component model to calculate T2. The high signal line above the subchondral bone was regarded as the deep radial and calcified cartilage. Depth and orientation dependence of T2*, fraction and T2 were analyzed with histopathology and polarized light microscopy (PLM), confirming normal regions of articular cartilage. An interleaved multi-echo UTE acquisition scheme was proposed for in vivo applications (n = 5). Results The short T2* values remained relatively constant across the cartilage depth while the long T2* values and long T2* fractions tended to increase from subchondral bone to the superficial cartilage. Long T2*s and T2s showed significant magic angle effect for all layers of cartilage from the medial to lateral facets, while the short T2* values and T2* fractions are insensitive to the magic angle effect. The deep radial and calcified cartilage showed a mean short T2* of 0.80 ± 0.05 ms and short T2* fraction of 39.93 ± 3.05% in vitro, and a mean short T2* of 0.93 ± 0.58 ms and short T2* fraction of 35.03 ± 4.09% in vivo. Conclusion UTE bi-component analysis can characterize the short and long T2* values and fractions across the cartilage depth, including the deep radial and calcified cartilage. The short T2* values and T2* fractions are magic angle insensitive. PMID:26382110

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.

Tunable magic wavelengths for trapping with focused Laguerre-Gaussian beams

NASA Astrophysics Data System (ADS)

Bhowmik, Anal; Dutta, Narendra Nath; Majumder, Sonjoy

2018-02-01

We present in this paper a theory of dynamic polarizability for an atomic state due to an external field of nonparaxial Laguerre-Gaussian (LG) beam using the sum-over-states technique. A highly correlated relativistic coupled-cluster theory is used to evaluate the most important and correlation-sensitive parts of the sum. The theory is applied on Sr+ to determine the magic wavelengths for 5 s1 /2→4 d3 /2,4 d5 /2 transitions. Results show the variation of magic wavelengths with the choice of orbital and spin angular momenta of the incident LG beam. Also, the tunability of the magic wavelengths is studied by using the focusing angle of the LG beam and its efficiency in the near-infrared region is observed. Evaluations of the wide spectrum of magic wavelengths from infrared to ultraviolet have substantial importance to experimentalists for carrying out high-precision measurements in fundamental physics. These magic wavelengths can be used to confine the atom or ion at the dark central node or at the high-intensity ring of the LG beam.

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.

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.

Methods for magnetic resonance analysis using magic angle technique

DOEpatents

Hu, Jian Zhi [Richland, WA; Wind, Robert A [Kennewick, WA; Minard, Kevin R [Kennewick, WA; Majors, Paul D [Kennewick, WA

2011-11-22

Methods of performing a magnetic resonance analysis of a biological object are disclosed that include placing the object in a main magnetic field (that has a static field direction) and in a radio frequency field; rotating the object at a frequency of less than about 100 Hz around an axis positioned at an angle of about 54.degree.44' relative to the main magnetic static field direction; pulsing the radio frequency to provide a sequence that includes a phase-corrected magic angle turning pulse segment; and collecting data generated by the pulsed radio frequency. In particular embodiments the method includes pulsing the radio frequency to provide at least two of a spatially selective read pulse, a spatially selective phase pulse, and a spatially selective storage pulse. Further disclosed methods provide pulse sequences that provide extended imaging capabilities, such as chemical shift imaging or multiple-voxel data acquisition.

The Illusory Beliefs Inventory: a new measure of magical thinking and its relationship with obsessive compulsive disorder.

PubMed

Kingdon, Bianca L; Egan, Sarah J; Rees, Clare S

2012-01-01

Magical thinking has been proposed to have an aetiological role in obsessive compulsive disorder (OCD). To address the limitations of existing measures of magical thinking we developed and validated a new 24-item measure of magical thinking, the Illusory Beliefs Inventory (IBI). The validation sample comprised a total of 1194 individuals across two samples recruited via an Internet based survey. Factor analysis identified three subscales representing domains relevant to the construct of magical thinking: Magical Beliefs, Spirituality, and Internal State and Thought Action Fusion. The scale had excellent internal consistency and evidence of convergent and discriminant validity. Evidence of criterion-related concurrent validity confirmed that magical thinking is a cognitive domain associated with OCD and is largely relevant to neutralizing, obsessing and hoarding symptoms. It is important for future studies to extend the evidence of the psychometric properties of the IBI in new populations and to conduct longitudinal studies to examine the aetiological role of magical thinking.

Accurate Molecular Orientation Analysis Using Infrared p-Polarized Multiple-Angle Incidence Resolution Spectrometry (pMAIRS) Considering the Refractive Index of the Thin Film Sample.

PubMed

Shioya, Nobutaka; Shimoaka, Takafumi; Murdey, Richard; Hasegawa, Takeshi

2017-06-01

Infrared (IR) p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) is a powerful tool for analyzing the molecular orientation in an organic thin film. In particular, pMAIRS works powerfully for a thin film with a highly rough surface irrespective of degree of the crystallinity. Recently, the optimal experimental condition has comprehensively been revealed, with which the accuracy of the analytical results has largely been improved. Regardless, some unresolved matters still remain. A structurally isotropic sample, for example, yields different peak intensities in the in-plane and out-of-plane spectra. In the present study, this effect is shown to be due to the refractive index of the sample film and a correction factor has been developed using rigorous theoretical methods. As a result, with the use of the correction factor, organic materials having atypical refractive indices such as perfluoroalkyl compounds ( n = 1.35) and fullerene ( n = 1.83) can be analyzed with high accuracy comparable to a compound having a normal refractive index of approximately 1.55. With this improved technique, we are also ready for discriminating an isotropic structure from an oriented sample having the magic angle of 54.7°.

Electron paramagnetic resonance, scanning electron microscopy with energy dispersion X-ray spectrometry, X-ray powder diffraction, and NMR characterization of iron-rich fired clays.

PubMed

Presciutti, Federica; Capitani, Donatella; Sgamellotti, Antonio; Brunetti, Brunetto Giovanni; Costantino, Ferdinando; Viel, Stéphane; Segre, Annalaura

2005-12-01

The aim of this study is to clarify the structure of an iron-rich clay and the structural changes involved in the firing process as a preliminary step to get information on ancient ceramic technology. To this purpose, illite-rich clay samples fired at different temperatures were characterized using a multitechnique approach, i.e., by electron paramagnetic resonance, scanning electron microscopy with electron dispersion X-ray spectrometry, X-ray powder diffraction, magic angle spinning and multiple quantum magic angle spinning NMR. During firing, four main reaction processes occur: dehydration, dehydroxylation, structural breakdown, and recrystallization. When the results are combined from all characterization methods, the following conclusions could be obtained. Interlayer H2O is located close to aluminum in octahedral sites and is driven off at temperatures lower than 600 degrees C. Between 600 and 700 degrees C dehydroxylation occurs whereas, between 800 and 900 degrees C, the aluminum in octahedral sites disappears, due to the breakdown of the illite structure, and all iron present is oxidized to Fe3+. In samples fired at 1000 and 1100 degrees C iron clustering was observed as well as large single crystals of iron with the occurrence of ferro- or ferrimagnetic effects. Below 900 degrees C the aluminum in octahedral sites presents a continuous distribution of chemical shift, suggesting the presence of slightly distorted sites. Finally, over the whole temperature range, the presence of at least two tetrahedral aluminum sites was revealed, characterized by different values of the quadrupolar coupling constant.

A novel dipolar dephasing method for the slow magic angle turning experiment.

PubMed

Hu, J Z; Taylor, C M; Pugmire, R J; Grant, D M

2001-09-01

Complete suppression of the resonances from protonated carbons in a slow magic angle spinning experiment can be achieved using five dipolar dephasing (Five-DD) periods distributed in one rotor period. This produces a spectrum containing only the spinning sidebands (SSB) from the nonprotonated carbons. It is shown that the SSB patterns corresponding to the nonprotonated carbons are not distorted over a wide range of dipolar dephasing times. Hence, this method can be used to obtain reliable principal values of the chemical shift tensors for each nonprotonated carbon. The Five-DD method can be readily incorporated into isotropic-anisotropic 2D experiments such as FIREMAT and 2D-PASS to facilitate the measurement of the (13)C chemical shift tensors in complex systems. Copyright 2001 Academic Press.

Non-Fermi-liquid magic angle effects in high magnetic fields

NASA Astrophysics Data System (ADS)

Lebed, A. G.

2016-07-01

We investigate a theoretical problem of electron-electron interactions in an inclined magnetic field in a quasi-one-dimensional (Q1D) conductor. We show that they result in strong non-Fermi-liquid corrections to a specific heat, provided that the direction of the magnetic field is far from the so-called Lebed's magic angles (LMAs). If magnetic field is directed close to one of the LMAs, the specific heat corrections become small and the Fermi-liquid picture restores. As a result, we predict Fermi-liquid-non-Fermi-liquid angular crossovers in the vicinities of the LMA directions of the field. We suggest to perform the corresponding experiment in the Q1D conductor (Per) 2Au (mnt) 2 under pressure in magnetic fields of the order of H ≃25 T .

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.

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.

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.

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.

Puzzles Pastimes Problems.

ERIC Educational Resources Information Center

Eperson, D. B.

1991-01-01

This section includes eight problems to which the journal invites readers to respond. Problem topics include angles in alternate segments, pentominoes, a new triangle of numbers, cricket scores, symmetrical pentagons, inequalities, a pythagorean dissection, and magic squares. (MDH)

Resolution enhancement in 13C and 15N magic-angle turning experiments with TPPM decoupling.

PubMed

McGeorge, G; Alderman, D W; Grant, D M

1999-03-01

Many solid-state spectra have been shown to have problems related to the poor proton decoupling of carbon nuclei in methylene groups under conditions of slow magic-angle turning. Two-pulse phase-modulation (TPPM) decoupling during the 2D PHORMAT chemical shift separation experiment is shown to be more effective in comparison to that obtainable at much higher spin rates using conventional CW decoupling. TPPM decoupling can also alleviate similar inadequacies when observing the 15N nucleus, particularly with NH2 groups. This is demonstrated in the 15N resonances of fully labeled l-arginine hydrochloride, where a line narrowing of about a factor of two was observed at moderate rotation rates. This significant advantage was also obtained at turning frequencies as low as 500 Hz. Copyright 1999 Academic Press.

Measurement of 13C chemical shift tensor principal values with a magic-angle turning experiment.

PubMed

Hu, J Z; Orendt, A M; Alderman, D W; Pugmire, R J; Ye, C; Grant, D M

1994-08-01

The magic-angle turning (MAT) experiment introduced by Gan is developed into a powerful and routine method for measuring the principal values of 13C chemical shift tensors in powdered solids. A large-volume MAT probe with stable rotation frequencies down to 22 Hz is described. A triple-echo MAT pulse sequence is introduced to improve the quality of the two-dimensional baseplane. It is shown that measurements of the principal values of chemical shift tensors in complex compounds can be enhanced by using either short contact times or dipolar dephasing pulse sequences to isolate the powder patterns from protonated or non-protonated carbons, respectively. A model compound, 1,2,3-trimethoxybenzene, is used to demonstrate these techniques, and the 13C principal values in 2,3-dimethylnaphthalene and Pocahontas coal are reported as typical examples.

Permanent magnet assembly producing a strong tilted homogeneous magnetic field: towards magic angle field spinning NMR and MRI.

PubMed

Sakellariou, Dimitris; Hugon, Cédric; Guiga, Angelo; Aubert, Guy; Cazaux, Sandrine; Hardy, Philippe

2010-12-01

We introduce a cylindrical permanent magnet design that generates a homogeneous and strong magnetic field having an arbitrary inclination with respect to the axis of the cylinder. The analytical theory of 3 D magnetostatics has been applied to this problem, and a hybrid magnet structure has been designed. This structure contains two magnets producing a longitudinal and transverse component for the magnetic field, whose amplitudes and homogeneities can be fully controlled by design. A simple prototype has been constructed using inexpensive small cube magnets, and its magnetic field has been mapped using Hall and NMR probe sensors. This magnet can, in principle, be used for magic angle field spinning NMR and MRI experiments allowing for metabolic chemical shift profiling in small living animals. Copyright © 2010 John Wiley & Sons, Ltd.

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.

Characterization of molecular disorder in vapor-deposited thin films of aluminum tris(quinoline-8-olate) by one-dimensional 27Al NMR under magic angle spinning.

PubMed

Utz, Marcel; Nandagopal, Magesh; Mathai, Mathew; Papadimitrakopoulos, Fotios

2006-01-21

Aluminum tris (quinoline-8-olate) (Alq3) is used as an electron-transport layer in organic light-emitting diodes. The material can be obtained in a wide range of different solid phases, both crystalline and amorphous, by deposition from the vapor phase or from solution under controlled conditions. While the structure of the crystalline polymorphs of Alq3 has been investigated thoroughly by x-ray diffraction as well as solid-state NMR, very little information is currently available on the amount of structural disorder in the amorphous forms of Alq3. In the present contribution, we report the use of 27Al NMR spectroscopy in the solid state under magic angle spinning to extract such information from amorphous vapor deposits of Alq3. The NMR spectra obtained from these samples exhibit different degrees of broadening, reflecting distributions of the electric-field gradient tensor at the site of the aluminum ion. These distributions can be obtained from the NMR spectra by solving the corresponding inverse problem. From these results, the magnitude of structural disorder in terms of molecular geometry has been estimated by density-functional theory calculations. It was found that the electric-field gradient anisotropy delta follows a bimodal distribution. Its majority component is centered around delta values comparable to the meridianal alpha crystal polymorph and has a width of about 10%, corresponding to distortions of the molecular geometry of a few degrees in the orientation of the ligands. Alq3 samples obtained at higher deposition rates exhibit higher degrees of disorder. The minor component, present at about 7%, has a much smaller anisotropy, suggesting that it may be due to the facial isomer of Alq3.

Solid effect in magic angle spinning dynamic nuclear polarization

NASA Astrophysics Data System (ADS)

Corzilius, Björn; Smith, Albert A.; Griffin, Robert G.

2012-08-01

For over five decades, the solid effect (SE) has been heavily utilized as a mechanism for performing dynamic nuclear polarization (DNP). Nevertheless, it has not found widespread application in contemporary, high magnetic field DNP experiments because SE enhancements display an ω _0 ^{ - 2} field dependence. In particular, for nominally forbidden zero and double quantum SE transitions to be partially allowed, it is necessary for mixing of adjacent nuclear spin states to occur, and this leads to the observed field dependence. However, recently we have improved our instrumentation and report here an enhancement of ɛ = 91 obtained with the organic radical trityl (OX063) in magic angle spinning experiments performed at 5 T and 80 K. This is a factor of 6-7 higher than previous values in the literature under similar conditions. Because the solid effect depends strongly on the microwave field strength, we attribute this large enhancement to larger microwave field strengths inside the sample volume, achieved with more efficient coupling of the gyrotron to the sample chamber. In addition, we develop a theoretical model to explain the dependence of the buildup rate of enhanced nuclear polarization and the steady-state enhancement on the microwave power. Buildup times and enhancements were measured as a function of 1H concentration for both trityl and Gd-DOTA. Comparison of the results indicates that for trityl the initial polarization step is the slower, rate-determining step. However, for Gd-DOTA the spread of nuclear polarization via homonuclear 1H spin diffusion is rate-limiting. Finally, we discuss the applicability of the solid effect at fields > 5 T and the requirements to address the unfavorable field dependence of the solid effect.

The relationship between magical thinking, inferential confusion and obsessive-compulsive symptoms.

PubMed

Goods, N A R; Rees, C S; Egan, S J; Kane, R T

2014-01-01

Inferential confusion is an under-researched faulty reasoning process in obsessive-compulsive disorder (OCD). Based on an overreliance on imagined possibilities, it shares similarities with the extensively researched construct of thought-action fusion (TAF). While TAF has been proposed as a specific subset of the broader construct of magical thinking, the relationship between inferential confusion and magical thinking is unexplored. The present study investigated this relationship, and hypothesised that magical thinking would partially mediate the relationship between inferential confusion and obsessive-compulsive symptoms. A non-clinical sample of 201 participants (M = 34.94, SD = 15.88) were recruited via convenience sampling. Regression analyses found the hypothesised mediating relationship was supported, as magical thinking did partially mediate the relationship between inferential confusion and OC symptoms. Interestingly, inferential confusion had the stronger relationship with OC symptoms in comparison to the other predictor variables. Results suggest that inferential confusion can both directly and indirectly (via magical thinking) impact on OC symptoms. Future studies with clinical samples should further investigate these constructs to determine whether similar patterns emerge, as this may eventually inform which cognitive errors to target in treatment of OCD.

CO₂ adsorption on amine-functionalized periodic mesoporous benzenesilicas.

PubMed

Sim, Kyohyun; Lee, Nakwon; Kim, Joonseok; Cho, Eun-Bum; Gunathilake, Chamila; Jaroniec, Mietek

2015-04-01

CO2 adsorption was investigated on amine-functionalized mesoporous silica (SBA-15) and periodic mesoporous organosilica (PMO) samples. Hexagonally (p6mm) ordered mesoporous SBA-15 and benzene-PMO (BPMO) samples were prepared in the presence of Pluronic P123 block copolymer template under acidic conditions. Three kinds of amine-containing organosilanes and polyethylenimine were used to functionalize SBA-15 and BPMO. Small-angle X-ray scattering and nitrogen adsorption isotherms showed that these samples featured ordered mesostructure, high surface area, and narrow pore size distributions. Solid-state (13)C- and (29)Si cross-polarization magic-angle spinning NMR spectra showed chemical linkage between amine-containing modifiers and the surface of mesoporous materials. The chemically linked amine-containing modifiers were found to be on both the inner and outer surfaces. N-[3-(trimethoxysilyl)propyl]ethylenediamine-modified BPMO (A2-BPMO) sample exhibited the highest CO2 uptake (i.e., ∼3.03 mmol/g measured on a volumetric adsorption analyzer) and the fastest adsorption rate (i.e., ∼13 min to attain 90% of the maximum amount) among all the samples studied. Selectivity and reproducibility measurements for the A2-BPMO sample showed quite good performance in flowing N2 gas at 40 mL/min and CO2 gas of 60 mL/min at 25 °C.

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.

Minimal-assumption inference from population-genomic data

NASA Astrophysics Data System (ADS)

Weissman, Daniel; Hallatschek, Oskar

Samples of multiple complete genome sequences contain vast amounts of information about the evolutionary history of populations, much of it in the associations among polymorphisms at different loci. Current methods that take advantage of this linkage information rely on models of recombination and coalescence, limiting the sample sizes and populations that they can analyze. We introduce a method, Minimal-Assumption Genomic Inference of Coalescence (MAGIC), that reconstructs key features of the evolutionary history, including the distribution of coalescence times, by integrating information across genomic length scales without using an explicit model of recombination, demography or selection. Using simulated data, we show that MAGIC's performance is comparable to PSMC' on single diploid samples generated with standard coalescent and recombination models. More importantly, MAGIC can also analyze arbitrarily large samples and is robust to changes in the coalescent and recombination processes. Using MAGIC, we show that the inferred coalescence time histories of samples of multiple human genomes exhibit inconsistencies with a description in terms of an effective population size based on single-genome data.

Analysis of periprosthetic capsular tissue from women with silicone breast implants by magic-angle spinning NMR.

PubMed

Garrido, L; Young, V L

1999-09-01

The amount of silicone (polydimethylsiloxane [PDMS]) in capsular tissue surgically removed from women with breast implants was measured by using (29)Si and (1)H magic-angle spinning solid-state NMR spectroscopy. Twelve women having smooth surface silicone gel-filled implants, including a subject with "low-bleed" double-lumen implants, had detectable levels of PDMS ranging from 0. 05 to 9.8% silicon in wet tissue (w/w). No silicon-containing compounds other than PDMS were detected. No correlation was found between the amount of PDMS measured in the capsular tissue and the length of implantation time (Pearson correlation coefficient, r = 0. 22). The results showed no relationship between higher amounts of PDMS and capsular contracture (p = 0.74) or other symptoms (p = 0. 53). Magn Reson Med 42:436-441, 1999. Copyright 1999 Wiley-Liss, Inc.

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.

Tissue Characterization with Quantitative High-Resolution Magic Angle Spinning Chemical Exchange Saturation Transfer Z-Spectroscopy.

PubMed

Zhou, Iris Yuwen; Fuss, Taylor L; Igarashi, Takahiro; Jiang, Weiping; Zhou, Xin; Cheng, Leo L; Sun, Phillip Zhe

2016-11-01

Chemical exchange saturation transfer (CEST) provides sensitive magnetic resonance (MR) contrast for probing dilute compounds via exchangeable protons, serving as an emerging molecular imaging methodology. CEST Z-spectrum is often acquired by sweeping radiofrequency saturation around bulk water resonance, offset by offset, to detect CEST effects at characteristic chemical shift offsets, which requires prolonged acquisition time. Herein, combining high-resolution magic angle spinning (HRMAS) with concurrent application of gradient and rf saturation to achieve fast Z-spectral acquisition, we demonstrated the feasibility of fast quantitative HRMAS CEST Z-spectroscopy. The concept was validated with phantoms, which showed excellent agreement with results obtained from conventional HRMAS MR spectroscopy (MRS). We further utilized the HRMAS Z-spectroscopy for fast ex vivo quantification of ischemic injury with rodent brain tissues after ischemic stroke. This method allows rapid and quantitative CEST characterization of biological tissues and shows potential for a host of biomedical applications.

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

Effect of science magic applied in interactive lecture demonstrations on conceptual understanding

NASA Astrophysics Data System (ADS)

Taufiq, Muhammad; Suhandi, Andi; Liliawati, Winny

2017-08-01

Research about the application of science magic-assisting Interactive Lecture Demonstrations (ILD) has been conducted. This research is aimed at providing description about the comparison of the improvement of the conceptual understanding of lesson on pressure between students who receive physics lesson through science magic-assisting ILD and students who receive physics lesson through ILD without science magic. This research used a quasi-experiment methods with Control Group Pretest-Posttest Design. The subject of the research is all students of class VIII in one of MTs (Islamic junior high school) in Pekalongan. Research samples were selected using random sampling technique. Data about students' conceptual understanding was collected using test instrument of conceptual understanding in the form of multiple choices. N-gain average calculation was performed in order to determine the improvement of students' conceptual understanding. The result of the research shows that conceptual understanding of students on lesson about pressure who received lesson with ILD using science magic <0.44> is higher than students who received lesson with ILD without science magic <0.25>. Therefore, the conclusion is that the application of science magic ILD is more effective to improve the conceptual understanding of lesson on pressure.

Scattering on a rectangular potential barrier in nodal-line Weyl semimetals

NASA Astrophysics Data System (ADS)

Khokhlov, D. A.; Rakhmanov, A. L.; Rozhkov, A. V.

2018-06-01

We investigate single-particle ballistic scattering on a rectangular barrier in the nodal-line Weyl semimetals. Since the system under study has a crystallographic anisotropy, the scattering properties are dependent on mutual orientation of the crystalline axis and the barrier. To account for the anisotropy, we examine two different barrier orientations. It is demonstrated that, for certain angles of incidence, the incoming particle passes through the barrier with probability of unity. This is a manifestation of the Klein tunneling, a familiar phenomenon in the context of graphene and semimetals with Weyl points. However, the Klein tunneling in the Weyl-ring systems is observed when the angle of incidence differs from 90∘, unlike the cases of graphene and Weyl-point semimetals. The reflectionless transmission also occurs for the so-called "magic angles." The values of the magic angles are determined by geometrical resonances between the barrier width and the de Broglie length of the scattered particle. In addition, we show that under certain conditions the wave function of the transmitted and reflected particles may be a superposition of two plane waves with unequal momenta. Such a feature is a consequence of the nontrivial structure of the isoenergy surfaces of the nodal-line semimetals. Conductance of the barrier is briefly discussed.

Conformational study of 13C-enriched fibroin in the solid state, using the cross polarization nuclear magnetic resonance method.

PubMed

Fujiwara, T; Kobayashi, Y; Kyogoku, Y; Kataoka, K

1986-01-05

Silk fibroin with the alanyl carboxyl carbon enriched with 13C was obtained by giving a diet containing 13C-enriched alanine to the larvae of Bombyx mori and Antheraea pernyi at the fifth instar. Sericin-free fibroin fibers were prepared from cocoons, and gut was made from the liquid silk in the gland. The final 13C content was about 13%. Cross polarization/magic angle sample spinning spectra at 25 MHz and 75 MHz were measured for each sample at different orientations. Spectra were simulated using the principal values and orientations of the shielding tensor in the alanine crystal. The results indicate that the beta-structure of the fibroin may be a little more flattened than the typical pleated sheet beta-structure.

MAGIC gamma-ray telescopes hunting for neutrinos and their sources

NASA Astrophysics Data System (ADS)

Góra, D.; Bernardini, E.; Satalecka, K.; Noda, K.; Manganaro, M.; López, M.; MAGIC Collaboration

2017-09-01

The discovery of an astrophysical flux of high-energy neutrinos by the IceCube Collaboration marks a major breakthrough in the ongoing search for the origin of cosmic rays. Presumably, the neutrinos, together with gamma rays, result from pion decay, following hadronic interactions of protons accelerated in astrophysical objects to ultra-relativistic energies. So far, the neutrino sky map shows no significant indication of astrophysical sources. Here, we report first results from follow-up observations, of sky regions where IceCube has detected muon tracks from energetic neutrinos, using the MAGIC telescopes which are sensitive to gamma rays at TeV energies. Furthermore, we show that MAGIC has the potential to distinguish air showers induced by tau neutrinos from the background of hadronic showers in the PeV-EeV energy range, employing a novel analysis method to the data obtained with high-zenith angle observations.

Limitations in the use of commercial humic acids in water and soil research

USGS Publications Warehouse

Malcolm, R.L.; MacCarthy, P.

1986-01-01

Seven samples of commercial "humic acids", purchased from five different suppliers, were studied, and their characteristics were compared with humic and fulvic acids isolated from streams, soils, peat, leonardite, and a dopplerite sample. Cross-polarization and magic-angle spinning 13C NMR spectroscopy clearly shows pronounced differences between the commercial materials and all other samples. Elemental and infrared spectroscopic data do not show such clear-cut differences but can be used as supportive evidence, with the 13C NMR data, to substantiate the above distinctions. As a result of these differences and due to the general lack of information relating to the source, method of isolation, or other pretreatment of the commercial materials, these commercial products are not considered to be appropriate for use as analogues of true soil and water humic substances, in experiments designed to evaluate the nature and reactivity of humic substances in natural waters and soils.

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

Magical ideation is related to questionnaire but not behavioural measures of handedness.

PubMed

Grimshaw, Gina M; Yelle, Serena K; Schoger, Jamie; Bright, Kathleen S

2008-01-01

Magical ideation has repeatedly been shown to be related to handedness, with mixed-handers exhibiting higher levels of magical thinking. However, most previous research has assessed hand preference with a questionnaire measure, leaving open the possibility that the correlation reflects some aspect of questionnaire-taking behaviour and not an underlying neuropsychological relationship. The present study addressed this issue by administering the Magical Ideation Scale (Eckblad & Chapman, 1983), the Waterloo Handedness Questionnaire-Revised (Elias, Bryden, & Bulman-Fleming, 1998), and a manual dot-filling task (Tapley & Bryden, 1985) as a behavioural measure of handedness to an undergraduate student sample. The expected relationship between magical ideation and handedness as assessed by the questionnaire was observed. However, magical ideation was not related to the behavioural measure of handedness. Results cast doubt on a neuropsychological interpretation of the relationship between handedness and magical ideation in sub-clinical populations.

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.

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.

Staging research of human lung cancer tissues by high-resolution magic angle spinning proton nuclear magnetic resonance spectroscopy (HRMAS 1 H NMR) and multivariate data analysis.

PubMed

Chen, Wenxue; Lu, Shaohua; Wang, Guifang; Chen, Fener; Bai, Chunxue

2017-10-01

High-resolution magic-angle spinning proton nuclear magnetic resonance (HRMAS 1 H NMR) spectroscopy technique was employed to analyze the metabonomic characterizations of lung cancer tissues in hope to identify potential diagnostic biomarkers for malignancy detection and staging research of lung tissues. HRMAS 1 H NMR spectroscopy technique can rapidly provide important information for accurate diagnosis and staging of cancer tissues owing to its noninvasive nature and limited requirement for the samples, and thus has been acknowledged as an excellent tool to investigate tissue metabolism and provide a more realistic insight into the metabonomics of tissues when combined with multivariate data analysis (MVDA) such as component analysis and orthogonal partial least squares-discriminant analysis in particular. HRMAS 1 H NMR spectra displayed the metabonomic differences of 32 lung cancer tissues at the different stages from 32 patients. The significant changes (P < 0.05) of some important metabolites such as lipids, aspartate and choline-containing compounds in cancer tissues at the different stages had been identified. Furthermore, the combination of HRMAS 1 H NMR spectroscopy and MVDA might potentially and precisely provided for a high sensitivity, specificity, prediction accuracy in the positive identification of the staging for the cancer tissues in contrast with the pathological data in clinic. This study highlighted the potential of metabonomics in clinical settings so that the techniques might be further exploited for the diagnosis and staging prediction of lung cancer in future. © 2016 John Wiley & Sons Australia, Ltd.

A comparison of various algorithms to extract Magic Formula tyre model coefficients for vehicle dynamics simulations

NASA Astrophysics Data System (ADS)

Vijay Alagappan, A.; Narasimha Rao, K. V.; Krishna Kumar, R.

2015-02-01

Tyre models are a prerequisite for any vehicle dynamics simulation. Tyre models range from the simplest mathematical models that consider only the cornering stiffness to a complex set of formulae. Among all the steady-state tyre models that are in use today, the Magic Formula tyre model is unique and most popular. Though the Magic Formula tyre model is widely used, obtaining the model coefficients from either the experimental or the simulation data is not straightforward due to its nonlinear nature and the presence of a large number of coefficients. A common procedure used for this extraction is the least-squares minimisation that requires considerable experience for initial guesses. Various researchers have tried different algorithms, namely, gradient and Newton-based methods, differential evolution, artificial neural networks, etc. The issues involved in all these algorithms are setting bounds or constraints, sensitivity of the parameters, the features of the input data such as the number of points, noisy data, experimental procedure used such as slip angle sweep or tyre measurement (TIME) procedure, etc. The extracted Magic Formula coefficients are affected by these variants. This paper highlights the issues that are commonly encountered in obtaining these coefficients with different algorithms, namely, least-squares minimisation using trust region algorithms, Nelder-Mead simplex, pattern search, differential evolution, particle swarm optimisation, cuckoo search, etc. A key observation is that not all the algorithms give the same Magic Formula coefficients for a given data. The nature of the input data and the type of the algorithm decide the set of the Magic Formula tyre model coefficients.

The role of magical thinking in Obsessive-Compulsive Disorder symptoms and cognitions in an analogue sample.

PubMed

Yorulmaz, Orçun; Inozu, Mujgan; Gültepe, Bedirhan

2011-06-01

In addition to clinical observations exemplifying biased reasoning styles (e.g., overemphasis of thoughts) and particular ritualistic behaviors, it is also empirically supported that magical beliefs are also associated with Obsessive-Compulsive Disorder (OCD) symptoms and some cognitions. It should be noted, however, that most empirical studies have been carried out on the samples from Western cultures, even though these beliefs were culturally determined. Thus, more research is needed in order to understand their roles in the OCD symptoms in different cultural contexts. The present study aimed to examine the impact of magical beliefs in OCD symptoms, cognitions and thought control in a non-Western analogue sample from Turkey. The measures of paranormal beliefs, fusion of thoughts-actions, obsessive beliefs, strategies of thought control and OCD symptoms were administered to an undergraduate sample. Consistent with findings in the literature, the analyses of group comparisons, correlation and regression showed that even after controlling general negative affect, magical beliefs were still associated with OCD symptoms, some beliefs and control strategies, namely the symptoms of obsessional thoughts and checking, fusions of thoughts and actions in likelihood, faulty beliefs in perfectionism-certainty and punishment. Some methodological concerns such as cross-sectional nature, inclusion of only non-clinical sample were major restrictions of the present study. Evidence that magical thinking is a critical factor in the OCD is supported once more in a different cultural context. Copyright © 2010 Elsevier Ltd. All rights reserved.

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.

Magical Thinking, Causation and Prediction: Psycholinguistic Implications for Reading Skills in Disturbed Children.

ERIC Educational Resources Information Center

Buescher, Thomas M.

Operant magical thinking (belief that thought can significantly alter reality) and reading comprehension were examined in samples of Pupils 7 to 13 years old identified as either gifted, normal, or emotionally disturbed. Sixty-eight children were sampled in a school for gifted children, in a regular suburban elementary school, and in an in-patient…

A High-Resolution 3D Separated-Local-Field Experiment by Means of Magic-Angle Turning

PubMed

Hu; Alderman; Pugmire; Grant

1997-05-01

A 3D separated-local-field (SLF) experiment based on the 2D PHORMAT technique is described. In the 3D experiment, the conventional 2D SLF powder pattern for each chemically inequivalent carbon is separated according to their different isotropic chemical shifts. The dipolar coupling constant of a C-H pair, hence the bond distance, and the relative orientation of the chemical-shift tensor to the C-H vector can all be determined for the protonated carbons with a single measurement. As the sample turns at only about 30 Hz in a MAT experiment, the SLF patterns obtained approach those of a stationary sample, and an accuracy in the measurement similar to that obtained on a stationary sample is expected. The technique is demonstrated on 2,6-dimethoxynaphthalene, where the 13 C-1 H separated-local-field powder patterns for the six chemically inequivalent carbons are clearly identified and measured. The observed dipolar coupling for the methoxy carbon is effectively reduced by the fast rotation of the group about its C3 symmetry axis. The average angle between the C-H bond direction and the C3 rotation axis in the OCH3 group is found to be about 66°.

Evaluation of magical thinking: validation of the Illusory Beliefs Inventory.

PubMed

Shihata, Sarah; Egan, Sarah J; Rees, Clare S

2014-01-01

Magical thinking has been related to obsessive-compulsive disorder; yet, little research has examined this construct in other anxiety disorders. The Illusory Beliefs Inventory (IBI) is a recently developed measure of magical thinking. The aim of this study was to investigate the psychometric properties of this new measure and to determine if magical thinking accounts for pathological worry beyond the well-researched constructs of intolerance of uncertainty (IU) and perfectionism. A sample of 502 participants completed an online survey. Confirmatory factor analysis identified a three-factor solution for the IBI, and the measure had good internal consistency (α = .92), test-retest reliability (r = .94) and discriminant validity. Magical thinking, IU, and perfectionism all predicted pathological worry; however, magical thinking accounted for less than 1% of unique variance in worry, suggesting that it is not strongly related to worry. Further investigation regarding the validity and clinical utility of the IBI is required.

Irrigation, fertilization and initial substrate quality effects on decomposing Loblolly pine litter chemistry

Treesearch

Felipe G. Sanchez

2004-01-01

Changes in carbon chemistry (i.e., carbon compound classes such as aromatics, phenolics, etc.) of loblolly pine (Pinus taeda L.) litter were examined during three years of decomposition under factorial combinations of irrigation and fertilization treatments. Cross polarization magic angle spinning 13C nuclear magnetic resonance...

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.

Sensitivity enhancements in MQ-MAS NMR of spin-5/2 nuclei using modulated rf mixing pulses

NASA Astrophysics Data System (ADS)

Vosegaard, Thomas; Massiot, Dominique; Grandinetti, Philip J.

2000-08-01

An X- overlineX pulse train with stepped modulation frequency was employed to enhance the multiple-quantum to single-quantum coherence transfer in the mixing period of the multiple-quantum magic-angle spinning (MQ-MAS) experiment for spin I=5/2 nuclei. Two MQ-MAS pulse sequences employing this mixing scheme for the triple-to-single and quintuple-to-single quantum coherence transfers have been designed and their performance is demonstrated for 27Al on samples of NaSi 3AlO 8 and 9Al 2O 3·2B 2O 3 . Compared to the standard single-pulse mixing sequences, the sensitivity is approximately doubled in the present experiments.

13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Cronin, J. R.; Pizzarello, S.; Frye, J. S.

1987-01-01

13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

Improved heteronuclear dipolar decoupling sequences for liquid-crystal NMR

NASA Astrophysics Data System (ADS)

Thakur, Rajendra Singh; Kurur, Narayanan D.; Madhu, P. K.

2007-04-01

Recently we introduced a radiofrequency pulse scheme for heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance under magic-angle spinning [R.S. Thakur, N.D. Kurur, P.K. Madhu, Swept-frequency two-pulse phase modulation for heteronuclear dipolar decoupling in solid-state NMR, Chem. Phys. Lett. 426 (2006) 459-463]. Variants of this sequence, swept-frequency TPPM, employing frequency modulation of different types have been further tested to improve the efficiency of heteronuclear dipolar decoupling. Among these, certain sequences that were found to perform well at lower spinning speeds are demonstrated here on a liquid-crystal sample of MBBA for application in static samples. The new sequences are compared with the standard TPPM and SPINAL schemes and are shown to perform better than them. These modulated schemes perform well at low decoupler radiofrequency power levels and are easy to implement on standard spectrometers.

Towards wide-angle neutron polarization analysis with a 3He spin filter for TOPAS and NEAT: Testing magic PASTIS on V20 at HZB

NASA Astrophysics Data System (ADS)

Babcock, Earl; Salhi, Zahir; Gainov, Ramil; Woracek, Robin; Soltner, Helmut; Pistel, Patrick; Beule, Fabian; Bussmann, Klaus; Heynen, Achim; Kämmerling, Hans; Suxdorf, Frank; Strobl, Marcus; Russina, Margarita; Voigt, Jörg; Ioffe, Alexander

2018-05-01

An XYZ polarization analysis solution has been developed for the new thermal time-of-flight spectrometer TOPAS [1], to be operated in the coming east neutron guide hall at the MLZ. This prototype is currently being prepared to use on NEAT at HZB [2]. Polarization Analysis Studies on a Thermal Inelastic Spectrometer, commonly called PASTIS [3], is based on polarized 3He neutron spin filters and an XYZ field configuration for the sample environment and a polarization-preserving neutron guide field. The complete system was designed to provide adiabatic transport of the neutron polarization to the sample position on TOPAS while maintaining the homogeneity of the XYZ field. This complete system has now been tested on the polarized time-of-flight ESS test beam line V20 at HZB [4]. We present results of this test and the next steps forward.

Correlated insulator behaviour at half-filling in magic-angle graphene superlattices

NASA Astrophysics Data System (ADS)

Cao, Yuan; Fatemi, Valla; Demir, Ahmet; Fang, Shiang; Tomarken, Spencer L.; Luo, Jason Y.; Sanchez-Yamagishi, Javier D.; Watanabe, Kenji; Taniguchi, Takashi; Kaxiras, Efthimios; Ashoori, Ray C.; Jarillo-Herrero, Pablo

2018-04-01

A van der Waals heterostructure is a type of metamaterial that consists of vertically stacked two-dimensional building blocks held together by the van der Waals forces between the layers. This design means that the properties of van der Waals heterostructures can be engineered precisely, even more so than those of two-dimensional materials. One such property is the ‘twist’ angle between different layers in the heterostructure. This angle has a crucial role in the electronic properties of van der Waals heterostructures, but does not have a direct analogue in other types of heterostructure, such as semiconductors grown using molecular beam epitaxy. For small twist angles, the moiré pattern that is produced by the lattice misorientation between the two-dimensional layers creates long-range modulation of the stacking order. So far, studies of the effects of the twist angle in van der Waals heterostructures have concentrated mostly on heterostructures consisting of monolayer graphene on top of hexagonal boron nitride, which exhibit relatively weak interlayer interaction owing to the large bandgap in hexagonal boron nitride. Here we study a heterostructure consisting of bilayer graphene, in which the two graphene layers are twisted relative to each other by a certain angle. We show experimentally that, as predicted theoretically, when this angle is close to the ‘magic’ angle the electronic band structure near zero Fermi energy becomes flat, owing to strong interlayer coupling. These flat bands exhibit insulating states at half-filling, which are not expected in the absence of correlations between electrons. We show that these correlated states at half-filling are consistent with Mott-like insulator states, which can arise from electrons being localized in the superlattice that is induced by the moiré pattern. These properties of magic-angle-twisted bilayer graphene heterostructures suggest that these materials could be used to study other exotic many-body quantum phases in two dimensions in the absence of a magnetic field. The accessibility of the flat bands through electrical tunability and the bandwidth tunability through the twist angle could pave the way towards more exotic correlated systems, such as unconventional superconductors and quantum spin liquids.

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.

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...

New mechanistic insights regarding Pd/Cu catalysts for the Sonogashira reaction: HRMAS NMR studies of silica-immobilized systems.

PubMed

Posset, Tobias; Blümel, Janet

2006-07-05

The title technique, high-resolution magic angle spinning NMR of suspensions, constitutes a powerful new tool for investigating the structures and mobilities of immobilized species and, thus, for optimizing heterobimetallic catalyst systems, such as the Sonogashira coupling of terminal alkynes and aryl halides.

Magic-angle spinning NMR of a class I filamentous bacteriophage virus.

PubMed

Abramov, Gili; Morag, Omry; Goldbourt, Amir

2011-08-11

The fd bacteriophage is a filamentous virus that is widely used for bio- and nanotechnology applications ranging from phage display to battery materials. The possibility of obtaining a detailed description of its structural properties regardless of its state is therefore essential not only for understanding its physical arrangement and its bacterial infection process but also for many other applications. Here we present a study of the fd phage by magic-angle spinning solid-state NMR. While current structures rely on a Y21M mutant, experiments performed on a strain bearing a wild-type capsid report on high symmetry of the phage and lack of explicit subunit polymorphism. Chemical shift analysis confirmed that the coat protein mostly consists of a rigid right-handed curved α-helix (residues 6-47 of 50), preceded by a flexible loop-structured N-terminus. We were able to qualitatively assign the resonances belonging to the DNA, including the deoxyribose sugars and the thymine bases. These chemical shifts are consistent with base stacking and a C2'-endo/C3'-exo sugar pucker. © 2011 American Chemical Society

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

A unified heteronuclear decoupling strategy for magic-angle-spinning solid-state NMR spectroscopy

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

Equbal, Asif; Bjerring, Morten; Nielsen, Niels Chr., E-mail: madhu@tifr.res.in, E-mail: ncn@inano.au.dk

2015-05-14

A unified strategy of two-pulse based heteronuclear decoupling for solid-state magic-angle spinning nuclear magnetic resonance is presented. The analysis presented here shows that different decoupling sequences like two-pulse phase-modulation (TPPM), X-inverse-X (XiX), and finite pulse refocused continuous wave (rCW{sup A}) are basically specific solutions of a more generalized decoupling scheme which incorporates the concept of time-modulation along with phase-modulation. A plethora of other good decoupling conditions apart from the standard, TPPM, XiX, and rCW{sup A} decoupling conditions are available from the unified decoupling approach. The importance of combined time- and phase-modulation in order to achieve the best decoupling conditions ismore » delineated. The consequences of different indirect dipolar interactions arising from cross terms comprising of heteronuclear and homonuclear dipolar coupling terms and also those between heteronuclear dipolar coupling and chemical-shift anisotropy terms are presented in order to unfold the effects of anisotropic interactions under different decoupling conditions. Extensive numerical simulation results are corroborated with experiments on standard amino acids.« less

Evaluation of Cancer Metabolomics Using ex vivo High Resolution Magic Angle Spinning (HRMAS) Magnetic Resonance Spectroscopy (MRS)

PubMed Central

Fuss, Taylor L.; Cheng, Leo L.

2016-01-01

According to World Health Organization (WHO) estimates, cancer is responsible for more deaths than all coronary heart disease or stroke worldwide, serving as a major public health threat around the world. High resolution magic angle spinning (HRMAS) magnetic resonance spectroscopy (MRS) has demonstrated its usefulness in the identification of cancer metabolic markers with the potential to improve diagnosis and prognosis for the oncology clinic, due partially to its ability to preserve tissue architecture for subsequent histological and molecular pathology analysis. Capable of the quantification of individual metabolites, ratios of metabolites, and entire metabolomic profiles, HRMAS MRS is one of the major techniques now used in cancer metabolomic research. This article reviews and discusses literature reports of HRMAS MRS studies of cancer metabolomics published between 2010 and 2015 according to anatomical origins, including brain, breast, prostate, lung, gastrointestinal, and neuroendocrine cancers. These studies focused on improving diagnosis and understanding patient prognostication, monitoring treatment effects, as well as correlating with the use of in vivo MRS in cancer clinics. PMID:27011205

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.

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.

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.

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

Managing Rock and Paleomagnetic Data Flow with the MagIC Database: from Measurement and Analysis to Comprehensive Archive and Visualization

NASA Astrophysics Data System (ADS)

Koppers, A. A.; Minnett, R. C.; Tauxe, L.; Constable, C.; Donadini, F.

2008-12-01

The Magnetics Information Consortium (MagIC) is commissioned to implement and maintain an online portal to a relational database populated by rock and paleomagnetic data. The goal of MagIC is to archive all measurements and derived properties for studies of paleomagnetic directions (inclination, declination) and intensities, and for rock magnetic experiments (hysteresis, remanence, susceptibility, anisotropy). Organizing data for presentation in peer-reviewed publications or for ingestion into databases is a time-consuming task, and to facilitate these activities, three tightly integrated tools have been developed: MagIC-PY, the MagIC Console Software, and the MagIC Online Database. A suite of Python scripts is available to help users port their data into the MagIC data format. They allow the user to add important metadata, perform basic interpretations, and average results at the specimen, sample and site levels. These scripts have been validated for use as Open Source software under the UNIX, Linux, PC and Macintosh© operating systems. We have also developed the MagIC Console Software program to assist in collating rock and paleomagnetic data for upload to the MagIC database. The program runs in Microsoft Excel© on both Macintosh© computers and PCs. It performs routine consistency checks on data entries, and assists users in preparing data for uploading into the online MagIC database. The MagIC website is hosted under EarthRef.org at http://earthref.org/MAGIC/ and has two search nodes, one for paleomagnetism and one for rock magnetism. Both nodes provide query building based on location, reference, methods applied, material type and geological age, as well as a visual FlashMap interface to browse and select locations. Users can also browse the database by data type (inclination, intensity, VGP, hysteresis, susceptibility) or by data compilation to view all contributions associated with previous databases, such as PINT, GMPDB or TAFI or other user-defined compilations. Query results are displayed in a digestible tabular format allowing the user to descend from locations to sites, samples, specimens and measurements. At each stage, the result set can be saved and, when supported by the data, can be visualized by plotting global location maps, equal area, XY, age, and depth plots, or typical Zijderveld, hysteresis, magnetization and remanence diagrams.

Magical ideation modulates spatial behavior.

PubMed

Mohr, Christine; Bracha, H Stefan; Brugger, Peter

2003-01-01

Previous research has found that animals as well as persons with psychotic disorders preferentially orient away from the cerebral hemisphere with the more active dopamine system. This study investigated the modulation of spatial behavior by a mode of thinking reminiscent of the positive symptoms of psychosis. In a non-treatment-seeking sample of healthy volunteers (20 women and 16 men), the authors assessed the lateral biases in turning and veering behavior and in line bisection as a function of their magical ideation, that is, a mild form of schizotypy. Across tasks, pronounced magical ideation was associated with reduced right-sided orientation preferences. This finding suggests a relative hyperdopaminergia of the right hemisphere as the biological basis of magical ideation.

Polymorphism in magic-sized Au144(SR)60 clusters

NASA Astrophysics Data System (ADS)

Jensen, Kirsten M. Ø.; Juhas, Pavol; Tofanelli, Marcus A.; Heinecke, Christine L.; Vaughan, Gavin; Ackerson, Christopher J.; Billinge, Simon J. L.

2016-06-01

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.

Measurement and interpretation of electron angle at MABE beam stop

NASA Astrophysics Data System (ADS)

Sanford, T. W. L.; Coleman, P. D.; Poukey, J. W.

1985-02-01

The mean angle of incidence at the beam stop of a 60 kA, 7 MV annular electron beam, in the 20 kG guide field of the MABE accelerator, was determined. Radiation dose measured in TLD arrays mounted downstream of the stop is compared with the radiation dose expected using a CYLTRAN Monte Carlo simulation of the electron/photon transport in the stop as a function of incident angles and energies. All radiation profiles measured are well fit, if the electrons are assumed to be incident with a polar angle theta of 15(0) + or - 2(0). A comparison of theta with that expected from the Adler-Miller model, and a MAGIC code simulation of beam behavior at the stop enables the mean transverse beam velocity to be estimated.

Measurement of electron angle at MABE beam stop

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

Sanford, T.W.L.; Coleman, P.D.; Poukey, J.W.

1984-01-01

The mean angle of incidence at the beam stop of a 60 KA, 7 MV annular electron beam, in the 20 kg guide field of the MABE accelerator, is determined. Radiation measured in TLD arrays mounted downstream of the stop is compared with the radiation expected using a CYLTRAN Monte Carlo simulation of the electron/photon transport in the stop as a function of incident angles and energies. All radiation profiles measured are well fit, if the electrons are assumed to be incident with a polar angle theta of 15/sup 0/ +- 2/sup 0/. Comparing theta with that expected from themore » Adler-Miller model, and a MAGIC code simulation of beam behavior at the stop enables the mean transverse beam velocity to be estimated.« less

Quantum phases of quadrupolar Fermi gases in coupled one-dimensional systems

NASA Astrophysics Data System (ADS)

Huang, Wen-Min; Lahrz, M.; Mathey, L.

2014-01-01

Following the recent proposal to create quadrupolar gases [Bhongale et al., Phys. Rev. Lett. 110, 155301 (2013), 10.1103/PhysRevLett.110.155301], we investigate what quantum phases can be created in these systems in one dimension. We consider a geometry of two coupled one-dimensional (1D) systems, and derive the quantum phase diagram of ultracold fermionic atoms interacting via quadrupole-quadrupole interactions within a Tomonaga-Luttinger-liquid framework. We map out the phase diagram as a function of the distance between the two tubes and the angle between the direction of the tubes and the quadrupolar moments. The latter can be controlled by an external field. We show that there are two magic angles θB,1c and θB,2c between 0 and π /2, where the intratube quadrupolar interactions vanish and change signs. Adopting a pseudospin language with regard to the two 1D systems, the system undergoes a spin-gap transition and displays a zigzag density pattern, above θB,2c and below θB,1c. Between the two magic angles, we show that polarized triplet superfluidity and a planar spin-density-wave order compete with each other. The latter corresponds to a bond-order solid in higher dimensions. We demonstrate that this order can be further stabilized by applying a commensurate periodic potential along the tubes.

Proton decoupling and recoupling under double-nutation irradiation in solid-state NMR

NASA Astrophysics Data System (ADS)

Takeda, Kazuyuki; Wakisaka, Asato; Takegoshi, K.

2014-12-01

The effect of 1H decoupling in magic-angle spinning solid-state NMR is studied under radiofrequency irradiation causing simultaneous nutations around a pair of orthogonal axes. Double-nutation with an arbitrary pair of nutation frequencies is implemented through modulation of the amplitude, phase, and frequency of the transmitting pulses. Similarity and difference of double-nutation decoupling and two-pulse phase-modulation decoupling schemes [A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, and R. G. Griffin, J. Chem. Phys. 103, 6951-6958 (1995) and I. Scholz, P. Hodgkinson, B. H. Meier, and M. Ernst, J. Chem. Phys. 130, 114510 (2009)] are discussed. The structure of recoupling bands caused by interference of the 1H spin nutation with sample spinning is studied by both experiments and numerical simulations.

Overhauser effects in non-conducting solids at 1.2 K

NASA Astrophysics Data System (ADS)

Ji, X.; Can, T. V.; Mentink-Vigier, F.; Bornet, A.; Milani, J.; Vuichoud, B.; Caporini, M. A.; Griffin, R. G.; Jannin, S.; Goldman, M.; Bodenhausen, G.

2018-01-01

Recently, it was observed that protons in non-conducting solids doped with 1,3-bisdiphenylene-2-phenylallyl (BDPA) or its sulfonated derivative (SA-BDPA) can be polarized through Overhauser effects via resonant microwave irradiation. These effects were present under magic angle spinning conditions in magnetic fields between 5 and 18.8 T and at temperatures near 100 K. This communication reports similar effects in static samples at 6.7 T and, more importantly, at temperatures as low as 1.2 K, in a different dynamic regime than in the previous study. Our results provide new information towards understanding the mechanism of the Overhauser effect in non-conducting solids. We discuss possible origins of the fluctuations that can give rise to an Overhauser effect at such low temperatures.

An fMRI investigation of expectation violation in magic tricks.

PubMed

Danek, Amory H; Öllinger, Michael; Fraps, Thomas; Grothe, Benedikt; Flanagin, Virginia L

2015-01-01

Magic tricks violate the expected causal relationships that form an implicit belief system about what is possible in the world around us. Observing a magic effect seemingly invalidates our implicit assumptions about what action causes which outcome. We aimed at identifying the neural correlates of such expectation violations by contrasting 24 video clips of magic tricks with 24 control clips in which the expected action-outcome relationship is upheld. Using fMRI, we measured the brain activity of 25 normal volunteers while they watched the clips in the scanner. Additionally, we measured the professional magician who had performed the magic tricks under the assumption that, in contrast to naïve observers, the magician himself would not perceive his own magic tricks as an expectation violation. As the main effect of magic - control clips in the normal sample, we found higher activity for magic in the head of the caudate nucleus (CN) bilaterally, the left inferior frontal gyrus and the left anterior insula. As expected, the magician's brain activity substantially differed from these results, with mainly parietal areas (supramarginal gyrus bilaterally) activated, supporting our hypothesis that he did not experience any expectation violation. These findings are in accordance with previous research that has implicated the head of the CN in processing changes in the contingency between action and outcome, even in the absence of reward or feedback.

Optimized multiple quantum MAS lineshape simulations in solid state NMR

NASA Astrophysics Data System (ADS)

Brouwer, William J.; Davis, Michael C.; Mueller, Karl T.

2009-10-01

The majority of nuclei available for study in solid state Nuclear Magnetic Resonance have half-integer spin I>1/2, with corresponding electric quadrupole moment. As such, they may couple with a surrounding electric field gradient. This effect introduces anisotropic line broadening to spectra, arising from distinct chemical species within polycrystalline solids. In Multiple Quantum Magic Angle Spinning (MQMAS) experiments, a second frequency dimension is created, devoid of quadrupolar anisotropy. As a result, the center of gravity of peaks in the high resolution dimension is a function of isotropic second order quadrupole and chemical shift alone. However, for complex materials, these parameters take on a stochastic nature due in turn to structural and chemical disorder. Lineshapes may still overlap in the isotropic dimension, complicating the task of assignment and interpretation. A distributed computational approach is presented here which permits simulation of the two-dimensional MQMAS spectrum, generated by random variates from model distributions of isotropic chemical and quadrupole shifts. Owing to the non-convex nature of the residual sum of squares (RSS) function between experimental and simulated spectra, simulated annealing is used to optimize the simulation parameters. In this manner, local chemical environments for disordered materials may be characterized, and via a re-sampling approach, error estimates for parameters produced. Program summaryProgram title: mqmasOPT Catalogue identifier: AEEC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEEC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 3650 No. of bytes in distributed program, including test data, etc.: 73 853 Distribution format: tar.gz Programming language: C, OCTAVE Computer: UNIX/Linux Operating system: UNIX/Linux Has the code been vectorised or parallelized?: Yes RAM: Example: (1597 powder angles) × (200 Samples) × (81 F2 frequency pts) × (31 F1 frequency points) = 3.5M, SMP AMD opteron Classification: 2.3 External routines: OCTAVE ( http://www.gnu.org/software/octave/), GNU Scientific Library ( http://www.gnu.org/software/gsl/), OPENMP ( http://openmp.org/wp/) Nature of problem: The optimal simulation and modeling of multiple quantum magic angle spinning NMR spectra, for general systems, especially those with mild to significant disorder. The approach outlined and implemented in C and OCTAVE also produces model parameter error estimates. Solution method: A model for each distinct chemical site is first proposed, for the individual contribution of crystallite orientations to the spectrum. This model is averaged over all powder angles [1], as well as the (stochastic) parameters; isotropic chemical shift and quadrupole coupling constant. The latter is accomplished via sampling from a bi-variate Gaussian distribution, using the Box-Muller algorithm to transform Sobol (quasi) random numbers [2]. A simulated annealing optimization is performed, and finally the non-linear jackknife [3] is applied in developing model parameter error estimates. Additional comments: The distribution contains a script, mqmasOpt.m, which runs in the OCTAVE language workspace. Running time: Example: (1597 powder angles) × (200 Samples) × (81 F2 frequency pts) × (31 F1 frequency points) = 58.35 seconds, SMP AMD opteron. References:S.K. Zaremba, Annali di Matematica Pura ed Applicata 73 (1966) 293. H. Niederreiter, Random Number Generation and Quasi-Monte Carlo Methods, SIAM, 1992. T. Fox, D. Hinkley, K. Larntz, Technometrics 22 (1980) 29.

Radiological properties of MAGIC normoxic polymer gel dosimetry

NASA Astrophysics Data System (ADS)

Aljamal, M.; Zakaria, A.; Shamsuddin, S.

2013-04-01

For a polymer gel dosimeter to be of use in radiation dosimetry, it should display water-equivalent radiological properties. In this study, the radiological properties of the MAGIC (Methacrylic and Ascorbic acid in Gelatin Initiated by Copper) normoxic polymer gels were investigated. The mass density (ρ) was determined based on Archimedes' principle. The weight fraction of elemental composition and the effective atomic number (Zeff) were calculated. The electron density was also measured with 90° scattering angle at room temperature. The linear attenuation coefficient (μ) of unirradiated gel, irradiated gel, and water were determined using Am-241 based on narrow beam geometry. Monte Carlo simulation was used to calculate the depth doses response of MAGIC gel and water for 6MV photon beam. The weight fractions of elements composition of MAGIC gel were close to that for water. The mass density was found to be 1027 ± 2 kg m-3, which is also very close to mass density of muscle tissue (1030 kg m-3) and 2.7% higher than that of water. The electron density (ρe) and atomic number (Zeff) were found to be 3.43 × 1029 e m-3 and 7.105, respectively. The electron density measured was 2.6% greater than that for water. The atomic number was very close to that for water. The prepared MAGIC gel was found to be water equivalent based on the study of element composition, mass density, electron density and atomic number. The linear attenuation coefficient of unirradiated gel was very close to that of water. The μ of irradiated gel was found to be linear with dose 2-40 Gy. The depth dose response for MAGIC gel from a 6 MV photon beam had a percentage dose difference to water of less than 1%. Therefore it satisfies the criteria to be a good polymer gel dosimeter for radiotherapy.

Polymorphism in magic-sized Au144(SR)60 clusters

DOE PAGES

Jensen, Kirsten M. O.; Juhas, Pavol; Tofanelli, Marcus A.; ...

2016-06-14

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. We present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. Our study reveals structural polymorphism in these archetypal nanoclusters. Additionally, in order to confirm the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. Finally,more » the discovery of polymorphism may open up a new dimension in nanoscale engineering.« less

Do cultural factors affect causal beliefs? Rational and magical thinking in Britain and Mexico.

PubMed

Subbotsky, Eugene; Quinteros, Graciela

2002-11-01

In two experiments, unusual phenomena (spontaneous destruction of objects in an empty wooden box) were demonstrated to adult participants living in rural communities in Mexico. These were accompanied by actions which had no physical link to the destroyed object but could suggest either scientifically based (the effect of an unknown physical device) or non-scientifically based (the effect of a 'magic spell') causal explanations of the event. The results were compared to the results of the matching two experiments from the earlier study made in Britain. The expectation that scientifically based explanations would prevail in British participants' judgments and behaviours, whereas Mexican participants would be more tolerant toward magical explanations, received only partial support. The prevalence of scientific explanations over magical explanations was evident in British participants' verbal judgments but not in Mexican participants' judgments. In their behavioural responses under the low-risk condition, British participants rejected magical explanations more frequently than did Mexican participants. However, when the risk of disregarding the possible causal effect of magic was increased, participants in both samples showed an equal degree of credulity in the possible effect of magic. The data are interpreted in terms of the relationships between scientific and 'folk' representations of causality and object permanence.

Metabolic profiling of lung granuloma in Mycobacterium tuberculosis infected guinea pigs: ex vivo 1H magic angle spinning NMR studies.

PubMed

Somashekar, B S; Amin, Anita G; Rithner, Christopher D; Troudt, JoLynn; Basaraba, Randall; Izzo, Angelo; Crick, Dean C; Chatterjee, Delphi

2011-09-02

A crucial and distinctive feature of tuberculosis infection is that Mycobacterium tuberculosis (Mtb) resides in granulomatous lesion at various stages of disease development and necrosis, an aspect that is little understood. We used a novel approach, applying high resolution magic angle spinning nuclear magnetic resonance spectroscopy (HRMAS NMR) directly to infected tissues, allowing us to study the development of tuberculosis granulomas in guinea pigs in an untargeted manner. Significant up-regulation of lactate, alanine, acetate, glutamate, oxidized and the reduced form of glutathione, aspartate, creatine, phosphocholine, glycerophosphocholine, betaine, trimethylamine N-oxide, myo-inositol, scyllo-inositol, and dihydroxyacetone was clearly visualized and was identified as the infection progressed. Concomitantly, phosphatidylcholine was down-regulated. Principal component analysis of NMR data revealed clear group separation between infected and uninfected tissues. These metabolites are suggestive of utilization of alternate energy sources by the infiltrating cells that generate much of the metabolites in the increasingly necrotic and hypoxic developing granuloma through the glycolytic, pentose phosphate, and tricarboxylic acid pathways. The most relevant changes seen are, surprisingly, very similar to metabolic changes seen in cancer during tumor development.

Q(n) species distribution in K2O.2SiO2 glass by 29Si magic angle flipping NMR.

PubMed

Davis, Michael C; Kaseman, Derrick C; Parvani, Sahar M; Sanders, Kevin J; Grandinetti, Philip J; Massiot, Dominique; Florian, Pierre

2010-05-06

Two-dimensional magic angle flipping (MAF) was employed to measure the Q((n)) distribution in a (29)Si-enriched potassium disilicate glass (K(2)O.2SiO(2)). Relative concentrations of [Q((4))] = 7.2 +/- 0.3%, [Q((3))] = 82.9 +/- 0.1%, and [Q((2))] = 9.8 +/- 0.6% were obtained. Using the thermodynamic model for Q((n)) species disproportionation, these relative concentrations yield an equilibrium constant k(3) = 0.0103 +/- 0.0008, indicating, as expected, that the Q((n)) species distribution is close to binary in the potassium disilicate glass. A Gaussian distribution of isotropic chemical shifts was observed for each Q((n)) species with mean values of -82.74 +/- 0.03, -91.32 +/- 0.01, and -101.67 +/- 0.02 ppm and standard deviations of 3.27 +/- 0.03, 4.19 +/- 0.01, and 5.09 +/- 0.03 ppm for Q((2)), Q((3)), and Q((4)), respectively. Additionally, nuclear shielding anisotropy values of zeta =-85.0 +/- 1.3 ppm, eta = 0.48 +/- 0.02 for Q((2)) and zeta = -74.9 +/- 0.2 ppm, eta = 0.03 +/- 0.01 for Q((3)) were observed in the potassium disilicate glass.

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.

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.

Chemical Shifts of the Carbohydrate Binding Domain of Galectin-3 from Magic Angle Spinning NMR and Hybrid Quantum Mechanics/Molecular Mechanics Calculations.

PubMed

Kraus, Jodi; Gupta, Rupal; Yehl, Jenna; Lu, Manman; Case, David A; Gronenborn, Angela M; Akke, Mikael; Polenova, Tatyana

2018-03-22

Magic angle spinning NMR spectroscopy is uniquely suited to probe the structure and dynamics of insoluble proteins and protein assemblies at atomic resolution, with NMR chemical shifts containing rich information about biomolecular structure. Access to this information, however, is problematic, since accurate quantum mechanical calculation of chemical shifts in proteins remains challenging, particularly for 15 N H . Here we report on isotropic chemical shift predictions for the carbohydrate recognition domain of microcrystalline galectin-3, obtained from using hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, implemented using an automated fragmentation approach, and using very high resolution (0.86 Å lactose-bound and 1.25 Å apo form) X-ray crystal structures. The resolution of the X-ray crystal structure used as an input into the AF-NMR program did not affect the accuracy of the chemical shift calculations to any significant extent. Excellent agreement between experimental and computed shifts is obtained for 13 C α , while larger scatter is observed for 15 N H chemical shifts, which are influenced to a greater extent by electrostatic interactions, hydrogen bonding, and solvation.

The NMR-Rosetta capsid model of M13 bacteriophage reveals a quadrupled hydrophobic packing epitope.

PubMed

Morag, Omry; Sgourakis, Nikolaos G; Baker, David; Goldbourt, Amir

2015-01-27

Filamentous phage are elongated semiflexible ssDNA viruses that infect bacteria. The M13 phage, belonging to the family inoviridae, has a length of ∼1 μm and a diameter of ∼7 nm. Here we present a structural model for the capsid of intact M13 bacteriophage using Rosetta model building guided by structure restraints obtained from magic-angle spinning solid-state NMR experimental data. The C5 subunit symmetry observed in fiber diffraction studies was enforced during model building. The structure consists of stacked pentamers with largely alpha helical subunits containing an N-terminal type II β-turn; there is a rise of 16.6-16.7 Å and a tilt of 36.1-36.6° between consecutive pentamers. The packing of the subunits is stabilized by a repeating hydrophobic stacking pocket; each subunit participates in four pockets by contributing different hydrophobic residues, which are spread along the subunit sequence. Our study provides, to our knowledge, the first magic-angle spinning NMR structure of an intact filamentous virus capsid and further demonstrates the strength of this technique as a method of choice to study noncrystalline, high-molecular-weight molecular assemblies.

The NMR–Rosetta capsid model of M13 bacteriophage reveals a quadrupled hydrophobic packing epitope

PubMed Central

Morag, Omry; Sgourakis, Nikolaos G.; Baker, David; Goldbourt, Amir

2015-01-01

Filamentous phage are elongated semiflexible ssDNA viruses that infect bacteria. The M13 phage, belonging to the family inoviridae, has a length of ∼1 μm and a diameter of ∼7 nm. Here we present a structural model for the capsid of intact M13 bacteriophage using Rosetta model building guided by structure restraints obtained from magic-angle spinning solid-state NMR experimental data. The C5 subunit symmetry observed in fiber diffraction studies was enforced during model building. The structure consists of stacked pentamers with largely alpha helical subunits containing an N-terminal type II β-turn; there is a rise of 16.6–16.7 Å and a tilt of 36.1–36.6° between consecutive pentamers. The packing of the subunits is stabilized by a repeating hydrophobic stacking pocket; each subunit participates in four pockets by contributing different hydrophobic residues, which are spread along the subunit sequence. Our study provides, to our knowledge, the first magic-angle spinning NMR structure of an intact filamentous virus capsid and further demonstrates the strength of this technique as a method of choice to study noncrystalline, high-molecular-weight molecular assemblies. PMID:25587134

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.

High-resolution diffusion and relaxation-edited magic angle spinning 1H NMR spectroscopy of intact liver tissue.

PubMed

Rooney, O M; Troke, J; Nicholson, J K; Griffin, J L

2003-11-01

High-resolution magic angle spinning (HRMAS) (1)H NMR spectroscopy is ideal for monitoring the metabolic environment within tissues, particularly when spectra are weighted by physical properties such as T(1) and T(2) relaxation times and apparent diffusion coefficients (ADCs). In this study, spectral-editing using T(1) and T(2) relaxation times and ADCs at variable diffusion times was used in conjunction with HRMAS (1)H NMR spectroscopy at 14.1 T in liver tissue. To enhance the sensitivity of ADC measurements to low molecular weight metabolites a T(2) spin echo was included in a standard stimulated gradient spin-echo sequence. Fatty liver induced in rats by chronic orotic acid feeding was investigated using this modified sequence. An increase in the combined ADC for the co-resonant peaks glucose, betaine, and TMAO during fatty liver disease was detected (ADCs = 0.60 +/- 0.11 and 0.35 +/- 0.1 * 10(-9) m(2)s(-1) (n = 3) for rats fed with and without orotic acid), indicative of a reduction in glucose and betaine and an increase in TMAO. Copyright 2003 Wiley-Liss, Inc.

Nuclear relaxation and critical fluctuations in membranes containing cholesterol

NASA Astrophysics Data System (ADS)

McConnell, Harden

2009-04-01

Nuclear resonance frequencies in bilayer membranes depend on lipid composition. Our calculations describe the combined effects of composition fluctuations and diffusion on nuclear relaxation near a miscibility critical point. Both tracer and gradient diffusion are included. The calculations involve correlation functions and a correlation length ξ =ξ0T/(T -Tc), where T -Tc is temperature above the critical temperature and ξ0 is a parameter of molecular length. Several correlation functions are examined, each of which is related in some degree to the Ising model correlation function. These correlation functions are used in the calculation of transverse deuterium relaxation rates in magic angle spinning and quadrupole echo experiments. The calculations are compared with experiments that report maxima in deuterium and proton nuclear relaxation rates at the critical temperature [Veatch et al., Proc. Nat. Acad. Sci. U.S.A. 104, 17650 (2007)]. One Ising-model-related correlation function yields a maximum 1/T2 relaxation rate at the critical temperature for both magic angle spinning and quadrupole echo experiments. The calculated rates at the critical temperature are close to the experimental rates. The rate maxima involve relatively rapid tracer diffusion in a static composition gradient over distances of up to 10-100 nm.

The chemical and dynamical influence of the anti-viral drug amantadine on the M2 proton channel transmembrane domain.

PubMed

Hu, Jun; Fu, Riqiang; Cross, Timothy A

2007-07-01

The M(2) proton channel plays a vital role in the life cycle of the influenza A virus. His(37), the key residue in the M(2) transmembrane domain (M(2)-TMD), plays a central role in the proton conductance mechanism. The anti-influenza drug, amantadine, inhibits the channel activity through binding to the pore of the M(2) channel. The nuclear spin relaxation data and polarization inversion spin exchange at the magic angle spectra show that both the polypeptide backbone and His(37) side chain are more constrained in the presence of amantadine. Using (15)N cross polarization magic-angle spinning NMR spectroscopy, the protonation of His(37) of M(2)-TMD in lipid bilayers was monitored in the absence and presence of amantadine as a function of pH. Binding amantadine lowers the His(37) pK(a) values by approximately three orders of magnitude compared with the first pK(a) of histidine in amantadine-free M(2)-TMD. Amantadine's influence on the His(37) chemical properties suggests a novel mechanism by which amantadine may inhibit proton conductance.

Measurement and interpretation of electron angle at MABE beam stop

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

Sanford, T.W.L.; Coleman, P.D.; Poukey, J.W.

1985-02-01

The mean angle of incidence at the beam stop of a 60 kA, 7 MV annular electron beam, in the 20 kG guide field of the MABE accelerator, is determined. Radiation dose measured in TLD arrays mounted downstream of the stop is compared with the radiation dose expected using a CYLTRAN Monte Carlo simulation of the electron/photon transport in the stop as a function of incident angles and energies. All radiation profiles measured are well fit, if the electrons are assumed to be incident with a polar angle theta of 15/sup 0/ +- 2/sup 0/. Comparing this theta with thatmore » expected from the Adler-Miller model, and a MAGIC code simulation of beam behavior at the stop enables the mean transverse beam velocity to be estimated.« less

Diamond-anvil cell for radial x-ray diffraction.

PubMed

Chesnut, G N; Schiferl, D; Streetman, B D; Anderson, W W

2006-06-28

We have designed a new diamond-anvil cell capable of radial x-ray diffraction to pressures of a few hundred GPa. The diffraction geometry allows access to multiple angles of Ψ, which is the angle between each reciprocal lattice vector g(hkl) and the compression axis of the cell. At the 'magic angle', Ψ≈54.7°, the effects of deviatoric stresses on the interplanar spacings, d(hkl), are significantly reduced. Because the systematic errors, which are different for each d(hkl), are significantly reduced, the crystal structures and the derived equations of state can be determined reliably. At other values of Ψ, the effects of deviatoric stresses on the diffraction pattern could eventually be used to determine elastic constants.

Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization

NASA Astrophysics Data System (ADS)

Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut; Vega, Shimon; Feintuch, Akiva

2015-09-01

Magic Angle Spinning (MAS) combined with Dynamic Nuclear Polarization (DNP) has been proven in recent years to be a very powerful method for increasing solid-state NMR signals. Since the advent of biradicals such as TOTAPOL to increase the nuclear polarization new classes of radicals, with larger molecular weight and/or different spin properties have been developed. These have led to unprecedented signal gain, with varying results for different experimental parameters, in particular the microwave irradiation strength, the static field, and the spinning frequency. Recently it has been demonstrated that sample spinning imposes DNP enhancement processes that differ from the active DNP mechanism in static samples as upon sample spinning the DNP enhancements are the results of energy level anticrossings occurring periodically during each rotor cycle. In this work we present experimental results with regards to the MAS frequency dependence of the DNP enhancement profiles of four nitroxide-based radicals at two different sets of temperature, 110 and 160 K. In fact, different magnitudes of reduction in enhancement are observed with increasing spinning frequency. Our simulation code for calculating MAS-DNP powder enhancements of small model spin systems has been improved to extend our studies of the influence of the interaction and relaxation parameters on powder enhancements. To achieve a better understanding we simulated the spin dynamics of a single three-spin system {ea -eb - n } during its steady state rotor periods and used the Landau-Zener formula to characterize the influence of the different anti-crossings on the polarizations of the system and their necessary action for reaching steady state conditions together with spin relaxation processes. Based on these model calculations we demonstrate that the maximum steady state nuclear polarization cannot become larger than the maximum polarization difference between the two electrons during the steady state rotor cycle. This study also shows the complexity of the MAS-DNP process and therefore the necessity to rely on numerical simulations for understanding parametric dependencies of the enhancements. Finally an extension of the spin system up to five spins allowed us to probe the first steps of the transfer of polarization from the nuclei coupled to the electrons to further away nuclei, demonstrating a decrease in the spin-diffusion barrier under MAS conditions.

Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization.

PubMed

Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut; Vega, Shimon; Feintuch, Akiva

2015-09-01

Magic Angle Spinning (MAS) combined with Dynamic Nuclear Polarization (DNP) has been proven in recent years to be a very powerful method for increasing solid-state NMR signals. Since the advent of biradicals such as TOTAPOL to increase the nuclear polarization new classes of radicals, with larger molecular weight and/or different spin properties have been developed. These have led to unprecedented signal gain, with varying results for different experimental parameters, in particular the microwave irradiation strength, the static field, and the spinning frequency. Recently it has been demonstrated that sample spinning imposes DNP enhancement processes that differ from the active DNP mechanism in static samples as upon sample spinning the DNP enhancements are the results of energy level anticrossings occurring periodically during each rotor cycle. In this work we present experimental results with regards to the MAS frequency dependence of the DNP enhancement profiles of four nitroxide-based radicals at two different sets of temperature, 110 and 160K. In fact, different magnitudes of reduction in enhancement are observed with increasing spinning frequency. Our simulation code for calculating MAS-DNP powder enhancements of small model spin systems has been improved to extend our studies of the influence of the interaction and relaxation parameters on powder enhancements. To achieve a better understanding we simulated the spin dynamics of a single three-spin system {ea-eb-n} during its steady state rotor periods and used the Landau-Zener formula to characterize the influence of the different anti-crossings on the polarizations of the system and their necessary action for reaching steady state conditions together with spin relaxation processes. Based on these model calculations we demonstrate that the maximum steady state nuclear polarization cannot become larger than the maximum polarization difference between the two electrons during the steady state rotor cycle. This study also shows the complexity of the MAS-DNP process and therefore the necessity to rely on numerical simulations for understanding parametric dependencies of the enhancements. Finally an extension of the spin system up to five spins allowed us to probe the first steps of the transfer of polarization from the nuclei coupled to the electrons to further away nuclei, demonstrating a decrease in the spin-diffusion barrier under MAS conditions. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Moderate MAS enhances local (1)H spin exchange and spin diffusion.

PubMed

Roos, Matthias; Micke, Peter; Saalwächter, Kay; Hempel, Günter

2015-11-01

Proton NMR spin-diffusion experiments are often combined with magic-angle spinning (MAS) to achieve higher spectral resolution of solid samples. Here we show that local proton spin diffusion can indeed become faster at low (<10 kHz) spinning rates as compared to static conditions. Spin diffusion under static conditions can thus be slower than the often referred value of 0.8 nm(2)/ms, which was determined using slow MAS (Clauss et al., 1993). The enhancement of spin diffusion by slow MAS relies on the modulation of the orientation-dependent dipolar couplings during sample rotation and goes along with transient level crossings in combination with dipolar truncation. The experimental finding and its explanation is supported by density matrix simulations, and also emphasizes the sensitivity of spin diffusion to the local coupling topology. The amplification of spin diffusion by slow MAS cannot be explained by any model based on independent spin pairs; at least three spins have to be considered. Copyright © 2015 Elsevier Inc. All rights reserved.

The molecular origin of a loading-induced black layer in the deep region of articular cartilage at the magic angle

PubMed Central

Wang, Nian; Kahn, David; Badar, Farid; Xia, Yang

2014-01-01

Purpose To investigate the molecular origin of an unusual low-intensity layer in the deep region of articular cartilage as seen in MRI when the tissue is imaged under compression and oriented at the magic angle. Materials and Methods Microscopic MRI (μMRI) T2 and T1ρ experiments were carried out for both native and degraded (treated with trypsin) 18 specimens. The glycosaminoglycan (GAG) concentrations in the specimens were quantified by both sodium ICP-OES and μMRI Gd(DTPA)2--contrast methods. The mechanical modulus of the specimens was also measured. Results Native tissue shows no load-induced layer, while the trypsin-degraded tissue shows clearly the low-intensity line at the deep part of tissue. The GAG reductions are confirmed by the sodium ICP-OES (from 81.7 ± 5.4 mg/ml to 9.2 ± 3.4 mg/ml), MRI GAG quantification (from 72.4 ± 6.7 mg/ml to 11.2 ± 2.9 mg/ml). The modulus reduction is confirmed by biomechanics (from 4.3 ± 0.7 MPa to 0.3 ± 0.1 MPa). Conclusion Both T2 and T1ρ profiles in native and degraded cartilage show strongly strain-, depth-, and angle-dependent using high resolution MRI. The GAG reduction is responsible for the visualization of a low-intensity layer in deep cartilage when it is loaded and orientated at 55°. PMID:24833266

Unconventional superconductivity in magic-angle graphene superlattices.

PubMed

Cao, Yuan; Fatemi, Valla; Fang, Shiang; Watanabe, Kenji; Taniguchi, Takashi; Kaxiras, Efthimios; Jarillo-Herrero, Pablo

2018-04-05

The behaviour of strongly correlated materials, and in particular unconventional superconductors, has been studied extensively for decades, but is still not well understood. This lack of theoretical understanding has motivated the development of experimental techniques for studying such behaviour, such as using ultracold atom lattices to simulate quantum materials. Here we report the realization of intrinsic unconventional superconductivity-which cannot be explained by weak electron-phonon interactions-in a two-dimensional superlattice created by stacking two sheets of graphene that are twisted relative to each other by a small angle. For twist angles of about 1.1°-the first 'magic' angle-the electronic band structure of this 'twisted bilayer graphene' exhibits flat bands near zero Fermi energy, resulting in correlated insulating states at half-filling. Upon electrostatic doping of the material away from these correlated insulating states, we observe tunable zero-resistance states with a critical temperature of up to 1.7 kelvin. The temperature-carrier-density phase diagram of twisted bilayer graphene is similar to that of copper oxides (or cuprates), and includes dome-shaped regions that correspond to superconductivity. Moreover, quantum oscillations in the longitudinal resistance of the material indicate the presence of small Fermi surfaces near the correlated insulating states, in analogy with underdoped cuprates. The relatively high superconducting critical temperature of twisted bilayer graphene, given such a small Fermi surface (which corresponds to a carrier density of about 10 11 per square centimetre), puts it among the superconductors with the strongest pairing strength between electrons. Twisted bilayer graphene is a precisely tunable, purely carbon-based, two-dimensional superconductor. It is therefore an ideal material for investigations of strongly correlated phenomena, which could lead to insights into the physics of high-critical-temperature superconductors and quantum spin liquids.

Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

DOE PAGES

Nishiyama, Y.; Kobayashi, T.; Malon, M.; ...

2015-02-16

Two-dimensional 1H{ 13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimensionmore » without resorting to 1H– 1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.« less

Proton decoupling and recoupling under double-nutation irradiation in solid-state NMR

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

Takeda, Kazuyuki, E-mail: takezo@kuchem.kyoto-u.ac.jp; Wakisaka, Asato; Takegoshi, K.

The effect of {sup 1}H decoupling in magic-angle spinning solid-state NMR is studied under radiofrequency irradiation causing simultaneous nutations around a pair of orthogonal axes. Double-nutation with an arbitrary pair of nutation frequencies is implemented through modulation of the amplitude, phase, and frequency of the transmitting pulses. Similarity and difference of double-nutation decoupling and two-pulse phase-modulation decoupling schemes [A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, and R. G. Griffin, J. Chem. Phys. 103, 6951–6958 (1995) and I. Scholz, P. Hodgkinson, B. H. Meier, and M. Ernst, J. Chem. Phys. 130, 114510 (2009)] are discussed. The structuremore » of recoupling bands caused by interference of the {sup 1}H spin nutation with sample spinning is studied by both experiments and numerical simulations.« less

Al3+ environments in nanostructured ZnAl2O4 and their effects on the luminescence properties.

PubMed

da Silva, Alison A; Gonçalves, Agnaldo S; Davolos, Marian R; Santagneli, Silvia H

2008-11-01

Single-phase zinc aluminate (ZnAl2O4) with the spinel structure was successfully obtained by the Pechini method at different calcining temperatures for 4 hours. The nanoparticles are highly crystalline with no impurities related to ZnO or Al2O3 residues. The microstructural environment of aluminium ions changes with heat treatment temperature, as observed by Fourier transform infrared spectroscopy. The spinel structure might present two different AlO6 sites as evidenced by 27Al solid-state magic-angle-spinning nuclear magnetic resonance spectra. Some AlO4 sites were also detected for samples calcined at a temperature lower than 900 degrees C. The photoluminescence spectra show that the emission can be tuned depending on the calcining temperature. This effect was discussed on the basis of symmetry and oxygen vacancies.

Transforming White Light into Rainbows: Segmentation Strategies for Successful School Tax Elections

ERIC Educational Resources Information Center

Senden, J. Bradford; Lifto, Don E.

2009-01-01

In the late 1600s, British physicist Sir Isaac Newton first demonstrated refraction and dispersion in a triangular prism. He discovered that a prism could decompose white light into a spectrum. Hold a prism up to the light at the correct angle and white light magically splits into vivid colors of the rainbow! So what do prisms and rainbows have to…

Beyond-use dating of lidocaine alone and in two "magic mouthwash" preparations.

PubMed

Kirk, Loren Madden; Brown, Stacy D; Luu, Yao; Ogle, Amanda; Huffman, Jessica; Lewis, Paul O

2017-05-01

Beyond-use dating (BUD) of lidocaine alone and in two "magic mouthwash" preparations stored in amber oral syringes at room temperature was determined. Two formulations of mouthwash containing oral topical lidocaine 2% (viscous), diphenhydramine 2.5 mg/mL, and aluminum hydroxide-magnesium hydroxide-simethicone were prepared in 1:1:1 and 1:2.5:2.5 ratios, divided into 3-mL samples, and stored in unit-dose oral amber syringes. Unit-dose single-product lidocaine samples were also prepared to serve as controls and stored in oral amber syringes. The lidocaine concentrations in these samples were measured periodically for 90 days. A stability-indicating high-performance liquid chromatographic method was developed and validated for system suitability, accuracy, repeatability, intermediate precision, specificity, linearity, and robustness. Based on the calculated percentages versus the initial concentration and the results from an analysis of variance comparing the two formulations, a BUD of 21 days is deemed appropriate for both magic mouthwash formulations. Based on the stability data, published safety concerns, and lack of efficacy in combination, packaging and dispensing lidocaine separately from other ingredients are recommended when administering magic mouthwash mixtures. Utilizing a 90-day BUD, lidocaine can be packaged separately from other magic mouthwash ingredients in individual dosage units and applied to the oral cavity using the swish-and-spit method. The delivery of the diphenhydramine and aluminum hydroxide-magnesium hydroxide-simethicone could be separated, allowing for a swish-and-swallow method of administration. A BUD of 21 days is recommended for lidocaine prepared with diphenhydramine and aluminum hydroxide-magnesium hydroxide-simethicone in ratios of 1:1:1 and 1:2.5:2.5 and stored at room temperature in amber oral plastic syringes. Copyright © 2017 by the American Society of Health-System Pharmacists, Inc. All rights reserved.

The Magnetics Information Consortium (MagIC)

NASA Astrophysics Data System (ADS)

Johnson, C.; Constable, C.; Tauxe, L.; Koppers, A.; Banerjee, S.; Jackson, M.; Solheid, P.

2003-12-01

The Magnetics Information Consortium (MagIC) is a multi-user facility to establish and maintain a state-of-the-art relational database and digital archive for rock and paleomagnetic data. The goal of MagIC is to make such data generally available and to provide an information technology infrastructure for these and other research-oriented databases run by the international community. As its name implies, MagIC will not be restricted to paleomagnetic or rock magnetic data only, although MagIC will focus on these kinds of information during its setup phase. MagIC will be hosted under EarthRef.org at http://earthref.org/MAGIC/ where two "integrated" web portals will be developed, one for paleomagnetism (currently functional as a prototype that can be explored via the http://earthref.org/databases/PMAG/ link) and one for rock magnetism. The MagIC database will store all measurements and their derived properties for studies of paleomagnetic directions (inclination, declination) and their intensities, and for rock magnetic experiments (hysteresis, remanence, susceptibility, anisotropy). Ultimately, this database will allow researchers to study "on the internet" and to download important data sets that display paleo-secular variations in the intensity of the Earth's magnetic field over geological time, or that display magnetic data in typical Zijderveld, hysteresis/FORC and various magnetization/remanence diagrams. The MagIC database is completely integrated in the EarthRef.org relational database structure and thus benefits significantly from already-existing common database components, such as the EarthRef Reference Database (ERR) and Address Book (ERAB). The ERR allows researchers to find complete sets of literature resources as used in GERM (Geochemical Earth Reference Model), REM (Reference Earth Model) and MagIC. The ERAB contains addresses for all contributors to the EarthRef.org databases, and also for those who participated in data collection, archiving and analysis in the magnetic studies. Integration with these existing components will guarantee direct traceability to the original sources of the MagIC data and metadata. The MagIC database design focuses around the general workflow that results in the determination of typical paleomagnetic and rock magnetic analyses. This ensures that individual data points can be traced between the actual measurements and their associated specimen, sample, site, rock formation and locality. This permits a distinction between original and derived data, where the actual measurements are performed at the specimen level, and data at the sample level and higher are then derived products in the database. These relations will also allow recalculation of derived properties, such as site means, when new data becomes available for a specific locality. Data contribution to the MagIC database is critical in achieving a useful research tool. We have developed a standard data and metadata template that can be used to provide all data at the same time as publication. Software tools are provided to facilitate easy population of these templates. The tools allow for the import/export of data files in a delimited text format, and they provide some advanced functionality to validate data and to check internal coherence of the data in the template. During and after publication these standardized MagIC templates will be stored in the ERR database of EarthRef.org from where they can be downloaded at all times. Finally, the contents of these template files will be automatically parsed into the online relational database.

The relationship between schizotypal facets and conspiracist beliefs via cognitive processes.

PubMed

Barron, David; Furnham, Adrian; Weis, Laura; Morgan, Kevin D; Towell, Tony; Swami, Viren

2018-01-01

This study sought to replicate previous work showing relationships between components of schizotypy and conspiracist beliefs, and extend it by examining the mediating role of cognitive processes. An international online sample of 411 women and men (mean age = 35.41 years) completed measures of the schizotypal facets of Odd Beliefs or Magical Thinking and Ideas of Reference, conspiracist beliefs, and cognitive processes related to need for cognition, analytic thinking, and cognitive insight. Path analysis confirmed the associations between both schizotypal facets and conspiracist beliefs in the present sample. Confirmatory evidence was found for the association between analytic thinking and conspiracist beliefs, and results also suggested an association between cognitive insight and conspiracist beliefs. Cognitive insight also mediated the link between Odd Beliefs or Magical Thinking and Ideas of Reference with conspiracist beliefs. However, analytic thinking provided a mediating link to conspiracy ideation for Odd Beliefs or Magical Thinking and not Ideas of Reference. Finally, there was an association between Odd Beliefs or Magical Thinking and need for cognition, but this path did not extend to conspiracist beliefs. These results suggest possible mediating roles for analytic thinking and self-certainty between schizotypy and conspiracist beliefs. Copyright © 2017 Elsevier B.V. All rights reserved.

Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts

NASA Astrophysics Data System (ADS)

Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard; Penner, Simon; Rameshan, Christoph

2014-05-01

An ultra-high vacuum (UHV) setup for "real" and "inverse" model catalyst preparation, depth-resolved near-surface spectroscopic characterization, and quantification of catalytic activity and selectivity under technologically relevant conditions is described. Due to the all-quartz reactor attached directly to the UHV-chamber, transfer of the catalyst for in situ testing without intermediate contact to the ambient is possible. The design of the UHV-compatible re-circulating batch reactor setup allows the study of reaction kinetics under close to technically relevant catalytic conditions up to 1273 K without contact to metallic surfaces except those of the catalyst itself. With the attached differentially pumped exchangeable evaporators and the quartz-microbalance thickness monitoring equipment, a reproducible, versatile, and standardised sample preparation is possible. For three-dimensional near-surface sample characterization, the system is equipped with a hemispherical analyser for X-ray photoelectron spectroscopy (XPS), electron-beam or X-ray-excited Auger-electron spectroscopy, and low-energy ion scattering measurements. Due the dedicated geometry of the X-ray gun (54.7°, "magic angle") and the rotatable sample holder, depth analysis by angle-resolved XPS measurements can be performed. Thus, by the combination of characterisation methods with different information depths, a detailed three-dimensional picture of the electronic and geometric structure of the model catalyst can be obtained. To demonstrate the capability of the described system, comparative results for depth-resolved sample characterization and catalytic testing in methanol steam reforming on PdGa and PdZn near-surface intermetallic phases are shown.

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

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

On the application of magic echo cycles for quadrupolar echo spectroscopy of spin-1 nuclei.

PubMed

Mananga, E S; Roopchand, R; Rumala, Y S; Boutis, G S

2007-03-01

Magic echo cycles are introduced for performing quadrupolar echo spectroscopy of spin-1 nuclei. An analysis is performed via average Hamiltonian theory showing that the evolution under chemical shift or static field inhomogeneity can be refocused simultaneously with the quadrupolar interaction using these cycles. Due to the higher convergence in the Magnus expansion, with sufficient RF power, magic echo based quadrupolar echo spectroscopy outperforms the conventional two pulse quadrupolar echo in signal to noise. Experiments highlighting a signal to noise enhancement over the entire bandwidth of the quadrupolar pattern of a powdered sample of deuterated polyethelene are shown.

Assessment of Magical Beliefs about Food and Health.

PubMed

Lindeman, M; Keskivaara, P; Roschier, M

2000-03-01

The Magical Beliefs About Food and Health scale (MFH) was developed to assess individual differences in the tendency to adopt eating and health instructions that many magazines, health care books and food ideologies regard as valid but which obey universal laws of similarity and contagion. In a study of 216 individuals, the total MFH score showed good internal consistency and it was associated with various validity criteria as hypothesized (e.g. vegetarianism and other ideological commitments to food choice, female gender, increased neuroticism, experiential thinking, positive attitudes towards alternative medicine, low sensation seeking and endorsement of universalism values). Factor analysis yielded two factors: General Magical Beliefs and Animal Products as Food Contaminants. In addition, three other items (the Animal Products as Personality Contaminants scale) cross-loaded on the two factors. The factor structure and test-retest reliability were confirmed with separate samples. The results showed that the total MFH score is a reliable and valid measure of magical food and health beliefs, and that the subscales may prove useful when a multidimensional assessment of magical beliefs is needed.

Magnetic resonance metabolomics of intact tissue: a biotechnological tool in cancer diagnostics and treatment evaluation.

PubMed

Bathen, Tone F; Sitter, Beathe; Sjøbakk, Torill E; Tessem, May-Britt; Gribbestad, Ingrid S

2010-09-01

Personalized medicine is increasingly important in cancer treatment for its role in staging and its potential to improve stratification of patients. Different types of molecules, genes, proteins, and metabolites are being extensively explored as potential biomarkers. This review discusses the major findings and potential of tissue metabolites determined by high-resolution magic angle spinning magnetic resonance spectroscopy for cancer detection, characterization, and treatment monitoring.

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

High-Resolution Magic-Angle-Spinning NMR and Magnetic Resonance Imaging Spectroscopies Distinguish Metabolome and Structural Properties of Maize Seeds from Plants Treated with Different Fertilizers and Arbuscular mycorrhizal fungi.

PubMed

Mazzei, Pierluigi; Cozzolino, Vincenza; Piccolo, Alessandro

2018-03-21

Both high-resolution magic-angle-spinning (HRMAS) and magnetic resonance imaging (MRI) NMR spectroscopies were applied here to identify the changes of metabolome, morphology, and structural properties induced in seeds (caryopses) of maize plants grown at field level under either mineral or compost fertilization in combination with the inoculation by arbuscular mycorrhizal fungi (AMF). The metabolome of intact caryopses was examined by HRMAS-NMR, while the morphological aspects, endosperm properties and seed water distribution were investigated by MRI. Principal component analysis (PCA) was applied to evaluate 1 H CPMG (Carr-Purcel-Meiboom-Gill) HRMAS spectra as well as several MRI-derived parameters ( T 1 , T 2 , and self-diffusion coefficients) of intact maize caryopses. PCA score-plots from spectral results indicated that both seeds metabolome and structural properties depended on the specific field treatment undergone by maize plants. Our findings show that a combination of multivariate statistical analyses with advanced and nondestructive NMR techniques, such as HRMAS and MRI, enables the evaluation of the effects induced on maize caryopses by different fertilization and management practices at field level. The spectroscopic approach adopted here may become useful for the objective appraisal of the quality of seeds produced under a sustainable agriculture.

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.

Towards high resolution ^1H NMR spectra of tannin colloidal aggregates

NASA Astrophysics Data System (ADS)

Mirabel, M.; Glories, Y.; Pianet, I.; Dufourc, E. J.

1999-10-01

The time dependent colloidal formation of tannins in hydro-alcoholic medium has been studied by 1H-NMR. Line broadening observed with time can be cancelled by making use of magic angle sample spinning (MASS) thus yielding sharp lines that allow structural studies. We used as an example catechin, a constitutive monomer of Bordeaux young red wine tannins. Chemical shift variations of polyphenol protons allow monitoring the time course of aggregation. La formation de tanins colloïdaux au cours du temps, en milieu hydroalcoolique, a été suivie par RMN-^1H. Un élargissement marqué des résonances est observé et peut être supprimé par la rotation de l'échantillon à l'angle magique ce qui ouvre tout un champ d'études structurales sur ces composés colloïdaux. L'exemple proposé est celui de la catéchine, monomère constitutif de tannins présents en grande quantité dans les vins rouges jeunes de Bordeaux. Des variations du déplacement chimique de certains protons polyphénoliques permettent de suivre l'évolution temporelle de l'agrégation.

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

Biological degradation of tannins in sericea lespedeza (Lespedeza cuneata) by the white rot fungi Ceriporiopsis subvermispora and Cyathus stercoreus analyzed by solid-state 13C nuclear magnetic resonance spectroscopy.

PubMed Central

Gamble, G R; Akin, D E; Makkar, H P; Becker, K

1996-01-01

Leaves of sericea lespedeza exhibit a high proportion of condensed tannin, resulting in poor forage quality. The white rot fungi Ceriporiopsis subvermispora and Cyathus sterocoreus are known to preferentially degrade lignin in a variety of plants and were evaluated for their ability to degrade condensed tannin from sericea leaves with the aim of improving digestibility. Relative levels of condensed tannin, cutin, pectin, and cellulose were monitored as a function of fungal treatment by solid-state cross-polarization and magic angle spinning 13C nuclear magnetic resonance spectroscopy. Total soluble phenolics, soluble tannins, and soluble and insoluble proanthocyanidin levels in fungus-treated and control samples were measured by established chemical techniques. Results indicate that both species of fungus preferentially degrade condensed tannin and that C. subvermispora is markedly superior to C. stercoreus in this capacity. PMID:8837414

A homonuclear spin-pair filter for solid-state NMR based on adiabatic-passage techniques

NASA Astrophysics Data System (ADS)

Verel, René; Baldus, Marc; Ernst, Matthias; Meier, Beat H.

1998-05-01

A filtering scheme for the selection of spin pairs (and larger spin clusters) under fast magic-angle spinning is proposed. The scheme exploits the avoided level crossing in spin pairs during an adiabatic amplitude sweep through the so-called HORROR recoupling condition. The advantages over presently used double-quantum filters are twofold. (i) The maximum theoretical filter efficiency is, due to the adiabatic variation, 100% instead of 73% as for transient methods. (ii) Since the filter does not rely on the phase-cycling properties of the double-quantum coherence, there is no need to obtain the full double-quantum intensity for all spins in the sample at one single point in time. The only important requirement is that all coupled spins pass through a two-spin state during the amplitude sweep. This makes the pulse scheme robust with respect to rf-amplitude missetting, rf-field inhomogeneity and chemical-shift offset.

Mechanisms of Dynamic Nuclear Polarization in Insulating Solids

PubMed Central

Can, T.V.; Ni, Q.Z.; Griffin, R.G.

2015-01-01

Dynamic nuclear polarization (DNP) is a technique used to enhance signal intensities in NMR experiments by transferring the high polarization of electrons to their surrounding nuclei. The past decade has witnessed a renaissance in the development of DNP, especially at high magnetic fields, and its application in several areas including biophysics, chemistry, structural biology and materials science. Recent technical and theoretical advances have expanded our understanding of established experiments: for example, the cross effect DNP in samples spinning at the magic angle. Furthermore, new experiments suggest that our understanding of the Overhauser effect and its applicability to insulating solids needs to be re-examined. In this article, we summarize important results of the past few years and provide quantum mechanical explanations underlying these results. We also discuss future directions of DNP and current limitations, including the problem of resolution in protein spectra recorded at 80–100 K. PMID:25797002

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.

15N CSA tensors and 15N-1H dipolar couplings of protein hydrophobic core residues investigated by static solid-state NMR

NASA Astrophysics Data System (ADS)

Vugmeyster, Liliya; Ostrovsky, Dmitry; Fu, Riqiang

2015-10-01

In this work, we assess the usefulness of static 15N NMR techniques for the determination of the 15N chemical shift anisotropy (CSA) tensor parameters and 15N-1H dipolar splittings in powder protein samples. By using five single labeled samples of the villin headpiece subdomain protein in a hydrated lyophilized powder state, we determine the backbone 15N CSA tensors at two temperatures, 22 and -35 °C, in order to get a snapshot of the variability across the residues and as a function of temperature. All sites probed belonged to the hydrophobic core and most of them were part of α-helical regions. The values of the anisotropy (which include the effect of the dynamics) varied between 130 and 156 ppm at 22 °C, while the values of the asymmetry were in the 0.32-0.082 range. The Leu-75 and Leu-61 backbone sites exhibited high mobility based on the values of their temperature-dependent anisotropy parameters. Under the assumption that most differences stem from dynamics, we obtained the values of the motional order parameters for the 15N backbone sites. While a simple one-dimensional line shape experiment was used for the determination of the 15N CSA parameters, a more advanced approach based on the ;magic sandwich; SAMMY pulse sequence (Nevzorov and Opella, 2003) was employed for the determination of the 15N-1H dipolar patterns, which yielded estimates of the dipolar couplings. Accordingly, the motional order parameters for the dipolar interaction were obtained. It was found that the order parameters from the CSA and dipolar measurements are highly correlated, validating that the variability between the residues is governed by the differences in dynamics. The values of the parameters obtained in this work can serve as reference values for developing more advanced magic-angle spinning recoupling techniques for multiple labeled samples.

[Polyhedron of Dürer's engraving Melancholia. I--a Nürnberg sketch representing the Archimedean body].

PubMed

Weitzel, Hans

2007-01-01

New mathematical hypotheses are postulated concerning the truncated rhombohedron in Dürer's engraving Melencolia.I as well as the relation of the rhombohedron to the magic square. The two free parameters of a truncated rhombohedron have to be chosen in a way that (i) its front orthogonal elevation is nearly quadratical and with the form of the magic square, and that (ii) it possesses approximately a circumscribed sphere. Both conditions result in a value of 79.2 degrees for the angle of the rhombohedron. Measuring two lengths of the rhombohedron of the engraving yields the same value. In the magic square, the numbers are positioned in a way that the connection lines between four numbers give the sum 34 for lines which are the projection lines of the edges of the rhombohedron. In the Nürnberg-Codex of Dürer's manuscripts, exists a page with some sketches of mostly archimedean solids. One sketch represents a pentagon with approximately the measures of the six lateral faces of the truncated rhombohedron. It has to be looked upon as a preliminary sketch for the solid of the engraving. In 1543 Augustin Hirschvogel from Nürnberg, as the next after Dürer, rediscovered a further archimedean solid; this rediscovering has been attributed to D. Barbaro until now.

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.

RF waveguide phase-directed power combiners

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

Nantista, Christopher D.; Dolgashev, Valery A.; Tantawi, Sami G.

2017-05-02

High power RF phase-directed power combiners include magic H hybrid and/or superhybrid circuits oriented in orthogonal H-planes and connected using E-plane bends and/or twists to produce compact 3D waveguide circuits, including 8.times.8 and 16.times.16 combiners. Using phase control at the input ports, RF power can be directed to a single output port, enabling fast switching between output ports for applications such as multi-angle radiation therapy.

Role of magical thinking in obsessive-compulsive symptoms in an undergraduate sample.

PubMed

Einstein, Danielle A; Menzies, Ross G

2004-01-01

Thought action fusion (TAF) is an important presenting feature of many individuals with obsessive-compulsive disorder (OCD). "Magical thinking" is a similar construct (developed within the literature on schizotypy) that may provide a more accurate depiction of difficulties encountered by individuals with OCD. This study seeks to examine relationships between components of magical thinking, TAF, and superstitiousness; establish the extent to which these constructs are independently related to OCD proneness; and establish the extent to which these biased reasoning styles are related to each of the major OCD symptom clusters (e.g., washing, checking). The Padua Inventory (PI), the Maudsley Obsessional-Compulsive Inventory (MOCI), the Magical Ideation Scale (MI), the Lucky Behaviours (Lbeh) and Lucky Beliefs (Lbel) Scales, and the Thought Action Fusion-Revised scale (TAF-R) were given to a cohort of 86 undergraduate students. Of all the measures, the MI scale was found to be the most strongly related to obsessive-compulsive symptoms. Large and significant relationships between MI scores and the two measures of OCD (i.e., MOCI and PI) were obtained even when alternative mediators (i.e., Lbeh, Lbel, TAF-R) were held constant. No other variable remained significantly related to the MOCI or PI when magical ideation scores were held constant. The findings suggest that a general magical thinking tendency may underpin previous observed links between superstitiousness, thought action fusion, and OCD severity. Copyright 2004 Wiley-Liss, Inc.

Unsaturation level decreased in bone marrow fat of postmenopausal women with low bone density using high resolution magic angle spinning (HRMAS) 1H NMR spectroscopy.

PubMed

Li, Xiaojuan; Shet, Keerthi; Xu, Kaipin; Rodríguez, Juan Pablo; Pino, Ana María; Kurhanewicz, John; Schwartz, Ann; Rosen, Clifford J

2017-12-01

There are increasing evidences suggesting bone marrow adiposity tissue (MAT) plays a critical role in affecting both bone quantity and quality. However, very limited studies that have investigated the association between the composition of MAT and bone mineral density (BMD). The goal of this study was to quantify MAT unsaturation profile of marrow samples from post-menopausal women using ex vivo high-resolution magic angle spinning (HRMAS) proton nuclear magnetic resonance ( 1 H NMR) spectroscopy, and to investigate the relationship between MAT composition and BMD. Bone marrow samples were obtained by iliac crest aspiration during surgical procedures from 24 postmenopausal women (65-89years) who had hip surgery due to bone fracture or arthroplasty. Marrow fat composition parameters, in particular, unsaturation level (UL), mono-unsaturation level (MUL) and saturation level (SL), were quantified using HRMAS 1 H NMR spectroscopy. The patients were classified into three groups based on the DXA BMD T-scores: controls, osteopenia and osteoporosis. Marrow fat composition was compared between these three groups as well as between subjects with and without factures using ANOCOVA, adjusted for age. Subjects with lower BMD (n=17) had significantly lower MUL (P=0.003) and UL (P=0.039), and significantly higher SL (P=0.039) compared to controls (n=7). When separating lower BMD into osteopenia (n=9) and osteoporosis (n=8) groups, subjects with osteopenia had significantly lower MUL (P=0.002) and UL (P=0.010), and significantly higher SL (P=0.010) compared to healthy controls. No significant difference was observed between subjects with osteopenia and osteoporosis. Using HRMAS 1 H NMR, significantly lower unsaturation and significantly higher saturation levels were observed in the marrow fat of subjects with lower BMD. HRMAS 1 H NMR was shown to be a powerful tool for identifying novel MR markers of marrow fat composition that are associated with bone quality and potentially fracture, and other bone pathologies and changes after treatment. A better understanding of the relationship between bone marrow composition and bone quality in humans may identify novel treatment targets, and provide guidance on novel interventions and therapeutic strategies for bone preservation. 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

Detergent Optimized Membrane Protein Reconstitution in Liposomes for Solid State NMR

PubMed Central

2015-01-01

For small helical membrane proteins, their structures are highly sensitive to their environment, and solid state NMR is a structural technique that can characterize these membrane proteins in native-like lipid bilayers and proteoliposomes. To date, a systematic method by which to evaluate the effect of the solubilizing detergent on proteoliposome preparations for solid state NMR of membrane proteins has not been presented in the literature. A set of experiments are presented aimed at determining the conditions most amenable to dialysis mediated reconstitution sample preparation. A membrane protein from M. tuberculosis is used to illustrate the method. The results show that a detergent that stabilizes the most protein is not always ideal and sometimes cannot be removed by dialysis. By focusing on the lipid and protein binding properties of the detergent, proteoliposome preparations can be readily produced, which provide double the signal-to-noise ratios for both the oriented sample and magic angle spinning solid state NMR. The method will allow more membrane protein drug targets to be structurally characterized in lipid bilayer environments. PMID:24665863

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.

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.

Angle-dependent quantum Otto heat engine based on coherent dipole-dipole coupling

NASA Astrophysics Data System (ADS)

Su, Shan-He; Luo, Xiao-Qing; Chen, Jin-Can; Sun, Chang-Pu

2016-08-01

Electromagnetic interactions between molecules or within a molecule have been widely observed in biological systems and exhibit broad application for molecular structural studies. Quantum delocalization of molecular dipole moments has inspired researchers to explore new avenues to utilize this physical effect for energy harvesting devices. Herein, we propose a simple model of the angle-dependent quantum Otto heat engine which seeks to facilitate the conversion of heat to work. Unlike previous studies, the adiabatic processes are accomplished by varying only the directions of the magnetic field. We show that the heat engine continues to generate power when the angle relative to the vector r joining the centres of coupled dipoles departs from the magic angle θm where the static coupling vanishes. A significant improvement in the device performance has to be attributed to the presence of the quantum delocalized levels associated with the coherent dipole-dipole coupling. These results obtained may provide a promising model for the biomimetic design and fabrication of quantum energy generators.

Sex Differences in Magical Ideation: A Community-Based Twin Study

PubMed Central

Karcher, Nicole R.; Slutske, Wendy S.; Kerns, John G.; Piasecki, Thomas M.; Martin, Nicholas G.

2014-01-01

Two questions regarding sex differences in magical ideation were investigated in this study: (1) whether there are mean level sex differences on the Magical Ideation Scale (MIS), and (2) whether there are quantitative and/or qualitative sex differences in the genetic contributions to variation on this scale. These questions were evaluated using data obtained from a large community sample of adult Australian twins (N=4,355) that included opposite-sex pairs. Participants completed a modified 15-item version of the MIS within a larger assessment battery. Women reported both higher means and variability on the MIS than men; this was also observed within families (in opposite-sex twin pairs). Biometric modeling indicated that the proportion of variation in MIS scores due to genetic influences (indicating quantitative sex differences) and the specific latent genetic contributions to this variation (indicating qualitative sex differences) were the same in men and women. These findings clarify the nature of sex differences in magical ideation and point to avenues for future research. PMID:24364500

Ambidexterity and magical ideation.

PubMed

Barnett, Kylie J; Corballis, Michael C

2002-01-01

In a sample of 250 healthy undergraduate students, scores on a scale of magical ideation rose to a peak at the point of ambilaterality on a scale of hand preference, and fell away with increasing right- or left-handedness. This effect mirrors that reported by Crow, Crow, Done, and Leask (1998) who found a dip in academic abilities at the point of ambilaterality, or what they call ''the point of hemispheric indecision''. We relate these findings to genetic theories of laterality in which one allele (RS+) codes for left-cerebral dominance while the other (RS-) leaves laterality to chance. RS-- homozygotes may be susceptible to a lack of dominance, resulting in a disposition to magical ideation and an increased risk of schizophrenia, but also enhanced creativity and lateral thinking.

Corrigendum to "Multiple-quantum spin counting in magic-angle-spinning NMR via low-power symmetry-based dipolar recoupling" [J. Magn. Reson. 236 (2013) 31-40

NASA Astrophysics Data System (ADS)

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

2017-03-01

The authors regret that an inappropriate NMR data processing, not known to all authors at the time of publication, was used to produce the multiple-quantum coherence (MQC) spin counting data presented in our article: this lead to artificially enhanced results, particularly concerning those obtained at long MQC excitation intervals (τexc). Here we reproduce Figs. 4-7 with correctly processed data.

Atomic-resolution structure of the CAP-Gly domain of dynactin on polymeric microtubules determined by magic angle spinning NMR spectroscopy.

PubMed

Yan, Si; Guo, Changmiao; Hou, Guangjin; Zhang, Huilan; Lu, Xingyu; Williams, John Charles; Polenova, Tatyana

2015-11-24

Microtubules and their associated proteins perform a broad array of essential physiological functions, including mitosis, polarization and differentiation, cell migration, and vesicle and organelle transport. As such, they have been extensively studied at multiple levels of resolution (e.g., from structural biology to cell biology). Despite these efforts, there remain significant gaps in our knowledge concerning how microtubule-binding proteins bind to microtubules, how dynamics connect different conformational states, and how these interactions and dynamics affect cellular processes. Structures of microtubule-associated proteins assembled on polymeric microtubules are not known at atomic resolution. Here, we report a structure of the cytoskeleton-associated protein glycine-rich (CAP-Gly) domain of dynactin motor on polymeric microtubules, solved by magic angle spinning NMR spectroscopy. We present the intermolecular interface of CAP-Gly with microtubules, derived by recording direct dipolar contacts between CAP-Gly and tubulin using double rotational echo double resonance (dREDOR)-filtered experiments. Our results indicate that the structure adopted by CAP-Gly varies, particularly around its loop regions, permitting its interaction with multiple binding partners and with the microtubules. To our knowledge, this study reports the first atomic-resolution structure of a microtubule-associated protein on polymeric microtubules. Our approach lays the foundation for atomic-resolution structural analysis of other microtubule-associated motors.

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

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.

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 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.

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

Analysis of the Electronic Structure of the Special Pair of a Bacterial Photosynthetic Reaction Center by 13 C Photochemically Induced Dynamic Nuclear Polarization Magic-Angle Spinning NMR Using a Double-Quantum Axis.

PubMed

Najdanova, Marija; Gräsing, Daniel; Alia, A; Matysik, Jörg

2018-01-01

The origin of the functional symmetry break in bacterial photosynthesis challenges since several decades. Although structurally very similar, the two branches of cofactors in the reaction center (RC) protein complex act very differently. Upon photochemical excitation, an electron is transported along one branch, while the other remains inactive. Photochemically induced dynamic nuclear polarization (photo-CIDNP) magic-angle spinning (MAS) 13 C NMR revealed that the two bacteriochlorophyll cofactors forming the "Special Pair" donor dimer are already well distinguished in the electronic ground state. These previous studies are relying solely on 13 C- 13 C correlation experiments as radio-frequency-driven recoupling (RFDR) and dipolar-assisted rotational resonance (DARR). Obviously, the chemical-shift assignment is difficult in a dimer of tetrapyrrole macrocycles, having eight pyrrole rings of similar chemical shifts. To overcome this problem, an INADEQUATE type of experiment using a POST C7 symmetry-based approach is applied to selectively isotope-labeled bacterial RC of Rhodobacter (R.) sphaeroides wild type (WT). We, therefore, were able to distinguish unresolved sites of the macromolecular dimer. The obtained chemical-shift pattern is in-line with a concentric assembly of negative charge within the common center of the Special Pair supermolecule in the electronic ground state. © 2017 The American Society of Photobiology.

Interplay of spherical closed shells and N /Z asymmetry in quasifission dynamics

NASA Astrophysics Data System (ADS)

Mohanto, G.; Hinde, D. J.; Banerjee, K.; Dasgupta, M.; Jeung, D. Y.; Simenel, C.; Simpson, E. C.; Wakhle, A.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; Palshetkar, C. S.; Rafferty, D. C.

2018-05-01

Background: Quasifission (QF) has gained tremendous importance in heavy-ion nuclear physics research because of its strong influence on superheavy-element synthesis. Collisions involving closed-shell nuclei in the entrance channel are found to affect the QF reaction mechanism. Hence, it is important to improve the understanding of their effect on QF. Apart from that, some recent studies show that the difference in N /Z of reaction partners influences the reaction dynamics. Since heavier doubly magic nuclei have different N /Z than lighter doubly magic nuclei, it is important to understand the effect of N /Z mismatch as well as the effect of shell closures. Purpose: To investigate the effect of entrance-channel shell closures and N /Z asymmetry on QF. The reactions were chosen to decouple these effects from the contributions of other entrance-channel parameters. Method: Fission fragment mass-angle distributions were measured using the CUBE fission spectrometer, consisting of two large area position-sensitive multi-wire proportional counters (MWPCs), for five reactions, namely, 50Cr+208Pb , 52Cr+Pb,208206 , 54Cr+Pb,208204 . Result: Two components were observed in the measured fragment mass angle distribution, a fast mass-asymmetric quasifission and a slow mass-symmetric component having a less significant mass-angle correlation. The ratio of these components was found to depend on spherical closed shells in the entrance channel nuclei and the magnitude of the N /Z mismatch between the two reaction partners, as well as the beam energy. Conclusions: Entrance-channel spherical closed shells can enhance compound nucleus formation provided the N /Z asymmetry is small. Increase in the N /Z asymmetry is expected to destroy the effect of entrance-channel spherical closed shells, through nucleon transfer reactions.

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.

Creating Magic Squares.

ERIC Educational Resources Information Center

Lyon, Betty Clayton

1990-01-01

One method of making magic squares using a prolongated square is illustrated. Discussed are third-order magic squares, fractional magic squares, fifth-order magic squares, decimal magic squares, and even magic squares. (CW)

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.

Ultrafast VHE Gamma-Ray Flares of IC 310

NASA Astrophysics Data System (ADS)

Barkov, Maxim V.; Aharonian, Felix; Khangulyan, Dmitriy V.

In 2012 November MAGIC detected a bright flare from IC 310. The flare consisted of two sharp peaks with a typical duration of ~ 5 min. The energy released during that event has been estimated to be at the level of 2 × 1044 erg s-1. In this work we derive an upper limit on the possible luminosity of flares generated in black hole (BH) magnetosphere, which depends very weakly on the mass of BH and is determined by disk magnetisation, viewing angle, and pair multiplicity. Since all these parameters are smaller than a unit, the luminosity 2 × 1043 erg s-1 can be taken as a strict upper limit for flare luminosity for several minutes variability time. This upper limit appears to be approximately an order of magnitude below the value measured with MAGIC. Thus, we conclude that it seems very unfeasible that the magnetospheric processes can be indeed behind the bright flaring activity recorded from IC 310.

Enhancing the Jamaica Defence Force Military Intelligence Unit’s Effectiveness to Conduct Counterdrug Missions

DTIC Science & Technology

2006-06-16

ecstasy and heroin but in quantities that constitute personal use or for local sampling. The apparent sporadic availability of drugs other than...is not just simply to say “fix the problem” and hope that by some stroke of magic all the intervening factors fall into place and the issue is 34...include those that are widely abused, such as Heroin, Cocaine. Ecstasy , LSD (Lysergic Acid Diethylamide), and Magic Mushrooms 2. Class B drugs

Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

PubMed

Dai, Weili; Wang, Chuanming; Yi, Xianfeng; Zheng, Anmin; Li, Landong; Wu, Guangjun; Guan, Naijia; Xie, Zaiku; Dyballa, Michael; Hunger, Michael

2015-07-20

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HRMAS NMR) for Studies of Reactive Fabrics

DTIC Science & Technology

2015-11-01

Group Chemistry, 2010, 9, 205-219. 6 C. A. S. Brevett and K. B. Sumpter, “ Sulfur Mustard Degradation on Ambient and Moist Concrete ”, ECBC Technical...reactions of reagents including chemical weapons on materials like concrete , soil, and sand, as well as reactive polymers.3,4,5,6,7 There are...Sumpter, G. W. Wagner, “Degradation of Mustard on Concrete : GC/MSD and SSMAS,” ECBC Technical Report ECBC-TR-482, Edgewood Chemical Biological Center

The Magical Number 7

ERIC Educational Resources Information Center

Richardson, Mary; Reischman, Diann

2011-01-01

This article describes an interactive activity that involves students participating in a memory recall test. Data collected from the activity may be used to illustrate the one-sample t test or one-sample sign test. (Contains 1 table and 1 figure.)

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).

Solving the challenges of data preprocessing, uploading, archiving, retrieval, analysis and visualization for large heterogeneous paleo- and rock magnetic datasets

NASA Astrophysics Data System (ADS)

Minnett, R.; Koppers, A. A.; Tauxe, L.; Constable, C.; Jarboe, N. A.

2011-12-01

The Magnetics Information Consortium (MagIC) provides an archive for the wealth of rock- and paleomagnetic data and interpretations from studies on natural and synthetic samples. As with many fields, most peer-reviewed paleo- and rock magnetic publications only include high level results. However, access to the raw data from which these results were derived is critical for compilation studies and when updating results based on new interpretation and analysis methods. MagIC provides a detailed metadata model with places for everything from raw measurements to their interpretations. Prior to MagIC, these raw data were extremely cumbersome to collect because they mostly existed in a lab's proprietary format on investigator's personal computers or undigitized in field notebooks. MagIC has developed a suite of offline and online tools to enable the paleomagnetic, rock magnetic, and affiliated scientific communities to easily contribute both their previously published data and data supporting an article undergoing peer-review, to retrieve well-annotated published interpretations and raw data, and to analyze and visualize large collections of published data online. Here we present the technology we chose (including VBA in Excel spreadsheets, Python libraries, FastCGI JSON webservices, Oracle procedures, and jQuery user interfaces) and how we implemented it in order to serve the scientific community as seamlessly as possible. These tools are now in use in labs worldwide, have helped archive many valuable legacy studies and datasets, and routinely enable new contributions to the MagIC Database (http://earthref.org/MAGIC/).

(14)N overtone transition in double rotation solid-state NMR.

PubMed

Haies, Ibraheem M; Jarvis, James A; Brown, Lynda J; Kuprov, Ilya; Williamson, Philip T F; Carravetta, Marina

2015-10-07

Solid-state NMR transitions involving outer energy levels of the spin-1 (14)N nucleus are immune, to first order in perturbation theory, to the broadening caused by the nuclear quadrupole interaction. The corresponding overtone spectra, when acquired in conjunction with magic-angle sample spinning, result in lines, which are just a few kHz wide, permitting the direct detection of nitrogen compounds without the need for labeling. Despite the success of this technique, "overtone" resonances are still broadened due to indirect, second order effects arising from the large quadrupolar interaction. Here we demonstrate that another order of magnitude in spectral resolution may be gained by using double rotation. This brings the width of the (14)N solid-state NMR lines much closer to the region commonly associated with high-resolution solid-state NMR spectroscopy of (15)N and demonstrates the improvements in resolution that may be possible through the development of pulsed methodologies to suppress these second order effects.

Mechanical, structural, and dynamical modifications of cholesterol exposed porcine aortic elastin.

PubMed

Bilici, Kubra; Morgan, Steven W; Silverstein, Moshe C; Wang, Yunjie; Sun, Hyung Jin; Zhang, Yanhang; Boutis, Gregory S

2016-11-01

Elastin is a protein of the extracellular matrix that contributes significantly to the elasticity of connective tissues. In this study, we examine dynamical and structural modifications of aortic elastin exposed to cholesterol by NMR spectroscopic and relaxation methodologies. Macroscopic measurements are also presented and reveal that cholesterol treatment may cause a decrease in the stiffness of tissue. 2 H NMR relaxation techniques revealed differences between the relative populations of water that correlate with the swelling of the tissue following cholesterol exposure. 13 C magic-angle-spinning NMR spectroscopy and relaxation methods indicate that cholesterol treated aortic elastin is more mobile than control samples. Molecular dynamics simulations on a short elastin repeat VPGVG in the presence of cholesterol are used to investigate the energetic and entropic contributions to the retractive force, in comparison to the same peptide in water. Peptide stiffness is observed to reduce following cholesterol exposure due to a decrease in the entropic force. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanical, Structural, and Dynamical Modifications of Cholesterol Exposed Porcine Aortic Elastin

PubMed Central

Bilici, Kubra; Morgan, Steven W.; Silverstein, Moshe C.; Wang, Yunjie; Sun, Hyung Jin; Zhang, Katherine; Boutis, Gregory S.

2016-01-01

Elastin is a protein of the extracellular matrix that contributes significantly to the elasticity of connective tissues. In this study, we examine dynamical and structural modifications of aortic elastin exposed to cholesterol by NMR spectroscopic and relaxation methodologies. Macroscopic measurements are also presented and reveal that cholesterol treatment may cause a decrease in the stiffness of tissue. 2H NMR relaxation techniques revealed differences between the relative populations of water that correlate with the swelling of the tissue following cholesterol exposure. 13C magic-angle-spinning NMR spectroscopy and relaxation methods indicate that cholesterol treated aortic elastin appears more mobile than control samples. Molecular dynamics simulations on a short elastin repeat VPGVG in the presence of cholesterol are used to investigate the energetic and entropic contributions to the retractive force, in comparison to the same peptide in water. Peptide stiffness is observed to reduce following cholesterol exposure due to a decrease in the entropic force. PMID:27648754

Quantitative (13)C Solid-State NMR Spectra by Multiple-Contact Cross-polarization for Drug Delivery: From Active Principles to Excipients and Drug Carriers.

PubMed

Saïdi, Fadila; Taulelle, Francis; Martineau, Charlotte

2016-08-01

In this contribution, we present an analysis of the main parameters influencing the efficiency of the (1)H → (13)C multiple-contact cross-polarization nuclear magnetic resonance (NMR) experiment in the context of solid pharmaceutical materials. Using the optimum experimental conditions, quantitative (13)C NMR spectra are then obtained for porous metal-organic frameworks (potential drug carriers) and for components present in drug formulations (active principle ingredient and excipients, amorphous or crystalline). Finally, we show that mixtures of components can also be quantified with this method and, hence, that it represents an ideal tool for quantification of pharmaceutical formulations by (13)C cross-polarization under magic-angle spinning NMR in the industry as it is robust and easy to set up, much faster than direct (13)C polarization and is efficient for samples at natural abundance. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

DNP-enhanced ultrawideline solid-state NMR spectroscopy: Studies of platinum in metal–organic frameworks

DOE PAGES

Kobayashi, Takeshi; Perras, Frederic A.; Goh, Tian Wei; ...

2016-06-06

Ultrawideline dynamic nuclear polarization (DNP)-enhanced 195Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal–organic frameworks (MOFs). The 195Pt SSNMR spectra, with breadths reaching 10,000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis- and trans-coordinated atomic Pt 2+ species supported on themore » UiO-66-NH 2 MOF. Here, the data revealed a dominance of kinetic effects in the formation of Pt 2+ complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt 2+ complex was confirmed in MOF-253.« less

Nuclear magnetic resonance studies of amino acids and proteins. Side-chain mobility of methionine in the crystalline amonio acid and in crystallne sperm whale (Physeter catodon) myoglobin

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

Keniry, M.A.; Rothgeb, T.M.; Smith, R.L.

1983-04-12

Deuterium (/sup 2/H) nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation times (T/sub 1/) were obtained of L-(epsilon-/sup 2/H/sub 3/)methionine, L-(epsilon-/sup 2/H/sub 3/)methionine in a D,L lattice, and (S-methyl-/sup 2/H/sub 3/)methionine in the crystalline solid state, as a function of temperature, in addition to obtaining /sup 2/H T/sub 1/ and line-width results as a function of temperature on (epsilon-/sup 2/H/sub 3/)methionine-labeled sperm whale (Physeter catodon) myoglobins by using the method of magnetic ordering. Also recorded were /sup 13/C cross-polarization ''magic-angle'' sample-spinning NMR spectra of (epsilon-/sup 13/C)methionine-labeled crystalline cyanoferrimyoglobin (at 37.7 MHz, corresponding to a magnetic field strength of 3.52 T)more » and of the same protein in aqueous solution. (JMT)« less

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.

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

Ionization behavior of polyphosphoinositides determined via the preparation of pH titration curves using solid-state 31P NMR.

PubMed

Graber, Zachary T; Kooijman, Edgar E

2013-01-01

Detailed knowledge of the degree of ionization of lipid titratable groups is important for the evaluation of protein-lipid and lipid-lipid interactions. The degree of ionization is commonly evaluated by acid-base titration, but for lipids localized in a multicomponent membrane interface this is not a suitable technique. For phosphomonoester-containing lipids such as the polyphosphoinositides, phosphatidic acid, and ceramide-1-phosphate, this is more conveniently accomplished by (31)P NMR. Here, we describe a solid-state (31)P NMR procedure to construct pH titration curves to determine the degree of ionization of phosphomonoester groups in polyphosphoinositides. This procedure can also be used, with suitable sample preparation conditions, for other important signaling lipids. Access to a solid-state, i.e., magic angle spinning, capable NMR spectrometer is assumed. The procedures described here are valid for a Bruker instrument, but can be adapted for other spectrometers as needed.

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

Flash spectroscopy of purple membrane.

PubMed Central

Xie, A H; Nagle, J F; Lozier, R H

1987-01-01

Flash spectroscopy data were obtained for purple membrane fragments at pH 5, 7, and 9 for seven temperatures from 5 degrees to 35 degrees C, at the magic angle for actinic versus measuring beam polarizations, at fifteen wavelengths from 380 to 700 nm, and for about five decades of time from 1 microsecond to completion of the photocycle. Signal-to-noise ratios are as high as 500. Systematic errors involving beam geometries, light scattering, absorption flattening, photoselection, temperature fluctuations, partial dark adaptation of the sample, unwanted actinic effects, and cooperativity were eliminated, compensated for, or are shown to be irrelevant for the conclusions. Using nonlinear least squares techniques, all data at one temperature and one pH were fitted to sums of exponential decays, which is the form required if the system obeys conventional first-order kinetics. The rate constants obtained have well behaved Arrhenius plots. Analysis of the residual errors of the fitting shows that seven exponentials are required to fit the data to the accuracy of the noise level. PMID:3580488

Flash spectroscopy of purple membrane.

PubMed

Xie, A H; Nagle, J F; Lozier, R H

1987-04-01

Flash spectroscopy data were obtained for purple membrane fragments at pH 5, 7, and 9 for seven temperatures from 5 degrees to 35 degrees C, at the magic angle for actinic versus measuring beam polarizations, at fifteen wavelengths from 380 to 700 nm, and for about five decades of time from 1 microsecond to completion of the photocycle. Signal-to-noise ratios are as high as 500. Systematic errors involving beam geometries, light scattering, absorption flattening, photoselection, temperature fluctuations, partial dark adaptation of the sample, unwanted actinic effects, and cooperativity were eliminated, compensated for, or are shown to be irrelevant for the conclusions. Using nonlinear least squares techniques, all data at one temperature and one pH were fitted to sums of exponential decays, which is the form required if the system obeys conventional first-order kinetics. The rate constants obtained have well behaved Arrhenius plots. Analysis of the residual errors of the fitting shows that seven exponentials are required to fit the data to the accuracy of the noise level.

Uploading, Searching and Visualizing of Paleomagnetic and Rock Magnetic Data in the Online MagIC Database

NASA Astrophysics Data System (ADS)

Minnett, R.; Koppers, A.; Tauxe, L.; Constable, C.; Donadini, F.

2007-12-01

The Magnetics Information Consortium (MagIC) is commissioned to implement and maintain an online portal to a relational database populated by both rock and paleomagnetic data. The goal of MagIC is to archive all available measurements and derived properties from paleomagnetic studies of directions and intensities, and for rock magnetic experiments (hysteresis, remanence, susceptibility, anisotropy). MagIC is hosted under EarthRef.org at http://earthref.org/MAGIC/ and will soon implement two search nodes, one for paleomagnetism and one for rock magnetism. Currently the PMAG node is operational. Both nodes provide query building based on location, reference, methods applied, material type and geological age, as well as a visual map interface to browse and select locations. Users can also browse the database by data type or by data compilation to view all contributions associated with well known earlier collections like PINT, GMPDB or PSVRL. The query result set is displayed in a digestible tabular format allowing the user to descend from locations to sites, samples, specimens and measurements. At each stage, the result set can be saved and, where appropriate, can be visualized by plotting global location maps, equal area, XY, age, and depth plots, or typical Zijderveld, hysteresis, magnetization and remanence diagrams. User contributions to the MagIC database are critical to achieving a useful research tool. We have developed a standard data and metadata template (version 2.3) that can be used to format and upload all data at the time of publication in Earth Science journals. Software tools are provided to facilitate population of these templates within Microsoft Excel. These tools allow for the import/export of text files and provide advanced functionality to manage and edit the data, and to perform various internal checks to maintain data integrity and prepare for uploading. The MagIC Contribution Wizard at http://earthref.org/MAGIC/upload.htm executes the upload and takes only a few minutes to process tens of thousands of data records. The standardized MagIC template files are stored in the digital archives of EarthRef.org where they remain available for download by the public (in both text and Excel format). Finally, the contents of these template files are automatically parsed into the online relational database, making the data available for online searches in the paleomagnetic and rock magnetic search nodes. During the upload process the owner has the option of keeping the contribution private so it can be viewed in the context of other data sets and visualized using the suite of MagIC plotting tools. Alternatively, the new data can be password protected and shared with a group of users at the contributor's discretion. Once they are published and the owner is comfortable making the upload publicly accessible, the MagIC Editing Committee reviews the contribution for adherence to the MagIC data model and conventions to ensure a high level of data integrity.

Illuminating the Depths of the MagIC (Magnetics Information Consortium) Database

NASA Astrophysics Data System (ADS)

Koppers, A. A. P.; Minnett, R.; Jarboe, N.; Jonestrask, L.; Tauxe, L.; Constable, C.

2015-12-01

The Magnetics Information Consortium (http://earthref.org/MagIC/) is a grass-roots cyberinfrastructure effort envisioned by the paleo-, geo-, and rock magnetic scientific community. Its mission is to archive their wealth of peer-reviewed raw data and interpretations from magnetics studies on natural and synthetic samples. Many of these valuable data are legacy datasets that were never published in their entirety, some resided in other databases that are no longer maintained, and others were never digitized from the field notebooks and lab work. Due to the volume of data collected, most studies, modern and legacy, only publish the interpreted results and, occasionally, a subset of the raw data. MagIC is making an extraordinary effort to archive these data in a single data model, including the raw instrument measurements if possible. This facilitates the reproducibility of the interpretations, the re-interpretation of the raw data as the community introduces new techniques, and the compilation of heterogeneous datasets that are otherwise distributed across multiple formats and physical locations. MagIC has developed tools to assist the scientific community in many stages of their workflow. Contributors easily share studies (in a private mode if so desired) in the MagIC Database with colleagues and reviewers prior to publication, publish the data online after the study is peer reviewed, and visualize their data in the context of the rest of the contributions to the MagIC Database. From organizing their data in the MagIC Data Model with an online editable spreadsheet, to validating the integrity of the dataset with automated plots and statistics, MagIC is continually lowering the barriers to transforming dark data into transparent and reproducible datasets. Additionally, this web application generalizes to other databases in MagIC's umbrella website (EarthRef.org) so that the Geochemical Earth Reference Model (http://earthref.org/GERM/) portal, Seamount Biogeosciences Network (http://earthref.org/SBN/), EarthRef Digital Archive (http://earthref.org/ERDA/) and EarthRef Reference Database (http://earthref.org/ERR/) benefit from its development.

Grade classification of neuroepithelial tumors using high-resolution magic-angle spinning proton nuclear magnetic resonance spectroscopy and pattern recognition.

PubMed

Chen, WenXue; Lou, HaiYan; Zhang, HongPing; Nie, Xiu; Lan, WenXian; Yang, YongXia; Xiang, Yun; Qi, JianPin; Lei, Hao; Tang, HuiRu; Chen, FenEr; Deng, Feng

2011-07-01

Clinical data have shown that survival rates vary considerably among brain tumor patients, according to the type and grade of the tumor. Metabolite profiles of intact tumor tissues measured with high-resolution magic-angle spinning proton nuclear magnetic resonance spectroscopy (HRMAS (1)H NMRS) can provide important information on tumor biology and metabolism. These metabolic fingerprints can then be used for tumor classification and grading, with great potential value for tumor diagnosis. We studied the metabolic characteristics of 30 neuroepithelial tumor biopsies, including two astrocytomas (grade I), 12 astrocytomas (grade II), eight anaplastic astrocytomas (grade III), three glioblastomas (grade IV) and five medulloblastomas (grade IV) from 30 patients using HRMAS (1)H NMRS. The results were correlated with pathological features using multivariate data analysis, including principal component analysis (PCA). There were significant differences in the levels of N-acetyl-aspartate (NAA), creatine, myo-inositol, glycine and lactate between tumors of different grades (P<0.05). There were also significant differences in the ratios of NAA/creatine, lactate/creatine, myo-inositol/creatine, glycine/creatine, scyllo-inositol/creatine and alanine/creatine (P<0.05). A soft independent modeling of class analogy model produced a predictive accuracy of 87% for high-grade (grade III-IV) brain tumors with a sensitivity of 87% and a specificity of 93%. HRMAS (1)H NMR spectroscopy in conjunction with pattern recognition thus provides a potentially useful tool for the rapid and accurate classification of human brain tumor grades.

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.

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.

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.

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.

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.

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.

Mississippi Magic: Summer Library Program, 1999.

ERIC Educational Resources Information Center

Hudspeth, Jean; Shurden, Lynn Fletcher

This manual for the 1999 Mississippi summer library program for preschool through elementary age children contains the following sections: (1) Introduction, including planning, promotional activities, sample radio spots and press releases, sample letters to parents, tips for including children with disabilities, a general bibliography, a…

High zenith angle observations of PKS 2155-304 with the MAGIC-I telescope

NASA Astrophysics Data System (ADS)

Aleksić, J.; Alvarez, E. A.; Antonelli, L. A.; Antoranz, P.; Asensio, M.; Backes, M.; Barres de Almeida, U.; Barrio, J. A.; Bastieri, D.; Becerra González, J.; Bednarek, W.; Berdyugin, A.; Berger, K.; Bernardini, E.; Biland, A.; Blanch, O.; Bock, R. K.; Boller, A.; Bonnoli, G.; Borla Tridon, D.; Braun, I.; Bretz, T.; Cañellas, A.; Carmona, E.; Carosi, A.; Colin, P.; Colombo, E.; Contreras, J. L.; Cortina, J.; Cossio, L.; Covino, S.; Dazzi, F.; De Angelis, A.; De Caneva, G.; De Cea del Pozo, E.; De Lotto, B.; Delgado Mendez, C.; Diago Ortega, A.; Doert, M.; Domínguez, A.; Dominis Prester, D.; Dorner, D.; Doro, M.; Eisenacher, D.; Elsaesser, D.; Ferenc, D.; Fonseca, M. V.; Font, L.; Fruck, C.; García López, R. J.; Garczarczyk, M.; Garrido, D.; Giavitto, G.; Godinović, N.; Gozzini, S. R.; Hadasch, D.; Häfner, D.; Herrero, A.; Hildebrand, D.; Höhne-Mönch, D.; Hose, J.; Hrupec, D.; Jogler, T.; Kellermann, H.; Klepser, S.; Krähenbühl, T.; Krause, J.; Kushida, J.; La Barbera, A.; Lelas, D.; Leonardo, E.; Lewandowska, N.; Lindfors, E.; Lombardi, S.; López, M.; López, R.; López-Oramas, A.; Lorenz, E.; Makariev, M.; Maneva, G.; Mankuzhiyil, N.; Mannheim, K.; Maraschi, L.; Marcote, B.; Mariotti, M.; Martínez, M.; Mazin, D.; Meucci, M.; Miranda, J. M.; Mirzoyan, R.; Moldón, J.; Moralejo, A.; Munar-Adrover, P.; Niedzwiecki, A.; Nieto, D.; Nilsson, K.; Nowak, N.; Orito, R.; Paiano, S.; Paneque, D.; Paoletti, R.; Pardo, S.; Paredes, J. M.; Partini, S.; Perez-Torres, M. A.; Persic, M.; Peruzzo, L.; Pilia, M.; Pochon, J.; Prada, F.; Prada Moroni, P. G.; Prandini, E.; Puerto Gimenez, I.; Puljak, I.; Reichardt, I.; Reinthal, R.; Rhode, W.; Ribó, M.; Rico, J.; Rügamer, S.; Saggion, A.; Saito, K.; Saito, T. Y.; Salvati, M.; Satalecka, K.; Scalzotto, V.; Scapin, V.; Schultz, C.; Schweizer, T.; Shayduk, M.; Shore, S. N.; Sillanpää, A.; Sitarek, J.; Snidaric, I.; Sobczynska, D.; Spanier, F.; Spiro, S.; Stamatescu, V.; Stamerra, A.; Steinke, B.; Storz, J.; Strah, N.; Sun, S.; Surić, T.; Takalo, L.; Takami, H.; Tavecchio, F.; Temnikov, P.; Terzić, T.; Tescaro, D.; Teshima, M.; Tibolla, O.; Torres, D. F.; Treves, A.; Uellenbeck, M.; Vankov, H.; Vogler, P.; Wagner, R. M.; Weitzel, Q.; Zabalza, V.; Zandanel, F.; Zanin, R.

2012-08-01

Context. The high frequency peaked BL Lac PKS 2155-304 with a redshift of z = 0.116 was discovered in 1997 in the very high energy (VHE, E > 100 GeV) γ-ray range by the University of Durham Mark VI γ-ray Cherenkov telescope in Australia with a flux corresponding to 20% of the Crab Nebula flux. It was later observed and detected with high significance by the southern Cherenkov observatory H.E.S.S. establishing this source as the best studied southern TeV blazar. Detection from the northern hemisphere is difficult due to challenging observation conditions under large zenith angles. In July 2006, the H.E.S.S. collaboration reported an extraordinary outburst of VHE γ-emission. During the outburst, the VHE γ-ray emission was found to be variable on the time scales of minutes and with a mean flux of ~7 times the flux observed from the Crab Nebula. Follow-up observations with the MAGIC-I standalone Cherenkov telescope were triggered by this extraordinary outburst and PKS 2155-304 was observed between 28 July to 2 August 2006 for 15 h at large zenith angles. Aims: We studied the behavior of the source after its extraordinary flare. Furthermore, we developed an analysis method in order to analyze these data taken under large zenith angles. Methods: Here we present an enhanced analysis method for data taken at high zenith angles. We developed improved methods for event selection that led to a better background suppression. Results: The quality of the results presented here is superior to the results presented previously for this data set: detection of the source on a higher significance level and a lower analysis threshold. The averaged energy spectrum we derived has a spectral index of (-3.5 ± 0.2) above 400 GeV, which is in good agreement with the spectral shape measured by H.E.S.S. during the major flare on MJD 53 944. Furthermore, we present the spectral energy distribution modeling of PKS 2155-304. With our observations we increased the duty cycle of the source extending the light curve derived by H.E.S.S. after the outburst. Finally, we find night-by-night variability with a maximal amplitude of a factor three to four and an intranight variability in one of the nights (MJD 53 945) with a similar amplitude.

Employing Theories Far beyond Their Limits - Linear Dichroism Theory.

PubMed

Mayerhöfer, Thomas G

2018-05-15

Using linear polarized light, it is possible in case of ordered structures, such as stretched polymers or single crystals, to determine the orientation of the transition moments of electronic and vibrational transitions. This not only helps to resolve overlapping bands, but also assigning the symmetry species of the transitions and to elucidate the structure. To perform spectral evaluation quantitatively, a sometimes "Linear Dichroism Theory" called approach is very often used. This approach links the relative orientation of the transition moment and polarization direction to the quantity absorbance. This linkage is highly questionable for several reasons. First of all, absorbance is a quantity that is by its definition not compatible with Maxwell's equations. Furthermore, absorbance seems not to be the quantity which is generally compatible with linear dichroism theory. In addition, linear dichroism theory disregards that it is not only the angle between transition moment and polarization direction, but also the angle between sample surface and transition moment, that influences band shape and intensity. Accordingly, the often invoked "magic angle" has never existed and the orientation distribution influences spectra to a much higher degree than if linear dichroism theory would hold strictly. A last point that is completely ignored by linear dichroism theory is the fact that partially oriented or randomly-oriented samples usually consist of ordered domains. It is their size relative to the wavelength of light that can also greatly influence a spectrum. All these findings can help to elucidate orientation to a much higher degree by optical methods than currently thought possible by the users of linear dichroism theory. Hence, it is the goal of this contribution to point out these shortcomings of linear dichroism theory to its users to stimulate efforts to overcome the long-lasting stagnation of this important field. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state NMR and computational studies of 4-methyl-2-nitroacetanilide.

PubMed

Harris, Robin K; Ghi, Phuong Y; Hammond, Robert B; Ma, Cai Yun; Roberts, Kevin J; Yates, Jonathan R; Pickard, Chris J

2006-03-01

Studies on the solid-state structure of two polymorphs of 4-methyl-2-nitroacetanilide (MNA) were conducted using magic-angle spinning (13)C, (15)N and (1)H NMR spectroscopy, together with first-principles computations of NMR shielding (including use of a program that takes explicit account of the translational symmetry inherent in crystalline structures). The effects on (13)C chemical shifts of side-chain rotations have been explored. Information derived from these studies was then incorporated within a systematic space-search methodology for elucidation of trial crystallographic structures from powder XRD.

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

Abject Magic: Reasoning Madness in Justine Larbalestier's "Magic or Madness" Trilogy

ERIC Educational Resources Information Center

Potter, Troy

2013-01-01

This paper explores the representation of magic and madness in Justine Larbalestier's "Magic or Madness" trilogy (2005-2007). Throughout the series, magic is constructed as an abject and disabling force that threatens to disable magic-wielders, either through madness or death. Despite being represented as a ubiquitous force, the…

Origins of magic: review of genetic and epigenetic effects.

PubMed

Ramagopalan, Sreeram V; Knight, Marian; Ebers, George C; Knight, Julian C

2007-12-22

To assess the evidence for a genetic basis to magic. Literature review. Harry Potter novels of J K Rowling. Muggles, witches, wizards, and squibs. Limited. Family and twin studies, magical ability, and specific magical skills. Magic shows strong evidence of heritability, with familial aggregation and concordance in twins. Evidence suggests magical ability to be a quantitative trait. Specific magical skills, notably being able to speak to snakes, predict the future, and change hair colour, all seem heritable. A multilocus model with a dominant gene for magic might exist, controlled epistatically by one or more loci, possibly recessive in nature. Magical enhancers regulating gene expressionmay be involved, combined with mutations at specific genes implicated in speech and hair colour such as FOXP2 and MCR1.

The Magic of Balanced Groups: Educational Applications of Magic Squares

ERIC Educational Resources Information Center

Bosse, Michael J.; Nandakumar, N. R.; Ore, Melanie L.

2007-01-01

This paper provides students with many interesting observations regarding the nature of magic squares, magic rectangles, and quasi-magic squares and provides tools for teachers to group students into ability-balanced cooperative learning groups.

Interdisciplinary Collaboration amongst Colleagues and between Initiatives with the Magnetics Information Consortium (MagIC) Database

NASA Astrophysics Data System (ADS)

Minnett, R.; Koppers, A. A. P.; Jarboe, N.; Tauxe, L.; Constable, C.; Jonestrask, L.; Shaar, R.

2014-12-01

Earth science grand challenges often require interdisciplinary and geographically distributed scientific collaboration to make significant progress. However, this organic collaboration between researchers, educators, and students only flourishes with the reduction or elimination of technological barriers. The Magnetics Information Consortium (http://earthref.org/MagIC/) is a grass-roots cyberinfrastructure effort envisioned by the geo-, paleo-, and rock magnetic scientific community to archive their wealth of peer-reviewed raw data and interpretations from studies on natural and synthetic samples. MagIC is dedicated to facilitating scientific progress towards several highly multidisciplinary grand challenges and the MagIC Database team is currently beta testing a new MagIC Search Interface and API designed to be flexible enough for the incorporation of large heterogeneous datasets and for horizontal scalability to tens of millions of records and hundreds of requests per second. In an effort to reduce the barriers to effective collaboration, the search interface includes a simplified data model and upload procedure, support for online editing of datasets amongst team members, commenting by reviewers and colleagues, and automated contribution workflows and data retrieval through the API. This web application has been designed to generalize to other databases in MagIC's umbrella website (EarthRef.org) so the Geochemical Earth Reference Model (http://earthref.org/GERM/) portal, Seamount Biogeosciences Network (http://earthref.org/SBN/), EarthRef Digital Archive (http://earthref.org/ERDA/) and EarthRef Reference Database (http://earthref.org/ERR/) will benefit from its development.

The Magnetics Information Consortium (MagIC) Online Database: Uploading, Searching and Visualizing Paleomagnetic and Rock Magnetic Data

NASA Astrophysics Data System (ADS)

Minnett, R.; Koppers, A.; Tauxe, L.; Constable, C.; Pisarevsky, S. A.; Jackson, M.; Solheid, P.; Banerjee, S.; Johnson, C.

2006-12-01

The Magnetics Information Consortium (MagIC) is commissioned to implement and maintain an online portal to a relational database populated by both rock and paleomagnetic data. The goal of MagIC is to archive all measurements and the derived properties for studies of paleomagnetic directions (inclination, declination) and intensities, and for rock magnetic experiments (hysteresis, remanence, susceptibility, anisotropy). MagIC is hosted under EarthRef.org at http://earthref.org/MAGIC/ and has two search nodes, one for paleomagnetism and one for rock magnetism. Both nodes provide query building based on location, reference, methods applied, material type and geological age, as well as a visual map interface to browse and select locations. The query result set is displayed in a digestible tabular format allowing the user to descend through hierarchical levels such as from locations to sites, samples, specimens, and measurements. At each stage, the result set can be saved and, if supported by the data, can be visualized by plotting global location maps, equal area plots, or typical Zijderveld, hysteresis, and various magnetization and remanence diagrams. User contributions to the MagIC database are critical to achieving a useful research tool. We have developed a standard data and metadata template (Version 2.1) that can be used to format and upload all data at the time of publication in Earth Science journals. Software tools are provided to facilitate population of these templates within Microsoft Excel. These tools allow for the import/export of text files and provide advanced functionality to manage and edit the data, and to perform various internal checks to maintain data integrity and prepare for uploading. The MagIC Contribution Wizard at http://earthref.org/MAGIC/upload.htm executes the upload and takes only a few minutes to process several thousand data records. The standardized MagIC template files are stored in the digital archives of EarthRef.org where they remain available for download by the public (in both text and Excel format). Finally, the contents of these template files are automatically parsed into the online relational database, making the data available for online searches in the paleomagnetic and rock magnetic search nodes. The MagIC database contains all data transferred from the IAGA paleomagnetic poles database (GPMDB), the lava flow paleosecular variation database (PSVRL), lake sediment database (SECVR) and the PINT database. Additionally, a substantial number of data compiled under the Time Averaged Field Investigations project is now included plus a significant fraction of the data collected at SIO and the IRM. Ongoing additions of legacy data include over 40 papers from studies on the Hawaiian Islands and Mexico, data compilations from archeomagnetic studies and updates to the lake sediment dataset.

Expertise among professional magicians: an interview study.

PubMed

Rissanen, Olli; Pitkänen, Petteri; Juvonen, Antti; Kuhn, Gustav; Hakkarainen, Kai

2014-01-01

The purpose of the present investigation was to analyse interviews of highly regarded Finnish magicians. Social network analysis (N = 120) was used to identify Finland's most highly regarded magicians (N = 16). The selected participants' careers in professional magic and various aspects of their professional conduct were examined by relying on semi-structured interviews. The results revealed that cultivation of professional level competence in magic usually requires an extensive period of time compared with other domains of expertise. Magic is a unique performing art and it differs from other professions focusing on deceiving the audience. A distinctive feature of magical expertise is that the process takes place entirely through informal training supported by communities of magical practitioners. Three interrelated aspects of magical activity were distinguished: magic tricks, performance, and audience. Although magic tricks constitute a central aspect of magic activity, the participants did not talk about their tricks extensively; this is in accordance with the secretive nature of magic culture. The interviews revealed that a core aspect of the magicians' activity is performance in front of an audience that repeatedly validates competence cultivated through years of practice. The interviewees reported investing a great deal of effort in planning, orchestrating, and reflecting on their performances. Close interaction with the audience plays an important role in most interviewees' activity. Many participants put a great deal of effort in developing novel magic tricks. It is common to borrow magic effects from fellow magicians and develop novel methods of implementation. Because magic tricks or programs are not copyrighted, many interviewees considered "stealing" an unacceptable and unethical aspect of magical activity. The interviewees highlighted the importance of personality and charisma in the successful pursuit of magic activity.

Expertise among professional magicians: an interview study

PubMed Central

Rissanen, Olli; Pitkänen, Petteri; Juvonen, Antti; Kuhn, Gustav; Hakkarainen, Kai

2014-01-01

The purpose of the present investigation was to analyse interviews of highly regarded Finnish magicians. Social network analysis (N = 120) was used to identify Finland's most highly regarded magicians (N = 16). The selected participants' careers in professional magic and various aspects of their professional conduct were examined by relying on semi-structured interviews. The results revealed that cultivation of professional level competence in magic usually requires an extensive period of time compared with other domains of expertise. Magic is a unique performing art and it differs from other professions focusing on deceiving the audience. A distinctive feature of magical expertise is that the process takes place entirely through informal training supported by communities of magical practitioners. Three interrelated aspects of magical activity were distinguished: magic tricks, performance, and audience. Although magic tricks constitute a central aspect of magic activity, the participants did not talk about their tricks extensively; this is in accordance with the secretive nature of magic culture. The interviews revealed that a core aspect of the magicians' activity is performance in front of an audience that repeatedly validates competence cultivated through years of practice. The interviewees reported investing a great deal of effort in planning, orchestrating, and reflecting on their performances. Close interaction with the audience plays an important role in most interviewees' activity. Many participants put a great deal of effort in developing novel magic tricks. It is common to borrow magic effects from fellow magicians and develop novel methods of implementation. Because magic tricks or programs are not copyrighted, many interviewees considered “stealing” an unacceptable and unethical aspect of magical activity. The interviewees highlighted the importance of personality and charisma in the successful pursuit of magic activity. PMID:25566156

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.

MAGIC database and interfaces: an integrated package for gene discovery and expression.

PubMed

Cordonnier-Pratt, Marie-Michèle; Liang, Chun; Wang, Haiming; Kolychev, Dmitri S; Sun, Feng; Freeman, Robert; Sullivan, Robert; Pratt, Lee H

2004-01-01

The rapidly increasing rate at which biological data is being produced requires a corresponding growth in relational databases and associated tools that can help laboratories contend with that data. With this need in mind, we describe here a Modular Approach to a Genomic, Integrated and Comprehensive (MAGIC) Database. This Oracle 9i database derives from an initial focus in our laboratory on gene discovery via production and analysis of expressed sequence tags (ESTs), and subsequently on gene expression as assessed by both EST clustering and microarrays. The MAGIC Gene Discovery portion of the database focuses on information derived from DNA sequences and on its biological relevance. In addition to MAGIC SEQ-LIMS, which is designed to support activities in the laboratory, it contains several additional subschemas. The latter include MAGIC Admin for database administration, MAGIC Sequence for sequence processing as well as sequence and clone attributes, MAGIC Cluster for the results of EST clustering, MAGIC Polymorphism in support of microsatellite and single-nucleotide-polymorphism discovery, and MAGIC Annotation for electronic annotation by BLAST and BLAT. The MAGIC Microarray portion is a MIAME-compliant database with two components at present. These are MAGIC Array-LIMS, which makes possible remote entry of all information into the database, and MAGIC Array Analysis, which provides data mining and visualization. Because all aspects of interaction with the MAGIC Database are via a web browser, it is ideally suited not only for individual research laboratories but also for core facilities that serve clients at any distance.

Application of a Resource Theory for Magic States to Fault-Tolerant Quantum Computing.

PubMed

Howard, Mark; Campbell, Earl

2017-03-03

Motivated by their necessity for most fault-tolerant quantum computation schemes, we formulate a resource theory for magic states. First, we show that robustness of magic is a well-behaved magic monotone that operationally quantifies the classical simulation overhead for a Gottesman-Knill-type scheme using ancillary magic states. Our framework subsequently finds immediate application in the task of synthesizing non-Clifford gates using magic states. When magic states are interspersed with Clifford gates, Pauli measurements, and stabilizer ancillas-the most general synthesis scenario-then the class of synthesizable unitaries is hard to characterize. Our techniques can place nontrivial lower bounds on the number of magic states required for implementing a given target unitary. Guided by these results, we have found new and optimal examples of such synthesis.

Intuition, Affect, and Peculiar Beliefs

PubMed Central

Boden, Matthew Tyler; Berenbaum, Howard; Topper, Maurice

2012-01-01

Research with college students has found that intuitive thinking (e.g., using hunches to ascribe meaning to experiences) and positive affect interactively predict ideas of reference and odd/magical beliefs. We investigated whether these results would generalize to a diverse community sample of adults that included individuals with elevated levels of peculiar perceptions and beliefs. We measured positive and negative affect and intuitive thinking through questionnaires, and peculiar beliefs (i.e., ideas of reference and odd/magical beliefs) through structured clinical interviews. We found that peculiar beliefs were associated with intuitive thinking and negative affect, but not positive affect. Furthermore, in no instance did the interaction of affect and intuitive thinking predict peculiar beliefs. These results suggest that there are important differences in the factors that contribute to peculiar beliefs between college students and clinically meaningful samples. PMID:22707815

Magic star puzzle for educational mathematics

NASA Astrophysics Data System (ADS)

Gan, Yee Siang; Fong, Wan Heng; Sarmin, Nor Haniza

2013-04-01

One of the interesting fields in recreational mathematics is the magic number arrangement. There are different kinds of arrays in the arrangement for a group of numbers. In particular, one of the arrays in magic number arrangement is called magic star. In fact, magic star involves combinatorics that contributes to geometrical analysis and number theory. Hence, magic star is suitable to be introduced as educational mathematics to cultivate interest in different area of mathematics. To obtain the solutions of normal magic stars of order six, the possible sets of numbers for every line in a magic star have been considered. Previously, the calculation for obtaining the solutions has been done manually which is time-consuming. Therefore, a programming code to generate all the fundamental solutions for normal magic star of order six without including the properties of rotation and reflection has been done. In this puzzle, a magic star puzzle is created by using Matlab software, which enables a user to verify the entries for the cells of magic star of order six. Moreover, it is also user-friendly as it provides interactive commands on the inputs given by the user, which enables the user to detect the incorrect inputs. In addition, user can also choose to view all the fundamental solutions as generated by the programming code.

77 FR 58416 - Large Scale Networking (LSN); Middleware and Grid Interagency Coordination (MAGIC) Team

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-20

... Coordination (MAGIC) Team AGENCY: The Networking and Information Technology Research and Development (NITRD.... Dates/Location: The MAGIC Team meetings are held on the first Wednesday of each month, 2:00-4:00pm, at... participation is available for each meeting. Please reference the MAGIC Team Web site for updates. Magic Web...

78 FR 70076 - Large Scale Networking (LSN)-Middleware and Grid Interagency Coordination (MAGIC) Team

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-22

... Coordination (MAGIC) Team AGENCY: The Networking and Information Technology Research and Development (NITRD... MAGIC Team meetings are held on the first Wednesday of each month, 2:00-4:00 p.m., at the National... for each meeting. Please reference the MAGIC Team Web site for updates. Magic Web site: The agendas...

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.

Emotional salience, emotional awareness, peculiar beliefs, and magical thinking.

PubMed

Berenbaum, Howard; Boden, M Tyler; Baker, John P

2009-04-01

Two studies with college student participants (Ns = 271 and 185) tested whether peculiar beliefs and magical thinking were associated with (a) the emotional salience of the stimuli about which individuals may have peculiar beliefs or magical thinking, (b) attention to emotion, and (c) clarity of emotion. Study 1 examined belief that a baseball team was cursed. Study 2 measured magical thinking using a procedure developed by P. Rozin and C. Nemeroff (2002). In both studies, peculiar beliefs and magical thinking were associated with Salience x Attention x Clarity interactions. Among individuals for whom the objects of the belief-magical thinking were highly emotionally salient and who had high levels of attention to emotion, higher levels of emotional clarity were associated with increased peculiar beliefs-magical thinking. In contrast, among individuals for whom the objects of the belief-magical thinking were not emotionally salient and who had high levels of attention to emotion, higher levels of emotional clarity were associated with diminished peculiar beliefs-magical thinking. (c) 2009 APA, all rights reserved.

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.

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.

[Magical thinking in healthy people and in schizophrenia].

PubMed

Jarosz, M

1996-01-01

Different conditions of magical thinking have been analyzed. A formation of the proportion "realistic thinking - magical thinking" in paranoid schizophrenia has been discussed and the characteristic features of magical thinking in schizophrenia have been indicated.

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.

Structural and interaction parameters of thermosensitive native α-elastin biohybrid microgel

NASA Astrophysics Data System (ADS)

Balaceanu, Andreea; Singh, Smriti; Demco, Dan E.; Möller, Martin

2014-09-01

The structural and water interaction parameters for native, α-elastin biohybrid microgel crosslinked with hydrophilic and hydrophobic crosslinkers are obtained from the volume phase transition temperature behaviour, 1H high-resolution magic-angle sample spinning transverse magnetization relaxation NMR, and modified Flory-Rehner swelling theory. Firstly, considering a homogeneous morphology the number of subchains in the biohybrid microgel, the residual water in deswollen state as a function of crosslink density and the temperature dependence of the Flory biopolymer-water interaction parameters are reported for the biohybrid microgels prepared with hydrophilic (PEG-DGE) and hydrophobic (BS3) crosslinkers. The Flory-Rehner classical approach is subsequently modified taking into account the heterogeneities observed by NMR transverse relaxation measurements. Two differently mobile regions are determined, a hydrophobic domain and a crosslinking domain with relative reduced mobility. For the first time, the influence of chain mobility on the Flory interaction parameter is investigated through a modified Flory state equation. The contributions of amino-acids located in the hydrophobic and crosslinking domains in the polypeptide sequence are separated while analyzing the biopolymer-water interaction.

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.

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.

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.

Dynamics and conformations of PEO chains chemically bonded on silica: comparison between 1H and 2H NMR.

PubMed

Tajouri, T; Hommel, H

2007-06-01

1H NMR was used to study the motion of monomer units in a layer of poly(ethylene oxide) chains grafted on silica. First, the dependence of the relaxation times on the grafting ratios is discussed qualitatively from a phenomenological point of view. Next, the NMR line narrowing effect by high-speed rotation is observed in the same samples with different grafting ratios. The magic angle spinning technique permits determination of two correlation times for each grafting ratio: tau(c) characteristic of an environment with a fast motion and tau(l) characteristic of an environment with a slow motion. In addition, the dynamics of these grafted chains are investigated by deuterium NMR (2H NMR), which is sensitive to the anisotropy of molecular motion. The evolution has been studied for two extreme grafting ratios and each time as a function of temperature. The anisotropy is more marked at low temperatures and for a low grafting ratio. The results are consistent with the 1H NMR relaxation times measured as a function of temperature. Copyright 2007 John Wiley & Sons, Ltd.

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

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.

DNP enhanced NMR with flip-back recovery

NASA Astrophysics Data System (ADS)

Björgvinsdóttir, Snædís; Walder, Brennan J.; Pinon, Arthur C.; Yarava, Jayasubba Reddy; Emsley, Lyndon

2018-03-01

DNP methods can provide significant sensitivity enhancements in magic angle spinning solid-state NMR, but in systems with long polarization build up times long recycling periods are required to optimize sensitivity. We show how the sensitivity of such experiments can be improved by the classic flip-back method to recover bulk proton magnetization following continuous wave proton heteronuclear decoupling. Experiments were performed on formulations with characteristic build-up times spanning two orders of magnitude: a bulk BDPA radical doped o-terphenyl glass and microcrystalline samples of theophylline, L-histidine monohydrochloride monohydrate, and salicylic acid impregnated by incipient wetness. For these systems, addition of flip-back is simple, improves the sensitivity beyond that provided by modern heteronuclear decoupling methods such as SPINAL-64, and provides optimal sensitivity at shorter recycle delays. We show how to acquire DNP enhanced 2D refocused CP-INADEQUATE spectra with flip-back recovery, and demonstrate that the flip-back recovery method is particularly useful in rapid recycling regimes. We also report Overhauser effect DNP enhancements of over 70 at 592.6 GHz/900 MHz.

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

PubMed Central

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

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

Quantitative comparison of structure and dynamics of elastin following three isolation schemes by 13C solid state NMR and MALDI mass spectrometry.

PubMed

Papaioannou, A; Louis, M; Dhital, B; Ho, H P; Chang, E J; Boutis, G S

2015-05-01

Methods for isolating elastin from fat, collagen, and muscle, commonly used in the design of artificial elastin based biomaterials, rely on exposing tissue to harsh pH levels and temperatures that usually denature many proteins. At present, a quantitative measurement of the modifications to elastin following isolation from other extracellular matrix constituents has not been reported. Using magic angle spinning (13)C NMR spectroscopy and relaxation methodologies, we have measured the modification in structure and dynamics following three known purification protocols. Our experimental data reveal that the (13)C spectra of the hydrated samples appear remarkably similar across the various purification methods. Subtle differences in the half maximum widths were observed in the backbone carbonyl suggesting possible structural heterogeneity across the different methods of purification. Additionally, small differences in the relative signal intensities were observed between purified samples. Lyophilizing the samples results in a reduction of backbone motion and reveals additional differences across the purification methods studied. These differences were most notable in the alanine motifs indicating possible changes in cross-linking or structural rigidity. The measured correlation times of glycine and proline moieties are observed to also vary considerably across the different purification methods, which may be related to peptide bond cleavage. Lastly, the relative concentration of desmosine cross-links in the samples quantified by MALDI mass spectrometry is reported. Copyright © 2015 Elsevier B.V. All rights reserved.

Recent on-beam tests of wide angle neutron polarization analysis with a 3He spin filter: Magic PASTIS on V20 at HZB

NASA Astrophysics Data System (ADS)

Babcock, E.; Salhi, Z.; Gainov, R.; Woracek, R.; Soltner, H.; Pistel, P.; Beule, F.; Bussmann, K.; Heynen, A.; Kämmerling, H.; Suxdorf, F.; Strobl, M.; Russina, M.; Voigt, J.; Ioffe, A.

2017-06-01

A complete XYZ polarization analysis solution is under development for the new thermal time of flight spectrometer TOPAS [1], to be operated in the coming east neutron guide hall at the MLZ. Polarization Analysis Studies on a Thermal Inelastic Spectrometer, commonly called PASTIS [2], is based on polarized 3He neutron spin filters and an XYZ field configuration for the sample environment and a polarization-preserving neutron guide field. The complete system was designed to provide adiabatic transport of the neutron polarization to the sample position while maintaining the homogeneity of the XYZ field. This system has now been tested on the polarized time-of-flight ESS test beam line V20 at HZB [3]. Down to the minimum wavelength of 1.6 Å on the instrument, the magnetic configuration worked ideally for neutron spin transport while giving full experimental freedom to change between the X, Y or Z field configuration. The 3He cell used was polarized at the 3He lab of the JCNS at the MLZ in Garching and transported to HZB in Berlin via car showing that such a transport is indeed feasible for such experiments. We present results of this test and the next steps forward.

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.

Magic 2010 RASR Team

DTIC Science & Technology

2010-12-15

MAGIC 2010 – FINAL REPORT RASR TEAM - CONTRACT NO: FA2386-10-1-4021 December 15, 2010 Final Report for AOARD Grant FA23861014021 – MAGIC ... MAGIC 2010 Competition - Robotic Research Team (RASR) Abstract: The RASR team developed a system for the coordination of groups of unmanned...accomplish those missions. Our team goal was to develop a system that can provide long term value to the war-fighter, utilizing MAGIC 2010 as a stepping

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

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

Study of lignification by noninvasive techniques in growing maize internodes. An investigation by Fourier transform infrared cross-polarization-magic angle spinning 13C-nuclear magnetic resonance spectroscopy and immunocytochemical transmission electron microscopy.

PubMed Central

Joseleau, J P; Ruel, K

1997-01-01

Noninvasive techniques were used for the study in situ of lignification in the maturing cell walls of the maize (Zea mays L.) stem. Within the longitudinal axis of a developing internode all of the stages of lignification can be found. The synthesis of the three types of lignins, p-hydroxyphenylpropane (H), guaiacyl (G), and syringyl (S), was investigated in situ by cross-polarization-magic angle spinning 13C-solid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, and immunocytochemical electron microscopy. The first lignin appearing in the parenchyma is of the G-type preceeding the incorporation of S nuclei in the later stages. However, in vascular bundles, typical absorption bands of S nuclei are visible in the Fourier transform infrared spectra at the earliest stage of lignification. Immunocytochemical determination of the three types of lignin in transmission electron microscopy was possible thanks to the use of antisera prepared against synthetic H, G, and the mixed GS dehydrogenative polymers (K. Ruel, O. Faix, J.P. Joseleau [1994] J Trace Microprobe Tech 12: 247-265). The specificity of the immunological probes demonstrated that there are differences in the relative temporal synthesis of the H, G, and GS lignins in the different tissues undergoing lignification. Considering the intermonomeric linkages predominating in the antigens used for the preparation of the immunological probes, the relative intensities of the labeling obtained provided, for the first time to our knowledge, information about the macromolecular nature of lignins (condensed versus noncondensed) in relation to their ultrastructural localization and development stage. PMID:9232887

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

Magic with Magic Squares.

ERIC Educational Resources Information Center

Wills, Herbert III

1989-01-01

Describes ways to make magic squares of 4 by 4 matrices. Presents two handouts: (1) Sets of 4 Numbers from 1 to 16 Whose Sum is 34; and (2) The Durer Square. Shows patterns which appeared in the magic squares, such as squares, chevrons, rhomboids, and trapezoids. (YP)

Controlling the magic and normal sizes of white CdSe quantum dots

NASA Astrophysics Data System (ADS)

Su, Yu-Sheng; Chung, Shu-Ru

2017-08-01

In this study, we have demonstrated a facile chemical route to prepare CdSe QDs with white light emission, and the performance of white CdSe-based white light emitting diode (WLED) is also exploded. An organic oleic acid (OA) is used to form Cd-OA complex first and hexadecylamine (HDA) and 1-octadecene (ODE) is used as surfactants. Meanwhile, by varying the reaction time from 1 s to 60 min, CdSe QDs with white light can be obtained. The result shows that the luminescence spectra compose two obvious emission peaks and entire visible light from 400 to 700 nm, when the reaction time less than 10 min. The wide emission wavelength combine two particle sizes of CdSe, magic and normal, and the magic-CdSe has band-edge and surface-state emission, while normal size only possess band-edge emission. The TEM characterization shows that the two different sizes with diameter of 1.5 nm and 2.7 nm for magic and normal size CdSe QDs can be obtained when the reaction time is 4 min. We can find that the magic size of CdSe is produced when the reaction time is less than 3 min. In the time ranges from 3 to 10 min, two sizes of CdSe QDs are formed, and with QY from 20 to 60 %. Prolong the reaction time to 60 min, only normal size of CdSe QD can be observed due to the Ostwald repining, and its QYs is 8 %. Based on the results we can conclude that the two emission peaks are generated from the coexistence of magic size and normal size CdSe to form the white light QDs, and the QY and emission wavelength of CdSe QDs can be increased with prolonging reaction time. The sample reacts for 2 (QY 30 %), 4 (QY 32 %) and 60 min (QY 8 %) are choosing to mixes with transparent acrylic-based UV curable resin for WLED fabrication. The Commission International d'Eclairage (CIE) chromaticity, color rendering index (CRI), and luminous efficacy for magic, mix, and normal size CdSe are (0.49, 0.44), 81, 1.5 lm/W, (0.35, 0.30), 86, 1.9 lm/W, and (0.39, 0.25), 40, 0.3 lm/W, respectively.

Magic Roundabouts? Teaching Conservation in Schools and Universities

ERIC Educational Resources Information Center

Leather, Simon R.; Helden, Alvin J.

2005-01-01

Pitfall trap sampling of Carabid beetle species on roundabouts in Bracknell, Berkshire, was used to assess the biodiversity of this taxon by its use as an indicator. The aim of the study was to discover the role of traffic islands in the provision of refugia for invertebrate fauna in fragmented urban habitats. Sampling was performed on 15…

Manufacturing Magic and Computational Creativity

PubMed Central

Williams, Howard; McOwan, Peter W.

2016-01-01

This paper describes techniques in computational creativity, blending mathematical modeling and psychological insight, to generate new magic tricks. The details of an explicit computational framework capable of creating new magic tricks are summarized, and evaluated against a range of contemporary theories about what constitutes a creative system. To allow further development of the proposed system we situate this approach to the generation of magic in the wider context of other areas of application in computational creativity in performance arts. We show how approaches in these domains could be incorporated to enhance future magic generation systems, and critically review possible future applications of such magic generating computers. PMID:27375533

Watching films with magical content facilitates creativity in children.

PubMed

Subbotsky, Eugene; Hysted, Claire; Jones, Nicola

2010-08-01

Two experiments examined the possible link between magical thinking and creativity in preschool children. In Exp. 1, 4- and 6-yr.-old children were shown a film with either a magical or nonmagical theme. Results indicated that the mean scores of children shown the magical film was significantly higher than that of children watching the nonmagical film on the majority of subsequent creativity tests for both age groups. This trend was also found for 6-yr.-olds' drawings of impossible items. In Exp. 2, Exp. 1 was replicated successfully with 6- and 8-yr.-old children. Exposing children to a film with a magical theme did not affect their beliefs about magic. The results were interpreted to accentuate the role of magical thinking in children's cognitive development. Classroom implications of the results were also discussed.

Polar and singular value decomposition of 3×3 magic squares

NASA Astrophysics Data System (ADS)

Trenkler, Götz; Schmidt, Karsten; Trenkler, Dietrich

2013-07-01

In this note, we find polar as well as singular value decompositions of a 3×3 magic square, i.e. a 3×3 matrix M with real elements where each row, column and diagonal adds up to the magic sum s of the magic square.

Magic Johnson and children's conceptions of AIDS.

PubMed

Quadagno, D; Eberstein, I W; Foster, K; Sittig, J E; Sly, D F; Kistner, J A

1997-08-01

Longitudinal data for a heterogeneous sample of 609 elementary school children are used to assess the long-term effects of Magic Johnson's announcement on children's HIV and AIDS conceptions. Four hypotheses are tested concerning these relationships, and background variables measured prior to Johnson's announcement are controlled. Findings suggest that Johnson's announcement increased children's HIV and AIDS knowledge and reduced their prejudice toward a hypothetical child with AIDS. No relationship is evident between the announcement and perceived vulnerability to HIV and AIDS. Males are more likely to be aware of Johnson's announcement, but its effects are more pronounced among blacks. Findings from the present research affirm the potential for celebrities like Johnson in HIV and AIDS education campaigns directed toward children.

Hand preference, magical thinking and left-right confusion.

PubMed

Jaspers-Fayer, Fern; Peters, Michael

2005-03-01

Several reports suggest a significant correlation between hand preference quotients and Magical Ideation Scale (MIS) scores, such that individuals with mixed preferences have higher MIS scores. In a sample of 156 male and 257 female undergraduate university students no significant correlation was found between MIS scores and hand preference; hand preference being defined in numerous ways, and using short and long hand preference questionnaires to assess handedness. An index of left-right confusion was significantly related to MIS score, but only in females. We suggest that the role of subjects' response style and general approach to filling out questionnaires should be fully explored before "neurological" causes of links between hand preference and other questionnaire-assessed behavioural variables are invoked.

The MAGIC (Manually Assisted Gaming of Integrated Combat) Model,

DTIC Science & Technology

1982-05-01

IP -6 7 6 7 Zo - A O - ?G O 6 7 9 N L mhhhhh1h8I 1-I THE MAGIC (MANUALLY ASSISTED GAMING OF INTEGRATED COMBAT) MODEL Milton G. Weiner May 1982 L io...Corporation Santa Monica, California 90406 - - ~-. - - -i 77 THE MAGIC (MANUALLY ASSISTED GAMING OF INTEGRATED COMBAT) MODEL Milton G. Weiner May 1982 THE... MAGIC (MANUALLY ASSISTED GAMING OF INTEGRATED COMBAT) MODEL Milton G. Weiner The Rand Corporation, Santa Monica, California The MAGIC model isn’Vt

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

DeMott, Paul J.; Hill, Thomas C. J.

This campaign augmented measurements obtained via deployment of the Atmospheric Radiation Measurement (ARM) Climate Research Facility’s ARM Mobile Facility (AMF) in the Marine ARM GPCI1 Investigation of Clouds (MAGIC) field campaign. The measurements, comprised of shipboard aerosol collections obtained during the five legs of the summer 2013 cruises, were sent for offline processing to measure ice nucleating particle (INP) number concentrations. The forty-three sample periods each represented, nominally, 24-hour segments during outbound and inbound transits of the Horizon Spirit. The samples were collected at locations between Los Angeles and Hawaii. Eight samples have been analyzed for immersion freezing temperature spectramore » thus far, using funding from other grants. Remaining samples are being frozen until support for further processing is obtained. Future analyses will investigate the inorganic/organic proportions of ice nuclei, in addition to determining the genetic composition of the overall biological community associated with INPs. Resulting correlations will be compared with other archived aerosol quantities, meteorological and ocean data (e.g., temperature, wind speed, sea surface temperature, etc…) and satellite ocean color products. These findings will ultimately aid in parameterizing oceanic (e.g., sea spray) INP emissions in regional and global scale models, when illustrating aerosol connections to cloud phases and properties. Independent future analyses of frozen filter samples, as proposed by collaborating investigators at the time of this report, will include single particle analyses of marine boundary layer aerosol compositions and morphology. The MAGIC-IN data are considered representative of the oligotrophic, low Chlorophyll-a (with the exception of near-shore) ocean regions, which exist along the MAGIC transect. Current analyses suggest that INP numbers in the marine boundary layer over this region are typically low, compared to existing measurements over marine areas and those collected in the laboratory as the result of realistic sea spray particle generation. These findings, along with separate studies, confirm the existence of highly variable emission sources for INP from oceans, (though weaker than land-based emissions at modestly cooled temperatures).« less

On Super Edge-magic Total Labeling of Modified Watermill Graph

NASA Astrophysics Data System (ADS)

Nurdin; Ungko, T. S.; Gormantara, J.; Abdullah, A.; Aulyah, S.; Nikita

2018-03-01

An edge-magic total labeling on a graph G is one-to-one map from V(G) ∪ E(G) onto the set of integers 1,2, ...,ν + e, where ν = |V(G)| and e = |E(G)|, with the property that, given any edge uv, f(u) + f(u, ν}) + f(ν) = k for every u,v ∈ V(G), and k is called magic valuation. An edge-magic total labeling f is called super edge-magic total if f(v(G)) = {1,2 ...,|V(G)|} and f(E(G)) = {|V(G)| + 1, |V(G)| + 2,... |V(G) + E(G)|}. In this paper we investigate edge-magic total labeling of a new graph called modified Watermill graph. Furthermore, the magic valuation of the modified Watermill graph WM(n) is k=\\frac{1}{2}(21n+3), for n odd, n ≥ 3.

MAGIC polymer gel for dosimetric verification in boron neutron capture therapy

PubMed Central

Heikkinen, Sami; Kotiluoto, Petri; Serén, Tom; Seppälä, Tiina; Auterinen, Iiro; Savolainen, Sauli

2007-01-01

Radiation‐sensitive polymer gels are among the most promising three‐dimensional dose verification tools developed to date. We tested the normoxic polymer gel dosimeter known by the acronym MAGIC (methacrylic and ascorbic acid in gelatin initiated by copper) to evaluate its use in boron neutron capture therapy (BNCT) dosimetry. We irradiated a large cylindrical gel phantom (diameter: 10 cm; length: 20 cm) in the epithermal neutron beam of the Finnish BNCT facility at the FiR 1 nuclear reactor. Neutron irradiation was simulated with a Monte Carlo radiation transport code MCNP. To compare dose–response, gel samples from the same production batch were also irradiated with 6 MV photons from a medical linear accelerator. Irradiated gel phantoms then underwent magnetic resonance imaging to determine their R2 relaxation rate maps. The measured and normalized dose distribution in the epithermal neutron beam was compared with the dose distribution calculated by computer simulation. The results support the feasibility of using MAGIC gel in BNCT dosimetry. PACS numbers: 87.53.Qc, 87.53.Wz, 87.66.Ff PMID:17592463

Creatures in the Classroom: Preservice Teacher Beliefs About Fantastic Beasts, Magic, Extraterrestrials, Evolution and Creationism

NASA Astrophysics Data System (ADS)

Losh, Susan Carol; Nzekwe, Brandon

2011-05-01

Faculty have long expressed concern about pseudoscience belief among students. Most US research on such beliefs examines evolution-creation issues among liberal arts students, the general public, and occasionally science educators. Because of their future influence on youth, we examined basic science knowledge and several pseudoscience beliefs among 540 female and 123 male upperclass preservice teachers, comparing them with representative samples of comparably educated American adults. Future teachers resembled national adults on basic science knowledge. Their scores on evolution; creationism; intelligent design; fantastic beasts; magic; and extraterrestrials indices depended on the topic. Exempting science education, preservice teachers rejected evolution, accepting Biblical creation and intelligent design accounts. Sizable minorities "awaited more evidence" about fantastic beasts, magic, or extraterrestrials. Although gender, disciplinary major, grade point average, science knowledge, and two religiosity measures related to beliefs about evolution-creation, these factors were generally unassociated with the other indices. The findings suggest more training is needed for preservice educators in the critical evaluation of material evidence. We also discuss the judicious use of pseudoscience beliefs in such training.

78 FR 7464 - Large Scale Networking (LSN)-Middleware And Grid Interagency Coordination (MAGIC) Team

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-01

... Coordination (MAGIC) Team AGENCY: The Networking and Information Technology Research and Development (NITRD... (703) 292-4873. Date/Location: The MAGIC Team meetings are held on the first Wednesday of each month, 2... basis. WebEx participation is available for each meeting. Please reference the MAGIC Team Web site for...

Z3 -vertex magic total labeling and Z3 -edge magic total labelingfor the extended duplicate graph of quadrilateral snake

NASA Astrophysics Data System (ADS)

Indira, P.; Selvam, B.; Thirusangu, K.

2018-04-01

Based on the works of Kotzig, Rosa and MacDougall et.al., we present algorithms and prove the existence of Z3-vertex magic total labeling and Z3-edge magic total labeling for the extended duplicate graph of quadrilateral snake.

57Fe Mössbauer study of the asbestiform silicates balangeroite and carlosturanite

NASA Astrophysics Data System (ADS)

Deriu, Antonio; Ferraris, Giovanni; Belluso, Elena

1994-08-01

57FeMössbauer spectra of the two silicate minerals balangeroite (BAL) and carlosturanite (CST) have been collected at 80 and 295 K under normal and magic angle geometry. For both minerals the spectra have been fitted with two ferrous and two ferric doublets; Fe2+ accounts for 80 and 62% of Fetot in Bal and CST, respectively. The number of doublets used to fit the spectra supports the hypotheses that: (i) in the serpentine-like structure of CST iron occupies only octahedra which lie between the tetrahedral silicate strips; (ii) the octahedral framework of BAL (actually monoclinic) is satisfactorily described with an orthorhombic sub-cell.

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.

In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

DOE PAGES

Alam, Todd M.; Osborn Popp, Thomas M.

2016-06-04

High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

The Magic of Magic: The Effect of Magic Tricks on Subsequent Engagement with Lecture Material

ERIC Educational Resources Information Center

Moss, Simon A.; Irons, Melanie; Boland, Martin

2017-01-01

Background and aims: Lecturers often present entertaining videos, or organize a variety of amusing demonstrations, to foster student engagement or to encourage critical analysis. Magic tricks, in particular, have been shown to activate neural circuits that underpin motivation or problem-solving and, therefore, could be beneficial during lectures.…

Characterization of completely k-magic regular graphs

NASA Astrophysics Data System (ADS)

Eniego, A. A.; Garces, I. J. L.

2017-10-01

Let k ∈ ℕ and c ∈ ℤ k . A graph G is said to be c-sum k-magic if there is a labeling ℓ : E(G) → ℤ k {0} such that Σ u∈N(v) ℓ(uv) ≡ c (mod k) for every vertex v of G, where N(v) is the neighborhood of v in G. We say that G is completely k-magic whenever it is c-sum k-magic for every c ∈ ℤ k . In this paper, we characterize all completely k-magic regular graphs.

Experimental Investigation of the Electronic Properties of Twisted Bilayer Graphene by STM and STS

NASA Astrophysics Data System (ADS)

Yin, Longjing; Qiao, Jiabin; Wang, Wenxiao; Zuo, Weijie; He, Lin

The electronic properties of graphene multilayers depend sensitively on their stacking order. A twisted angle is treated as a unique degree of freedom to tune the electronic properties of graphene system. Here we study electronic structures of the twisted bilayers by scanning tunneling microscopy (STM) and spectroscopy (STS). We demonstrate that the interlayer coupling strength affects both the Van Hove singularities and the Fermi velocity of twisted bilayers dramatically. This removes the discrepancy about the Fermi velocity renormalization in the twisted bilayers and provides a consistent interpretation of all current data. Moreover, we report the experimental evidence for non-Abelian gauge potentials in twisted graphene bilayers by STM and STS. At a magic twisted angle, about 1.11°, a pronounced sharp peak is observed in the tunnelling spectra due to the action of the non-Abelian gauge fields. Because of the effective non-Abelian gauge fields, the rotation angle could transfer the charge carriers in the twisted bilayers from massless Dirac fermions into well localized electrons, or vice versa, efficiently. This provides a new route to tune the electronic properties of graphene systems, which will be essential in future graphene nanoelectronics.

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

Sleightly Persuasive: Using Magic To Teach Principles of Persuasion.

ERIC Educational Resources Information Center

Frasier, C. Jay

Magic can be used in the communication classroom as a means for introducing and/or illustrating the subject of persuasion. A magical effect which fools the class can lead to an early discussion of the need to be a critical consumer of persuasive messages. Magic can also be used to introduce the subject of ethics in persuasion. Each student can be…

Science meets magic: photonic metamaterials

NASA Astrophysics Data System (ADS)

Ozbay, Ekmel

2012-05-01

The word "magic" is usually associated with movies, fiction, children stories, etc. but seldom with the natural sciences. Recent advances in metamaterials have changed this notion, in which we can now speak of "almost magical" properties that scientists could only dream about only a decade ago. In this article, we review some of the recent "almost magical" progress in the field of meta-materials.

Science meets magic: photonic metamaterials

NASA Astrophysics Data System (ADS)

Ozbay, Ekmel

2012-03-01

The word "magic" is usually associated with movies, fiction, children stories, etc. but seldom with the natural sciences. Recent advances in metamaterials have changed this notion, in which we can now speak of "almost magical" properties that scientists could only dream about only a decade ago. In this article, we review some of the recent "almost magical" progress in the field of meta-materials.

Magical Ideation, Creativity, Handedness, and Cerebral Asymmetries: A Combined Behavioural and fMRI Study

ERIC Educational Resources Information Center

Badzakova-Trajkov, Gjurgjica; Haberling, Isabelle S.; Corballis, Michael C.

2011-01-01

Magical ideation has been shown to be related to measures of hand preference, in which those with mixed handedness exhibit higher levels of magical ideation than those with either consistent left- or right-handedness. It is unclear whether the relation between magical ideation and hand preference is the result of a bias in questionnaire-taking…

Compact Magic-T using microstrip-slotline transitions

NASA Technical Reports Server (NTRS)

U-Yen, Kongpop (Inventor); Wollack, Edward J. (Inventor); Doiron, Terence (Inventor); Moseley, Samuel H. (Inventor)

2010-01-01

The design of a compact low-loss Magic-T is described. The planar Magic-T incorporates a compact microstrip-slotline tee junction and small microstrip-slotline transition area to reduce slotline radiation. The Magic-T produces broadband in-phase and out-of-phase power combiner/divider responses, has low in-band insertion loss, and small in-band phase and amplitude imbalance.

Magical ideation associated social cognition in adolescents: signs of a negative facial affect recognition deficit.

PubMed

Canli, Derya; Ozdemir, Hatice; Kocak, Orhan Murat

2015-08-01

Studies provide evidence for impaired social cognition in schizotypy and its association with negative symptoms. Cognitive features related to magical ideation - a component of the positive dimension of schizotypy - have been less investigated. We aimed to assess social cognitive functioning among adolescents with high magical ideation scores, mainly focusing on face and emotion recognition. 22 subjects with magical ideation scale scores above the cut off level and 22 controls with lowest scores from among 250 students screened with this scale were included in the study. A face and emotion recognition n-back test, the empathy quotient, theory of mind tests and the Physical Anhedonia Scale were applied to both magical ideation and control groups. The magical ideation group performed significantly worse than controls on both face and emotion recognition tests. Emotion recognition performance was found to be affected by memory load, with sadness, among emotions, revealing a difference between the two groups. Empathy and theory of mind tests did not distinguish the magical ideation group from controls. Our findings provide evidence for a deficit in negative emotion recognition affected by memory load associated with magical ideation in adolescents. Copyright © 2015 Elsevier Inc. All rights reserved.

Magical ideation, creativity, handedness, and cerebral asymmetries: a combined behavioural and fMRI study.

PubMed

Badzakova-Trajkov, Gjurgjica; Häberling, Isabelle S; Corballis, Michael C

2011-08-01

Magical ideation has been shown to be related to measures of hand preference, in which those with mixed handedness exhibit higher levels of magical ideation than those with either consistent left- or right-handedness. It is unclear whether the relation between magical ideation and hand preference is the result of a bias in questionnaire-taking behaviour or of some neuropsychological concomitant of cerebral specialization. We sought to replicate this finding and further investigate how magical ideation is related to other measures of laterality, including handedness based on finger-tapping performance, and cerebral asymmetries for language, spatial judgment, and face processing as revealed by fMRI. Creative achievement was also assessed by questionnaire and correlated with magical ideation and the other measures. Magical ideation and creativity were positively correlated, and both were negatively correlated with absolute hand preference but not with hand performance or with any of the cerebral asymmetries being assessed. The results do not support the notion that the observed association between magical ideation, creativity and hand preference has a neuropsychological explanation based on reduced cerebral lateralization. Copyright © 2011 Elsevier Ltd. All rights reserved.

Old and New Magic Numbers

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

Talmi, Igal

2008-11-11

The discovery of magic numbers led to the shell model. They indicated closure of major shells and are robust: proton magic numbers are rather independent of the occupation of neutron orbits and vice versa. Recently the magic property became less stringent and we hear a lot about the discovery of new magic numbers. These, however, indicate sub-shell closures and strongly depend on occupation numbers and hence, may be called quasi-magic numbers. Some of these have been known for many years and the mechanism for their appearance as well as disappearance, was well understood within the simple shell model. The situationmore » will be illustrated by a few examples which demonstrate the simple features of the shell model. Will this simplicity emerge from the complex computations of nuclear many-body theory?.« less

The magic words: Using computers to uncover mental associations for use in magic trick design.

PubMed

Williams, Howard; McOwan, Peter W

2017-01-01

The use of computational systems to aid in the design of magic tricks has been previously explored. Here further steps are taken in this direction, introducing the use of computer technology as a natural language data sourcing and processing tool for magic trick design purposes. Crowd sourcing of psychological concepts is investigated; further, the role of human associative memory and its exploitation in magical effects is explored. A new trick is developed and evaluated: a physical card trick partially designed by a computational system configured to search for and explore conceptual spaces readily understood by spectators.

Mechanics of a granular skin

NASA Astrophysics Data System (ADS)

Karmakar, Somnath; Sane, Anit; Bhattacharya, S.; Ghosh, Shankar

2017-04-01

Magic sand, a hydrophobic toy granular material, is widely used in popular science instructions because of its nonintuitive mechanical properties. A detailed study of the failure of an underwater column of magic sand shows that these properties can be traced to a single phenomenon: the system self-generates a cohesive skin that encapsulates the material inside. The skin, consisting of pinned air-water-grain interfaces, shows multiscale mechanical properties: they range from contact-line dynamics in the intragrain roughness scale, to plastic flow at the grain scale, all the way to sample-scale mechanical responses. With decreasing rigidity of the skin, the failure mode transforms from brittle to ductile (both of which are collective in nature) to a complete disintegration at the single-grain scale.

[French translations and adaptations of questionnaires of magical thinking (MIS, Eckblad and Chapman, 1983) and perception disorders (PAS, Chapman et al., 1978)].

PubMed

Dumas, P; Saoud, M; Gutknecht, C; Dalery, J; d'Amato, T

1999-01-01

Meehl used the term "schizotype" to refer to individuals who possess an underlying vulnerability for schizophrenia. Because of the extremely varying degrees of the schizotype's clinical expression, he recommended assessing schizotypic signs through objective measures rather than clinical judgement. In this way, Chapman et al. have developed symptom-oriented scales based on Meehl's manual, such as the Social Anhedonia (SA) and Physical Anhedonia (PhA) Scales, the Magical Ideation Scale (MIS), the Perceptual Aberration Scale (PAS) and the Impulsive Nonconformity Scale (IN). Whereas Chapman's scales of psychosis proneness are the most internationally used instruments for the assessment of schizotypy, some of them, such as MIS and PAS, were still not available in French. Therefore, the first aim of this report was to offer French translations of the Magical Ideation and the Perceptual Aberration Scales; the agreement of the original authors were obtained for both translated versions and their back translations. The second aim of our study was to establish French norms for each of these scales. The preliminary norms presented here [MIS: 19/30 (for females) and 20/30 (for males); PAS: 18/35 (for both genders)] were obtained by administering both scales to a sample of 134 French students. They are very close to those found by Chapman et al. for University of Wisconsin undergraduate students. We will confirm them with a larger sample of French students.

Polarization and photometric observations of the gamma-ray blazar PG 1553+113

NASA Astrophysics Data System (ADS)

Andruchow, I.; Combi, J. A.; Muñoz-Arjonilla, A. J.; Romero, G. E.; Cellone, S. A.; Martí, J.

2011-07-01

We present the results of an observational photo-polarimetry campaign of the blazar PG 1553+113 at optical wavelengths. The blazar was recently detected at very high energies (>100 GeV) by the HESS and MAGIC γ-ray Cherenkov telescopes. Our high-temporal resolution data show significant variations in the linear polarization percentage and position angle at inter-night time-scales, while at shorter (intra-night) time-scales both parameters varied less significantly, if at all. Changes in the polarization angle seem to be common in γ-ray emitting blazars. Simultaneous differential photometry (through the B and R bands) shows no significant variability in the total optical flux. We provide B and R magnitudes, along with a finding chart, for a set of field stars suitable for differential photometry. Based on observations collected at the Centro Astronómico Hispano Alemán (CAHA) at Calar Alto, operated jointly by the Max-Planck Institut für Astronomie and the Instituto de Astrofísica de Andalucía (CSIC).

Mathematical Construction of Magic Squares Utilizing Base-N Arithmetic

ERIC Educational Resources Information Center

O'Brien, Thomas D.

2006-01-01

Magic squares have been of interest as a source of recreation for over 4,500 years. A magic square consists of a square array of n[squared] positive and distinct integers arranged so that the sum of any column, row, or main diagonal is the same. In particular, an array of consecutive integers from 1 to n[squared] forming an nxn magic square is…

Magical ideation -- defense mechanism or neuropathology? A study with multiple sclerosis patients.

PubMed

te Wildt, Bert Theodor; Schultz-Venrath, Ulrich

2004-01-01

The major psychological stress factor in multiple sclerosis (MS) is loss of control of life. In MS patients with impaired cognition, magical ideation might be a characteristic way of thinking. Proof for this may be the high frequency of alternative treatments used by individuals with MS. The study investigates whether the level of magical ideation in MS patients is higher compared to healthy control subjects and, in case of positive confirmation, with which somatic and psychological features it is associated. Moreover, it is aimed to discuss the modalities of magical ideation in general. A German version of the Magical Ideation Scale was validated with a group of 69 healthy subjects. Ninety-four MS patients were additionally assessed with the Dissociative Experience Scale, the Symptom-Check-List-90-Revised and 5 neuropsychological tests. The Magical Ideation Scale did not reveal a significant difference between MS patients and healthy controls (p = 0.968). Among the MS patients, magical ideation shows a correlation neither with age nor with disability, but a positive correlation (p = 0.007; r = 0.329) with the grade of neuropsychological deficiency. Among the psychological parameters, the highest positive correlation with magical ideation was found in dissociation (p = 0.000; r = 0.520). Magical ideation, sharing common features with dissociation, can be viewed as an early defense mechanism when perceiving a loss of control of life, particularly in early stages of MS. In late stages, when developing neuropsychological deficits, it may occur as a substitute for cognitive coping. The data may encourage clinicians to identify magical ideation. In young and previously diagnosed patients, it is important to acknowledge helplessness and support a rather rational way of coping. Training cognitive skills could be crucial to prevent older patients from losing touch with reality. More generally, the occurrence of a significant amount of magical ideation is discussed both as a psychological and a neurophysiologic regression of thinking. Copyright 2004 S. Karger AG, Basel

Back-extraction of trace elements from organometallic-halide extracts for determination by flameless atomic absorption spectrometry

USGS Publications Warehouse

Clark, J.R.; Viets, J.G.

1981-01-01

The Methyl isobutyl ketone-Amine synerGistic Iodkte Complex (MAGIC) extraction system offers the advantage that a large number of trace elements can be rapidly determined with a single sample preparation procedure. However, many of the elements extracted by the MAGIC system form volatile organometallic halide salts when the organic extract is heated in the graphite furnace. High concentrations of some elements such as Cu and Zn extracted by the system from anomalous geological samples produce serious interferences when certain other elements are determined by flameless atomic absorption. Stripping systems have been developed using solutions of HNO3, H2SO4, and CH3COOH individually or combined with H2O2 in order to circumvent these problems. With these systems most of the elements in the organic extract can be sequentially stripped into an aqueous phase. Organometallic volatilization and the most serious interelement interferences, therefore, can be eliminated by stripping with various combinations of reagents in a series of steps.

Magic at the Marketplace: Choice Blindness for the Taste of Jam and the Smell of Tea

ERIC Educational Resources Information Center

Hall, Lars; Johansson, Petter; Tarning, Betty; Sikstrom, Sverker; Deutgen, Therese

2010-01-01

We set up a tasting venue at a local supermarket and invited passerby shoppers to sample two different varieties of jam and tea, and to decide which alternative in each pair they preferred the most. Immediately after the participants had made their choice, we asked them to again sample the chosen alternative, and to verbally explain why they chose…

Children's and adults' reactions to magical and ordinary suggestion: are suggestibility and magical thinking psychologically close relatives?

PubMed

Subbotsky, Eugene

2007-11-01

In Experiment 1, 6- and 9-year-old children and adults were asked to imagine various types of objects. The experimenter then attempted to change the image of those objects in participants' minds by either suggesting that the objects may change against the participants' will, or by asking participants to change the objects as a favor to the experimenter. Two types of suggestive causation were employed: Magical-suggestion (a magic spell was cast with the aim of changing the imagined objects) and ordinary-suggestion (participants were told that the objects in their minds could alter against their will). Ordinary-suggestion was as effective as magical-suggestion in changing the participants' imagined objects. For adults, a direct request for compliance produced a stronger effect than did magical suggestion. This effect was not found in children. In Experiment 2, the two types of suggestion were tested on an alternative type of imagined objects. Adult participants were asked to imagine their futures. It was then proposed that (a) a magic spell could be cast on their futures with the aim of changing them either for the worse or for the better (magical-suggestion), or (b) changing a numerical pattern on a computer screen could change their futures (ordinary-suggestion). All participants denied that changing a numerical pattern on a computer screen could affect their lives, yet in their actions they demonstrated an element of belief in this possibility. As in Experiment 1, in Experiment 2 ordinary suggestion was as effective as magical suggestion. The hypothesis of an historic contiguity between magical causality and ordinary suggestion is discussed.

A Note on Magic Squares

ERIC Educational Resources Information Center

Williams, Horace E.

1974-01-01

A method for generating 3x3 magic squares is developed. A series of questions relating to these magic squares is posed. An invesitgation using matrix methods is suggested with some questions for consideration. (LS)

The Versatile Magic Square.

ERIC Educational Resources Information Center

Watson, Gale A.

2003-01-01

Demonstrates the transformations that are possible to construct a variety of magic squares, including modifications to challenge students from elementary grades through algebra. Presents an example of using magic squares with students who have special needs. (YDS)

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.

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

In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

PubMed

Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

2013-01-02

We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

Ion implantation modified stainless steel as a substrate for hydroxyapatite deposition. Part I. Surface modification and characterization.

PubMed

Pramatarova, L; Pecheva, E; Krastev, V; Riesz, F

2007-03-01

Material surfaces play critical role in biology and medicine since most biological reactions occur on surfaces and interfaces. There are many examples showing that the surface properties of the materials control and are directly involved in biological reactions and processes in-vitro like blood compatibility, protein absorption, cell development, etc. The rules that govern the diversity of biological surface phenomenon are fundamental physical laws. Stainless steel doped with Cr, Ni and Mo is widely used material in medicine and dentistry due to its excellent corrosion resistance and mechanical properties. The interest in this material has stimulated extensive studies on improving its bone-bonding properties. This paper describes the surface modification of Cr-Ni stainless steel (AISI 316) by a whole surface sequential implantation of Ca and P ions (the basic ions of hydroxyapatite). Three groups of stainless steel samples are prepared: (i) ion-implanted, (ii) ion-implanted and thermally treated at 600( composite function)C in air for 1 h and (iii) initials. The surface chemistry and topography before and after the surface modification are characterized by X-ray photoelectron spectroscopy, Auger electron spectroscopy, magic mirror method, atomic force microscopy and contact angle measurements.

Quasi-equilibria in reduced Liouville spaces.

PubMed

Halse, Meghan E; Dumez, Jean-Nicolas; Emsley, Lyndon

2012-06-14

The quasi-equilibrium behaviour of isolated nuclear spin systems in full and reduced Liouville spaces is discussed. We focus in particular on the reduced Liouville spaces used in the low-order correlations in Liouville space (LCL) simulation method, a restricted-spin-space approach to efficiently modelling the dynamics of large networks of strongly coupled spins. General numerical methods for the calculation of quasi-equilibrium expectation values of observables in Liouville space are presented. In particular, we treat the cases of a time-independent Hamiltonian, a time-periodic Hamiltonian (with and without stroboscopic sampling) and powder averaging. These quasi-equilibrium calculation methods are applied to the example case of spin diffusion in solid-state nuclear magnetic resonance. We show that there are marked differences between the quasi-equilibrium behaviour of spin systems in the full and reduced spaces. These differences are particularly interesting in the time-periodic-Hamiltonian case, where simulations carried out in the reduced space demonstrate ergodic behaviour even for small spins systems (as few as five homonuclei). The implications of this ergodic property on the success of the LCL method in modelling the dynamics of spin diffusion in magic-angle spinning experiments of powders is discussed.

Broadband excitation and indirect detection of nitrogen-14 in rotating solids using Delays Alternating with Nutation (DANTE)

NASA Astrophysics Data System (ADS)

Vitzthum, Veronika; Caporini, Marc A.; Ulzega, Simone; Bodenhausen, Geoffrey

2011-09-01

A train of short rotor-synchronized pulses in the manner of Delays Alternating with Nutations for Tailored Excitation (DANTE) applied to nitrogen-14 nuclei ( I = 1) in samples spinning at the magic angle at high frequencies (typically νrot = 62.5 kHz so that τrot = 16 μs) allows one to achieve uniform excitation of a great number of spinning sidebands that arise from large first-order quadrupole interactions, as occur for aromatic nitrogen-14 nuclei in histidine. With routine rf amplitudes ω1( 14N)/(2 π) = 60 kHz and very short pulses of a typical duration 0.5 < τp < 2 μs, efficient excitation can be achieved with 13 rotor-synchronized pulses in 13 τrot = 208 μs. Alternatively, with 'overtone' DANTE sequences using 2, 4, or 8 pulses per rotor period one can achieve efficient broadband excitation in fewer rotor periods, typically 2-4 τrot. These principles can be combined with the indirect detection of 14N nuclei via spy nuclei with S = ½ such as 1H or 13C in the manner of Dipolar Heteronuclear Multiple-Quantum Correlation (D-HMQC).

Characterization of nicergoline polymorphs crystallized in several organic solvents.

PubMed

Malaj, Ledjan; Censi, Roberta; Capsoni, Doretta; Pellegrino, Luca; Bini, Marcella; Ferrari, Stefania; Gobetto, Roberto; Massarotti, Vincenzo; Di Martino, Piera

2011-07-01

Nicergoline (NIC), a poorly water-soluble semisynthetic ergot derivative, was crystallized from several organic solvents, obtaining two different polymorphic forms, the triclinic form I and the orthorhombic form II. NIC samples were then characterized by several techniques such as (13)C cross-polarization magic angle spinning solid-state spectroscopy, room-temperature and high-temperature X-ray powder diffraction, differential scanning calorimetry, and by analysis of weight loss, solvent content, powder density, morphology, and particle size. Solubility and intrinsic dissolution rates determined for the two polymorphic forms in water and hydrochloride solutions (HCl 0.1 N) were always higher for form II than for form I, which is actually the form used for the industrial preparation of NIC medicinal products. Preformulation studies might encourage industry for the evaluation of polymorph II, as it is more suitable for pharmaceutical applications. Results in drug delivery, as well as those obtained by the above-mentioned techniques, and the application of Burger-Ramberger's rules make it possible to conclude that there is a thermodynamic relation of monotropy between the two polymorphs. This last assumption may help formulators in predicting the relative stability of the two forms. Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association

Differential network analysis reveals the genome-wide landscape of estrogen receptor modulation in hormonal cancers

PubMed Central

Hsiao, Tzu-Hung; Chiu, Yu-Chiao; Hsu, Pei-Yin; Lu, Tzu-Pin; Lai, Liang-Chuan; Tsai, Mong-Hsun; Huang, Tim H.-M.; Chuang, Eric Y.; Chen, Yidong

2016-01-01

Several mutual information (MI)-based algorithms have been developed to identify dynamic gene-gene and function-function interactions governed by key modulators (genes, proteins, etc.). Due to intensive computation, however, these methods rely heavily on prior knowledge and are limited in genome-wide analysis. We present the modulated gene/gene set interaction (MAGIC) analysis to systematically identify genome-wide modulation of interaction networks. Based on a novel statistical test employing conjugate Fisher transformations of correlation coefficients, MAGIC features fast computation and adaption to variations of clinical cohorts. In simulated datasets MAGIC achieved greatly improved computation efficiency and overall superior performance than the MI-based method. We applied MAGIC to construct the estrogen receptor (ER) modulated gene and gene set (representing biological function) interaction networks in breast cancer. Several novel interaction hubs and functional interactions were discovered. ER+ dependent interaction between TGFβ and NFκB was further shown to be associated with patient survival. The findings were verified in independent datasets. Using MAGIC, we also assessed the essential roles of ER modulation in another hormonal cancer, ovarian cancer. Overall, MAGIC is a systematic framework for comprehensively identifying and constructing the modulated interaction networks in a whole-genome landscape. MATLAB implementation of MAGIC is available for academic uses at https://github.com/chiuyc/MAGIC. PMID:26972162

Is {sup 276}U a doubly magic nucleus?

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

Liliani, N., E-mail: netta.liliani@gmail.com; Sulaksono, A.

2016-04-19

We investigate a possible new doubly magic heavy nucleus by using a relativistic mean-field (RMF) model with the addition of a cross interaction term of omega-rho mesons and an electromagnetic exchange term. We propose that {sup 276}U is a doubly magic nucleus. The evidence for {sup 276}U being a doubly magic nucleus is shown through the two-nucleon gaps, the single-particle energies, and the neutron skin thickness of the nucleus. We have also found that the prediction of {sup 276}U as a doubly magic nucleus by the RMF model is not affected by the inclusion of isoscalar-isovector and electromagnetic exchange couplings.

Bound states for magic state distillation in fault-tolerant quantum computation.

PubMed

Campbell, Earl T; Browne, Dan E

2010-01-22

Magic state distillation is an important primitive in fault-tolerant quantum computation. The magic states are pure nonstabilizer states which can be distilled from certain mixed nonstabilizer states via Clifford group operations alone. Because of the Gottesman-Knill theorem, mixtures of Pauli eigenstates are not expected to be magic state distillable, but it has been an open question whether all mixed states outside this set may be distilled. In this Letter we show that, when resources are finitely limited, nondistillable states exist outside the stabilizer octahedron. In analogy with the bound entangled states, which arise in entanglement theory, we call such states bound states for magic state distillation.

The magic words: Using computers to uncover mental associations for use in magic trick design

PubMed Central

2017-01-01

The use of computational systems to aid in the design of magic tricks has been previously explored. Here further steps are taken in this direction, introducing the use of computer technology as a natural language data sourcing and processing tool for magic trick design purposes. Crowd sourcing of psychological concepts is investigated; further, the role of human associative memory and its exploitation in magical effects is explored. A new trick is developed and evaluated: a physical card trick partially designed by a computational system configured to search for and explore conceptual spaces readily understood by spectators. PMID:28792941

Magic Physics?

ERIC Educational Resources Information Center

Featonby, David

2010-01-01

This article examines several readily available "magic tricks" which base their "trickery" on physics principles, and questions the use of the word "magic" in the 21st century, both in popular children's science and in everyday language. (Contains 18 figures.)

Magical thinking and memory: distinctiveness effect for tv commercials with magical content.

PubMed

Subbotsky, Eugene; Mathews, Jayne

2011-10-01

The aim of this study was to examine whether memorizing advertised products of television advertisements with magical effects (i.e., talking animals, inanimate objects which turn into humans, objects that appear from thin air or instantly turn into other objects) is easier than memorizing products of advertisements without such effects, by testing immediate and delayed retention. Adolescents and adults viewed two films containing television advertisements and were asked to recall and recognize the films' characters, events, and advertised products. Film 1 included magical effects, but Film 2 did not. On a free-recall test, no differences in the number of items recalled were noted for the two films. On the immediate recognition test, adolescents, but not adults, showed significantly better recognition for the magical than the nonmagical film. When this test was repeated two weeks later, results were reversed: adults, but not adolescents, recognized a significantly larger number of items from the magical film than the nonmagical one. These results are interpreted to accentuate the role of magical thinking in cognitive processes.

MAGIC Computer Simulation. Volume 2: Analyst Manual, Part 1

DTIC Science & Technology

1971-05-01

A review of the subject Magic Computer Simulation User and Analyst Manuals has been conducted based upon a request received from the US Army...1971 4. TITLE AND SUBTITLE MAGIC Computer Simulation Analyst Manual Part 1 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6...14. ABSTRACT The MAGIC computer simulation generates target description data consisting of item-by-item listings of the target’s components and air

NTRFACE for MAGIC

DTIC Science & Technology

1989-07-31

40. NO NO ACCESSION NO N7 ?I TITLE (inWijuod Security Claisification) NTRFACE FOR MAGIC 𔃼 PERSONAL AUTHOR(S) N.T. GLADD PE OF REPORT T b TIME...the MAGIC Particle-in-Cell Simulation Code. 19 ABSTRACT (Contianue on reverse if nceary and d ntiy by block number) The NTRFACE system was developed...made concret by applying it to a specific application- a mature, highly complex plasma physics particle in cell simulation code name MAGIC . This

Physical aging in graphite/epoxy composites

NASA Technical Reports Server (NTRS)

Kong, E. S. W.

1983-01-01

Sub-Tg annealing has been found to affect the properties of graphite/epoxy composites. The network epoxy studied was based on the chemistry of tetraglycidyl 4,4'-diamino-diphenyl methane (TGDDM) crosslinked by 4,4'-diamino-diphenyl sulfone (DDS). Differential scanning calorimetry, thermal mechanical analysis, and solid-state cross-polarized magic-angle-spinning nuclear magnetic resonance spectroscopy have been utilized in order to characterize this process of recovery towards thermodynamic equilibrium. The volume and enthalpy recovery as well as the 'thermoreversibility' aspects of the physical aging are discussed. This nonequilibrium and time-dependent behavior of network epoxies are considered in view of the increasingly wide applications of TGDDM-DDS epoxies as matrix materials of structural composites in the aerospace industry.

The Influence of Chemical Modification on Linker Rotational Dynamics in Metal-Organic Frameworks.

PubMed

Damron, Joshua T; Ma, Jialiu; Kurz, Ricardo; Saalwächter, Kay; Matzger, Adam J; Ramamoorthy, Ayyalusamy

2018-05-21

The robust synthetic flexibility of metal-organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid-state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated-local-field NMR approach to show how specific intraframework chemical modifications to MOF UiO-66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical SAPO‐34 Architectures with Tailored Acid Sites using Sustainable Sugar Templates

PubMed Central

Miletto, Ivana; Ivaldi, Chiara; Paul, Geo; Chapman, Stephanie; Marchese, Leonardo; Raja, Robert

2018-01-01

Abstract In a distinct, bottom‐up synthetic methodology, monosaccharides (fructose and glucose) and disaccharides (sucrose) have been used as mesoporogens to template hierarchical SAPO‐34 catalysts. Detailed materials characterization, which includes solid‐state magic angle spinning NMR and probe‐based FTIR, reveals that, although the mesopore dimensions are modified by the identity of the sugar template, the desirable acid characteristics of the microporous framework are retained. When the activity of the hierarchical SAPO‐34 catalysts was evaluated in the industrially relevant Beckmann rearrangement, under liquid‐phase conditions, the enhanced mass‐transport properties of sucrose‐templated hierarchical SAPO‐34 were found to deliver a superior yield of ϵ‐caprolactam. PMID:29686961

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.

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.

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.

Quadrupolar magic angle spinning NMR spectra fitted using the Pearson IV function.

PubMed

Mironenko, Roman M; Belskaya, Olga B; Talsi, Valentin P; Likholobov, Vladimir A

2014-01-01

The Pearson IV function was used to fit the asymmetric solid-state (27)Al NMR spectra of alumina based catalysts. A high convergence (correlation coefficient is no less than 0.997) between experimental and simulated spectra was achieved. The decomposition of the (27)Al NMR spectra of zinc/aluminum mixed oxides with different Zn/Al molar ratio revealed an increased fraction (6-9%) of pentacoordinated aluminum atoms in these oxides as compared to γ-Al2O3. As the Zn/Al ratio is raised, the fraction of [AlO6] octahedral units decreases, while the fraction of [AlO4] tetrahedra increases. Copyright © 2014 Elsevier Inc. All rights reserved.

Solid-state NMR studies of form I of atorvastatin calcium.

PubMed

Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

2012-03-22

Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

Heterogeneous data fusion for brain tumor classification.

PubMed

Metsis, Vangelis; Huang, Heng; Andronesi, Ovidiu C; Makedon, Fillia; Tzika, Aria

2012-10-01

Current research in biomedical informatics involves analysis of multiple heterogeneous data sets. This includes patient demographics, clinical and pathology data, treatment history, patient outcomes as well as gene expression, DNA sequences and other information sources such as gene ontology. Analysis of these data sets could lead to better disease diagnosis, prognosis, treatment and drug discovery. In this report, we present a novel machine learning framework for brain tumor classification based on heterogeneous data fusion of metabolic and molecular datasets, including state-of-the-art high-resolution magic angle spinning (HRMAS) proton (1H) magnetic resonance spectroscopy and gene transcriptome profiling, obtained from intact brain tumor biopsies. Our experimental results show that our novel framework outperforms any analysis using individual dataset.

Access to aliphatic protons as reporters in non-deuterated proteins by solid-state NMR.

PubMed

Vasa, Suresh Kumar; Rovó, Petra; Giller, Karin; Becker, Stefan; Linser, Rasmus

2016-03-28

Interactions within proteins, with their surrounding, and with other molecules are mediated mostly by hydrogen atoms. In fully protonated, inhomogeneous, or larger proteins, however, aliphatic proton shifts tend to show little dispersion despite fast Magic-Angle Spinning. 3D correlations dispersing aliphatic proton shifts by their better resolved amide N/H shifts can alleviate this problem. Using inverse second-order cross-polarization (iSOCP), we here introduce dedicated and improved means to sensitively link site-specific chemical shift information from aliphatic protons with a backbone amide resolution. Thus, even in cases where protein deuteration is impossible, this approach may enable access to various aspects of protein functions that are reported on by protons.

Met-Activating Genetically Improved Chimeric Factor-1 Promotes Angiogenesis and Hypertrophy in Adult Myogenesis.

PubMed

Ronzoni, Flavio; Ceccarelli, Gabriele; Perini, Ilaria; Benedetti, Laura; Galli, Daniela; Mulas, Francesca; Balli, Martina; Magenes, Giovanni; Bellazzi, Riccardo; De Angelis, Gabriella C; Sampaolesi, Maurilio

2017-01-01

Myogenic progenitor cells (activated satellite cells) are able to express both HGF and its receptor cMet. After muscle injury, HGF-Met stimulation promotes activation and primary division of satellite cells. MAGIC-F1 (Met-Activating Genetically Improved Chimeric Factor-1) is an engineered protein that contains two human Met-binding domains that promotes muscle hypertrophy. MAGIC-F1 protects myogenic precursors against apoptosis and increases their fusion ability enhancing muscle differentiation. Hemizygous and homozygous Magic-F1 transgenic mice displayed constitutive muscle hypertrophy. Here we describe microarray analysis on Magic-F1 myogenic progenitor cells showing an altered gene signatures on muscular hypertrophy and angiogenesis compared to wild-type cells. In addition, we performed a functional analysis on Magic-F1+/+ transgenic mice versus controls using treadmill test. We demonstrated that Magic-F1+/+ mice display an increase in muscle mass and cross-sectional area leading to an improvement in running performance. Moreover, the presence of MAGIC-F1 affected positively the vascular network, increasing the vessel number in fast twitch fibers. Finally, the gene expression profile analysis of Magic-F1+/+ satellite cells evidenced transcriptomic changes in genes involved in the control of muscle growth, development and vascularisation. We showed that MAGIC-F1-induced muscle hypertrophy affects positively vascular network, increasing vessel number in fast twitch fibers. This was due to unique features of mammalian skeletal muscle and its remarkable ability to adapt promptly to different physiological demands by modulating the gene expression profile in myogenic progenitors. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Finding All Solutions to the Magic Hexagram

ERIC Educational Resources Information Center

Holland, Jason; Karabegov, Alexander

2008-01-01

In this article, a systematic approach is given for solving a magic star puzzle that usually is accomplished by trial and error or "brute force." A connection is made to the symmetries of a cube, thus the name Magic Hexahedron.

MAGIC Computer Simulation. Volume 1: User Manual

DTIC Science & Technology

1970-07-01

vulnerability and MAGIC programs. A three-digit code is assigned to each component of the target, such as armor, gun tube; and a two-digit code is assigned to...A review of the subject Magic Computer Simulation User and Analyst Manuals has been conducted based upon a request received from the US Army...1970 4. TITLE AND SUBTITLE MAGIC Computer Simulation 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT

An Overview of the MAGIC Project

DTIC Science & Technology

1993-12-01

unlimnitedj_ _______ 13. ABSTRACT (Mxmwn WO0 words) This note provides an overview of the MAGIC project1 which is developing a high-speed, wide-area...298Rv.9 16. PRICE COASSDE 3.1 17. SEURITY18. SEURITY19. SEURITY2930.2BIA NO An Overview of the M 93B0000173 MAGIC Project December 1993 Barbara B...Intelligence Division ii ABSTRACT This note provides an overview of the MAGIC project, which is developing a high-speed, wide- area networking testbed

Secrets of the Chinese magic mirror replica

NASA Astrophysics Data System (ADS)

Mak, Se-yuen; Yip, Din-yan

2001-03-01

We examine the structure of five Chinese magic mirror replicas using a special imaging technique developed by the authors. All mirrors are found to have a two-layered structure. The reflecting surface that gives rise to a projected magic pattern on the screen is hidden under a polished half-reflecting top layer. An alternative method of making the magic mirror using ancient technology has been proposed. Finally, we suggest a simple method of reconstructing a mirror replica in the laboratory.

Magic in the machine: a computational magician's assistant.

PubMed

Williams, Howard; McOwan, Peter W

2014-01-01

A human magician blends science, psychology, and performance to create a magical effect. In this paper we explore what can be achieved when that human intelligence is replaced or assisted by machine intelligence. Magical effects are all in some form based on hidden mathematical, scientific, or psychological principles; often the parameters controlling these underpinning techniques are hard for a magician to blend to maximize the magical effect required. The complexity is often caused by interacting and often conflicting physical and psychological constraints that need to be optimally balanced. Normally this tuning is done by trial and error, combined with human intuitions. Here we focus on applying Artificial Intelligence methods to the creation and optimization of magic tricks exploiting mathematical principles. We use experimentally derived data about particular perceptual and cognitive features, combined with a model of the underlying mathematical process to provide a psychologically valid metric to allow optimization of magical impact. In the paper we introduce our optimization methodology and describe how it can be flexibly applied to a range of different types of mathematics based tricks. We also provide two case studies as exemplars of the methodology at work: a magical jigsaw, and a mind reading card trick effect. We evaluate each trick created through testing in laboratory and public performances, and further demonstrate the real world efficacy of our approach for professional performers through sales of the tricks in a reputable magic shop in London.

Migration to Current Open Source Technologies by MagIC Enables a More Responsive Website, Quicker Development Times, and Increased Community Engagement

NASA Astrophysics Data System (ADS)

Jarboe, N.; Minnett, R.; Koppers, A.; Constable, C.; Tauxe, L.; Jonestrask, L.

2017-12-01

The Magnetics Information Consortium (MagIC) supports an online database for the paleo, geo, and rock magnetic communities ( https://earthref.org/MagIC ). Researchers can upload data into the archive and download data as selected with a sophisticated search system. MagIC has completed the transition from an Oracle backed, Perl based, server oriented website to an ElasticSearch backed, Meteor based thick client website technology stack. Using JavaScript on both the sever and the client enables increased code reuse and allows easy offloading many computational operations to the client for faster response. On-the-fly data validation, column header suggestion, and spreadsheet online editing are some new features available with the new system. The 3.0 data model, method codes, and vocabulary lists can be browsed via the MagIC website and more easily updated. Source code for MagIC is publicly available on GitHub ( https://github.com/earthref/MagIC ). The MagIC file format is natively compatible with the PmagPy ( https://github.com/PmagPy/PmagPy) paleomagnetic analysis software. MagIC files can now be downloaded from the database and viewed and interpreted in the PmagPy GUI based tool, pmag_gui. Changes or interpretations of the data can then be saved by pmag_gui in the MagIC 3.0 data format and easily uploaded to the MagIC database. The rate of new contributions to the database has been increasing with many labs contributing measurement level data for the first time in the last year. Over a dozen file format conversion scripts are available for translating non-MagIC measurement data files into the MagIC format for easy uploading. We will continue to work with more labs until the whole community has a manageable workflow for contributing their measurement level data. MagIC will continue to provide a global repository for archiving and retrieving paleomagnetic and rock magnetic data and, with the new system in place, be able to more quickly respond to the community's requests for changes and improvements.

A Simple Parameterization of 3 x 3 Magic Squares

ERIC Educational Resources Information Center

Trenkler, Gotz; Schmidt, Karsten; Trenkler, Dietrich

2012-01-01

In this article a new parameterization of magic squares of order three is presented. This parameterization permits an easy computation of their inverses, eigenvalues, eigenvectors and adjoints. Some attention is paid to the Luoshu, one of the oldest magic squares.

The role of magical thinking in hallucinations. Comparisons of clinical and non-clinical groups.

PubMed

García-Montes, José M; Pérez-Álvarez, Marino; Odriozola-González, Paula; Vallina-Fernández, Oscar; Perona-Garcelán, Salvador

2014-11-01

Magical thinking consists of accepting the possibility that events that, according to the causal concepts of a culture, cannot have any causal relationship, but might somehow nevertheless have one. Magical thinking has been related to both obsessive-compulsive disorder and schizophrenia. The purpose of this study was to investigate the role of magical thinking in hallucinations of patients diagnosed with schizophrenia. Four groups were recruited for this purpose from a clinical population (hallucinating schizophrenic patients, patients diagnosed with psychoses who had never hallucinated, obsessive-compulsive disorder patients and a clinical control group) and a non-clinical control group, who were given the Magical Ideation Scale. The results show that magical ideation differentiates the group of schizophrenic patients with auditory hallucinations from the rest of the groups that participated in the design. Items related to "mind reading", to the presence of auditory illusions in response to sound stimuli, and to the sense of sometimes being accompanied by an evil presence are the most closely related to the presence of auditory hallucinations. Magical thinking, understood as beliefs in non-consensual modes of causation, is closely linked to auditory hallucinations in patients diagnosed with schizophrenia.

Early Childhood Corner: Take the Magic Out of Your Classroom!

ERIC Educational Resources Information Center

Andrews, Angela Giglio

1995-01-01

Students are often as mystified by mathematical procedures as they are by magic tricks. This article suggests ways of making the estimation of how many jelly beans in a jar and the 20-questions game less magical and more understandable. (MKR)

Magical thinking by inpatient staff members.

PubMed

Pilette, W L

1983-01-01

Magical thinking is a primitive form of mental activity which, nevertheless, the author contends, is common among mental health professionals. Four examples of magical thinking by inpatient staff members are presented and briefly explored, in order to shed light on our work and ourselves.

[Further Distinctions between Magic, Reality, Religion, and Fiction. Commentaries.

ERIC Educational Resources Information Center

Boyer, Pascal; Taylor, Marjorie; Harris, Paul L.; Chandler, Michael; Johnson, Carl N.

1997-01-01

Contains the following commentaries: "Further Distinctions between Magic, Reality, Religion, and Fiction"; "The Role of Creative Control and Culture in Children's Fantasy/Reality Judgments"; "The Last of the Magicians? Children, Scientists, and the Invocation of Hidden Causal Powers"; "Rescuing Magical Thinking…

The Magic Background of Pearl Harbor. Volume 1 (February 14, 1941 - May 12, 1941)

DTIC Science & Technology

1977-01-01

1977 2. REPORT TYPE 3. DATES COVERED 00-00-1977 to 00-00-1977 4. TITLE AND SUBTITLE The ’ Magic ’ Background of Pearl Harbor. Volume 1: February...34 MAGIC " BACKGROUND OF PEARL HARBOR VOLUME I (February 14, 1941-May 12,1941) /- / DEPARTMENT OF DEFENSE UNITED STATES OF AMERICA For sale by the...The Department of Defense is releasing for public use and research this multi-volume study giving the " MAGIC " or communications intelligence background

Further Studies of the NRL Collective Particle Accelerator VIA Numerical Modeling with the MAGIC Code.

DTIC Science & Technology

1984-08-01

COLLFCTIVF PAPTTCLE ACCELERATOR VIA NUMERICAL MODFLINC WITH THF MAGIC CODE Robert 1. Darker Auqust 19F4 Final Report for Period I April. qI84 - 30...NUMERICAL MODELING WITH THE MAGIC CODE Robert 3. Barker August 1984 Final Report for Period 1 April 1984 - 30 September 1984 Prepared for: Scientific...Collective Final Report Particle Accelerator VIA Numerical Modeling with April 1 - September-30, 1984 MAGIC Code. 6. PERFORMING ORG. REPORT NUMBER MRC/WDC-R

[Magical thinking and self development].

PubMed

Resch, F

1994-01-01

Based on a historical survey of the term "magic thinking" structural aspects of primary process and prelogical thinking will be elucidated. Developmental necessities for the emergence of magic interpretations in children of pre-school age are proposed. The thesis will be formulated, that magic interpretations may help the developing self in the management of life-circumstances during a period of cognitive egocentrism: feelings of non-competence may be compensated, and the locus of control may be held in the face of experiences of inferiority.

[The magic universe of cures: the role of magic practices and witchcraft in the universe of 17th century Mato Grosso].

PubMed

Sá, Mario

2009-01-01

The article analyzes the role of healing agents played by practitioners of magic and witchcraft in Mato Grosso society during the 17th century. It observes that magic and witchcraft were developed as competitors, alternatives or associated with other forms of healing (official and lay). It points out how such roles contributed to the process of subjugating its practitioners, especially Africans, Indians and their descendents, and were appropriated as an opportunity for survival in the colonial slave society. The pastoral visit made by Bruno Pinna in 1785 to Cuiabá and nearby areas served as the principal source of knowledge regarding the practices and practitioners of magic and witchcraft.

When "Holiday Magic" Hurts.

ERIC Educational Resources Information Center

Goldstein, Karen

2001-01-01

Claims that religious messages in public school are not acceptable and are hurtful to kids who do not subscribe to the beliefs expressed in those messages. Describes the author's personal experience in helping a teacher transform the script for "Christmas Magic" into the more inclusive "Holiday Magic." (RS)

[Investigation into the formation of proportions of "realistic thinking vs magical thinking" in paranoid schizophrenia].

PubMed

Jarosz, M; Pankiewicz, Z; Buczek, I; Poprawska, I; Rojek, J; Zaborowski, A

1993-01-01

Both magical thinking among healthy persons and magical and symbolic thinking in schizophrenia were discussed. The investigation covered 100 paranoid schizophrenics. They also underwent an examination in connection with the formation of the remaining 3 proportions. Both "realistic thinking and magical thinking" scales were used. An ability to think realistically was preserved, to a varying degree, in all patients, with 50% of those examined having shown an explicit or very explicit ability to follow realistic thinking. The above findings deviate from a simplified cognitive model within the discussed range. It was further confirmed that realistic thinking may coexist with magical thinking, and, in some cases, it concerns the same events. That type of disorders of the content of thinking are referred to as magical-realistic interpenetration. The results, and particularly high coefficient of negative correlation within the scales of the examined proportions, confirm the correctness of the assumption that the investigated modes of thinking form an antithetic bipolarity of proportions, aggregating antithetic values, therefore being also complementary.

Magical attachment: Children in magical relations with hospital clowns

PubMed Central

2012-01-01

The aim of the present study was to achieve a theoretical understanding of several different-age children's experiences of magic relations with hospital clowns in the context of medical care, and to do so using psychological theory and a child perspective. The method used was qualitative and focused on nine children. The results showed that age was important to consider in better understanding how the children experienced the relation with the hospital clowns, how they described the magical aspects of the encounter and how they viewed the importance of clown encounters to their own well-being. The present theoretical interpretation characterized the encounter with hospital clowns as a magical safe area, an intermediate area between fantasy and reality. The discussion presented a line of reasoning concerning a magical attachment between the child and the hospital clowns, stating that this attachment: a) comprised a temporary relation; b) gave anonymity; c) entailed reversed roles; and d) created an emotional experience of boundary-transcending opportunities. PMID:22371813

The presence of magical thinking in obsessive compulsive disorder.

PubMed

Einstein, Danielle A; Menzies, Ross G

2004-05-01

Two research groups have raised the possibility that magical ideation may be a fundamental feature of obsessive-compulsive disorder. It has been proposed to underlie thought action fusion and superstitious beliefs. In this study, the Magical Ideation scale, the Lucky Behaviours and Lucky Beliefs scales, the Thought Action Fusion-Revised scale, the Padua Inventory, and the Obsessive Compulsive Inventory-Short Version were completed by 60 obsessive compulsive patients at a hospital clinic. Of all the measures, the Magical Ideation (MI) scale was found to be the most strongly related to obsessive compulsive symptoms. Large and significant relationships between MI scores and the measures of OCD were obtained even when alternative constructs (Lucky Behaviours, Lucky Beliefs, Thought Action Fusion-Revised scales) were held constant. No other variable remained significantly related to the Obsessive Compulsive Inventory-Short Version when magical ideation scores were held constant. The findings suggest that a general magical thinking tendency may underpin previous observed links between superstitiousness, thought action fusion and OCD severity.

Hall Plateaus at magic angles in ultraquantum Bismuth

NASA Astrophysics Data System (ADS)

Benoît, Fauqué.

2009-03-01

The behaviour of a three-dimensional electron gas in the presence of a magnetic field strong enough to put all carriers in the first Landau level (i.e. beyond the quantum limit) is a longstanding question of theoretical condensed matter physics [1]. This issue has been recently explored by two high-field experiments on elemental semi-metal Bismuth. In a first study of transport coefficients (which are dominated by hole-like carriers), the Nernst coefficient presented three unexpected maxima that are concomitant with quasi-plateaux in the Hall coefficient [2]. In a second series of experiments, torque magnetometry (which mainly probes the three Dirac valley electron pockets) detected a field-induced phase transition [3]. The full understanding of the electron and hole behaviours above the quantum limit of pure Bi is therefore still under debate. In this talk, we will present our measurement of the Hall resistivity and torque magnetometry with magnetic field up to 31 T and rotating in the trigonal-bisectrix plane [4]. The Hall response is dominated by the hole pockets according to its sign as well as the period and the angular dependence of its quantum oscillations. In the vicinity of the quantum limit, it presents additional anomalies which are the fingerprints of the electron pockets. We found that for particular orientations of the magnetic field (namely ``magic angles''), the Hall response becomes field-independent within the experimental resolution around 20T. This drastic dependence of the plateaux on the field orientation provides strong constraints for theoretical scenarios. [4pt] [1] Bertrand I. Halperin, Japanese Journal of Applied Physics, 26, Supplement 26-3 (1987).[0pt] [2] Kamran Behnia, Luis Balicas, Yakov Kopelevich, Science, 317, 1729 (2008).[0pt] [3] Lu Li, J. G. Checkelsky, Y. S. Hor, C. Uher, A. F. Hebard, R. J. Cava, and N. P. Ong , Science, 321, 5888 (2008).[0pt] [4] Benoît Fauqu'e, Luis Balicas, Ilya Sheikin, Jean Paul Issi and Kamran Behnia, to be published

71Ga-77Se connectivities and proximities in gallium selenide crystal and glass probed by solid-state NMR

NASA Astrophysics Data System (ADS)

Nagashima, Hiroki; Trébosc, Julien; Calvez, Laurent; Pourpoint, Frédérique; Mear, François; Lafon, Olivier; Amoureux, Jean-Paul

2017-09-01

We introduce two-dimensional (2D) 71Ga-77Se through-bond and through-space correlation experiments. Such correlations are achieved using (i) the J-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (J-RINEPT) method with 71Ga excitation and 77Se Carr-Purcell-Meiboon-Gill (CPMG) detection, as well as (ii) the J- or dipolar-mediated Hetero-nuclear Multiple-Quantum Correlation (J- or D-HMQC) schemes with 71Ga excitation and quadrupolar CPMG (QCPMG) detection. These methods are applied to the crystalline β-Ga2Se3 and the 0.2Ga2Se3-0.8GeSe2 glass. Such glass leads to a homogeneous and reproducible glass-ceramic, which is a good alternative to single-crystalline Ge and polycrystalline ZnSe materials for making lenses transparent in the IR range for thermal imaging applications. We show that 2D 71Ga-77Se correlation experiments allow resolving the 77Se signals of molecular units, which are not resolved in the 1D 77Se CPMG spectrum. Additionally, the build-up curves of the J-RINEPT and the J-HMQC experiments allow the estimate of the 71Ga-77Se J-couplings via one and three-bonds in the three-dimensional network of β-Ga2Se3. Furthermore, these build-up curves show that the one-bond 1J71Ga-77Se couplings in the 0.2Ga2Se3-0.8GeSe2 glass are similar to those measured for β-Ga2Se3. We also report 2D 71Ga Satellite Transition Magic-Angle Spinning (STMAS) spectrum of β-Ga2Se3 using QCPMG detection at high magnetic field and high Magic-Angle Spinning frequency using large radio frequency field. Such spectrum allows separating the signal of β-Ga2Se3 and that of an impurity.

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.

Evaluation of toxicological effects induced by tributyltin in clam Ruditapes decussatus using high-resolution magic angle spinning nuclear magnetic resonance spectroscopy: Study of metabolic responses in heart tissue and detection of a novel metabolite.

PubMed

Hanana, H; Simon, G; Kervarec, N; Cérantola, S

2014-01-01

Tributyltin (TBT) is a highly toxic pollutant present in many aquatic ecosystems. Its toxicity in mollusks strongly affects their performance and survival. The main purpose of this study was to elucidate the mechanisms of TBT toxicity in clam Ruditapes decussatus by evaluating the metabolic responses of heart tissues, using high-resolution magic angle-spinning nuclear magnetic resonance (HRMAS NMR), after exposure to TBT (10 -9 , 10 -6 and 10 -4 M) during 24 h and 72 h. Results show that responses of clam heart tissue to TBT exposure are not dose dependent. Metabolic profile analyses indicated that TBT 10 -6 M, contrary to the two other doses tested, led to a significant depletion of taurine and betaine. Glycine levels decreased in all clam groups treated with the organotin. It is suggested that TBT abolished the cytoprotective effect of taurine, betaine and glycine thereby inducing cardiomyopathie. Moreover, results also showed that TBT induced increase in the level of alanine and succinate suggesting the occurrence of anaerobiosis particularly in clam group exposed to the highest dose of TBT. Taken together, these results demonstrate that TBT is a potential toxin with a variety of deleterious effects on clam and this organotin may affect different pathways depending to the used dose. The main finding of this study was the appearance of an original metabolite after TBT treatment likely N-glycine-N'-alanine. It is the first time that this molecule has been identified as a natural compound. Its exact role is unknown and remains to be elucidated. We suppose that its formation could play an important role in clam defense response by attenuating Ca 2+ dependent cell death induced by TBT. Therefore this compound could be a promising biomarker for TBT exposure.

Magic in the machine: a computational magician's assistant

PubMed Central

Williams, Howard; McOwan, Peter W.

2014-01-01

A human magician blends science, psychology, and performance to create a magical effect. In this paper we explore what can be achieved when that human intelligence is replaced or assisted by machine intelligence. Magical effects are all in some form based on hidden mathematical, scientific, or psychological principles; often the parameters controlling these underpinning techniques are hard for a magician to blend to maximize the magical effect required. The complexity is often caused by interacting and often conflicting physical and psychological constraints that need to be optimally balanced. Normally this tuning is done by trial and error, combined with human intuitions. Here we focus on applying Artificial Intelligence methods to the creation and optimization of magic tricks exploiting mathematical principles. We use experimentally derived data about particular perceptual and cognitive features, combined with a model of the underlying mathematical process to provide a psychologically valid metric to allow optimization of magical impact. In the paper we introduce our optimization methodology and describe how it can be flexibly applied to a range of different types of mathematics based tricks. We also provide two case studies as exemplars of the methodology at work: a magical jigsaw, and a mind reading card trick effect. We evaluate each trick created through testing in laboratory and public performances, and further demonstrate the real world efficacy of our approach for professional performers through sales of the tricks in a reputable magic shop in London. PMID:25452736

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

Two-dimensional nuclear magnetic resonance of quadrupolar systems

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

Wang, Shuanhu

1997-09-01

This dissertation describes two-dimensional nuclear magnetic resonance theory and experiments which have been developed to study quadruples in the solid state. The technique of multiple-quantum magic-angle spinning (MQMAS) is extensively reviewed and expanded upon in this thesis. Specifically, MQMAS is first compared with another technique, dynamic-angle spinning (DAS). The similarity between the two techniques allows us to extend much of the DAS work to the MQMAS case. Application of MQMAS to a series of aluminum containing materials is then presented. The superior resolution enhancement through MQMAS is exploited to detect the five- and six-coordinated aluminum in many aluminosilicate glasses. Combiningmore » the MQMAS method with other experiments, such as HETCOR, greatly expands the possibility of the use of MQMAS to study a large range of problems and is demonstrated in Chapter 5. Finally, the technique switching-angle spinning (SAS) is applied to quadrupolar nuclei to fully characterize a quadrupolar spin system in which all of the 8 NMR parameters are accurately determined. This dissertation is meant to demonstrate that with the combination of two-dimensional NMR concepts and new advanced spinning technologies, a series of multiple-dimensional NMR techniques can be designed to allow a detailed study of quadrupolar nuclei in the solid state.« less

Chinese "Magic" Mirrors.

ERIC Educational Resources Information Center

Swinson, Derek B.

1992-01-01

Chinese "magic" mirrors are made from bronze with the front side a mirror and the reverse side a molded image. When light is reflected from the mirror,the image on the reverse side appears. Discusses reflections of conventional mirrors, possible explanations for the magic mirror phenomenon, and applications of the phenomenon to…

U.S. EPA, Pesticide Product Label, FLEAGO THE MAGIC CRYSTAL, 07/09/1997

EPA Pesticide Factsheets

2011-04-21

... Fleago The Magic Crystal '~~~:ul~~i~;~i~~!;~i~~fat~~I~~n~w~~~~: W~?~:~iA~~~~~r~Y '~~;: ... lhe Magic Crystal ...

"You Will": Technology, Magic, and the Cultural Contexts of Technical Communication.

ERIC Educational Resources Information Center

Kitalong, Karla Saari

2000-01-01

Provides some background on the use of magical language in technical contexts, gives examples of magical discourse in technology advertisements and newsmagazine articles, and proposes a technical communication pedagogy of media analysis. Notes that the proposed pedagogy involves students conducting diagnostic critiques of media texts and affords…

Magical Landscapes: Two Love Stories.

ERIC Educational Resources Information Center

Moore, John Noell

2002-01-01

Introduces two books about magic, one a collection of essays "Ex Libris: Confessions of a Common Reader," which describes the author's inherited lifelong passion for books and reading; and the other a novel, "Mangos, Bananas and Coconuts: A Cuban Love Story," which tells a story of love and magic that seems both real and…

Magical Mysteries. Texas Reading Club, 1984. A Librarian's Planning Handbook.

ERIC Educational Resources Information Center

Oliver, Jim

Designed to encourage library use by Texas youth, the Texas Reading Club programs usually include a structured reading program and a variety of entertaining literature-related storyhours, puppet shows, films, and other attractive happenings. This handbook for the 1984 theme--"magical mysteries"--focuses on mysteries, magic, and adventure…

Redefining the magic square on numerical characters

NASA Astrophysics Data System (ADS)

Nasution, M. K. M.; Sawaluddin

2018-02-01

As a number system, the magic square is different from the others. Characteristic depends not only on size but also depends on numerical character in computation. This paper has redefined the term of magic square formally, by exposing the inductive general characteristics of cases to numerical ordering of numbers.

Magic User’s Manual 2006

DTIC Science & Technology

2006-12-01

K (M) M issioin Research MRC/WDC-R-556 MAGIC USER’S MANUAL 2006 Author(s): Larry Ludeking ATK Mission Research Contract No.: F49620-03-C-0030 L¾[iJiD... Magic Tool Suite for Windows. It uses the standard Windows Help so it is pretty self-explanatory. You can use the panel to the left to scan through... MAGIC Go to Part 2. MCL Commands Go to Part 3. Tirnc and Space Go to Part 4. Spatial Extensions Go to Part 5. Properties Go to Part 6. Algorithms Go

A Compact Low-loss Magic-T using Microstrip-Slotline Transitions

NASA Technical Reports Server (NTRS)

U-yen, Kongpop; Wollack, Edward J.; Moseley, Samuel H.; Papapolymerou, John; Laskar, Joy

2007-01-01

The design of a compact low-loss magic-T is proposed. The planar magic-T incorporates the compact microstrip-slotline tee junction and small microstrip-slotline transition area to reduce slotline radiation. The experimental results show that the magic-T produces broadband in-phase and out-of-phase power combiner/divider responses, has an average in-band insertion loss of 0.3 dB and small in-band phase and amplitude imbalance of less than plus or minus 1.6 deg. and plus or minus 0.3 dB, respectively.

Lenz's Law Magic Trick

NASA Astrophysics Data System (ADS)

Ruiz, Michael J.

2006-02-01

The demonstration of Lenz's law by dropping a powerful magnet down a nonmagnetic metal pipe has become a classic lecture-hall demonstration.1,2 An inexpensive version is packaged as a professional magic trick3 called "Newton's Nightmare." Combining sleight-of-hand with a demonstration of Lenz's law is a surefire way to heighten student interest. The subsequent student discussion motivated by a desire to understand the magic trick can lead to a memorable physics lesson. This paper will discuss Lenz's law magic and review literature that reveals the subtlety of the physics.

The use of magical plants by curanderos in the Ecuador highlands

PubMed Central

Cavender, Anthony P; Albán, Manuel

2009-01-01

Although the use of plants for treating supernaturally caused illnesses (e.g., soul loss, evil wind, witchcraft) has been documented in the Ecuador highlands, so-called magical plants have received much less focused attention than plants used for treating naturalistic disorders. Drawing on interviews done in 2002 and 2003 with 116 curanderos residing in the Ecuador highlands, this paper examines the characteristics of plants identified as magical, how they are used, and how the study of magical plants provides insights into the mindscape of residents of the highlands. PMID:19161618

Modernizing the MagIC Paleomagnetic and Rock Magnetic Database Technology Stack to Encourage Code Reuse and Reproducible Science

NASA Astrophysics Data System (ADS)

Minnett, R.; Koppers, A. A. P.; Jarboe, N.; Jonestrask, L.; Tauxe, L.; Constable, C.

2016-12-01

The Magnetics Information Consortium (https://earthref.org/MagIC/) develops and maintains a database and web application for supporting the paleo-, geo-, and rock magnetic scientific community. Historically, this objective has been met with an Oracle database and a Perl web application at the San Diego Supercomputer Center (SDSC). The Oracle Enterprise Cluster at SDSC, however, was decommissioned in July of 2016 and the cost for MagIC to continue using Oracle became prohibitive. This provided MagIC with a unique opportunity to reexamine the entire technology stack and data model. MagIC has developed an open-source web application using the Meteor (http://meteor.com) framework and a MongoDB database. The simplicity of the open-source full-stack framework that Meteor provides has improved MagIC's development pace and the increased flexibility of the data schema in MongoDB encouraged the reorganization of the MagIC Data Model. As a result of incorporating actively developed open-source projects into the technology stack, MagIC has benefited from their vibrant software development communities. This has translated into a more modern web application that has significantly improved the user experience for the paleo-, geo-, and rock magnetic scientific community.

Science Magic: Making a Difference

ERIC Educational Resources Information Center

Tidel, L. L.

2004-01-01

In this narrative article, the author fondly takes a look back at her own personal experiences with a memorable science teacher who showed his students that science was a living, breathing world. Whether he assigned his class to collect water samples from local ponds (to look at microscopic organisms), bring in rocks to class for identification,…

Narrative Magic and the Construction of Selfhood in Antidepressant Advertising

ERIC Educational Resources Information Center

Stepnisky, Jeffrey N.

2007-01-01

This article examines the way in which selfhood is constructed in direct-to-consumer advertisements for antidepressant medications. The sample consists of advertisements that appeared in nine popular magazines between 1997 and 2005, television commercials that ran between 2003 and 2005, and online promotional Web sites. The analysis is divided…

Harry Potter in Translation: Making Language Learning Magical

ERIC Educational Resources Information Center

Eaton, Sarah Elaine

2012-01-01

This guidebook for teachers documents the "Harry Potter in Translation" project undertaken at the Language Research Centre at the University of Calgary. The guide also offers 5 sample lesson plans for teachers of grades three to twelve for teaching world languages using the Harry Potter books in translation to engage students. (Contains…

Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach

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

Fletcher, Thomas; Pugmire, Ronald

2015-01-01

Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogensmore » were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.« less

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).

Rapid and Simple Phenotypic Assay for Drug Susceptibility of Human Immunodeficiency Virus Type 1 Using CCR5-Expressing HeLa/CD4+ Cell Clone 1-10 (MAGIC-5)

PubMed Central

Hachiya, Atsuko; Aizawa-Matsuoka, Saori; Tanaka, Mari; Takahashi, Yukiko; Ida, Setsuko; Gatanaga, Hiroyuki; Hirabayashi, Yoshihiro; Kojima, Asato; Tatsumi, Masashi; Oka, Shinichi

2001-01-01

We describe a rapid and simple novel phenotypic assay for drug susceptibility of human immunodeficiency virus type-1 (HIV-1) using a CCR5-expressing HeLa/CD4+ cell clone 1-10 (MAGIC-5). MAGIC-5 cells produced large amounts of HIV-1 in culture supernatants, which enabled us to perform the phenotypic resistance assay. Determination of HIV-1 susceptibility to various protease inhibitors (PI) and nucleoside reverse transcriptase inhibitors was completed within 15 days in T-cell-tropic (X4) and macrophage-tropic (R5) viruses using fresh plasma samples containing at least 104 copies/ml. The nucleotide sequence of the envelope V3 region of HIV-1 in plasma was almost identical to that of the virus isolated by MAGIC-5 cells, suggesting a lack of selection bias in our assay. The assay variability was confined to within five-fold in all drugs examined. Accordingly, we used a 10-fold increase in the 50% inhibitory concentration as the cutoff value for viral resistance in the present assay. HIV-1 resistant to lamivudine, which was not detected by conventional genotypic assays, was isolated. In HIV-1 with PI-associated primary amino acid substitutions, our assay showed that drug resistance profiles correlated well with previously reported genotypic-assay data. Furthermore, our assay provided comprehensive results regarding PI resistance in the presence of multiple mutations. The novel assay successfully quantified the level of resistance of clinical HIV-1 isolates to a battery of anti-HIV drugs, indicating its clinical usefulness, particularly in patients who failed to respond to antiretroviral chemotherapy. PMID:11158746

Structural Changes Associated with Transthyretin Misfolding and Amyloid Formation Revealed by Solution and Solid-State NMR

DOE PAGES

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

2016-03-21

Elucidation of structural changes involved in protein misfolding and amyloid formation is crucial for unraveling the molecular basis of amyloid formation. We report structural analyses of the amyloidogenic intermediate and amyloid aggregates of transthyretin using solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. These NMR solution results show that one of the two main β-sheet structures (CBEF β-sheet) is maintained in the aggregation-competent intermediate, while the other DAGH β-sheet is more flexible on millisecond time scales. Magic-angle-spinning solid-state NMR revealed that AB loop regions interacting with strand A in the DAGH β-sheet undergo conformational changes, leading to the destabilized DAGHmore » β-sheet.« less

Monitoring Cocrystal Formation via In Situ Solid-State NMR.

PubMed

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

2014-10-02

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

Observation of shape isomers states in fission fragments

NASA Astrophysics Data System (ADS)

Kamanin, D. V.; Pyatkov, Yu V.; Alexandrov, A. A.; Alexandrova, I. A.; Mkaza, N.; Malaza, V.; Kuznetsova, E. A.; Strekalovsky, A. O.; Strekalovsky, O. V.; Zhuchko, V. E.

2017-06-01

We discuss the manifestations of a new original effect appeared at crossing of the metal foils by fission fragments. We have observed significant mass deficit in the total mass Ms of the fission fragments detected in coincidence with ions knocked out from the foil. It was shown that at the large angles of scattering of the knocked-out ions from the foil predominantly conventional elastic Rutherford scattering takes place. As the result Ms corresponds to the mean mass of the mother system after emission of fission neutrons (no missing mass). In contrast, in near frontal impacts fission fragment misses essential part of its mass. Residual nuclei at least for the fragments from the heavy mass peak show magic nucleon composition.

Algebra Magic Tricks: Algecadabra! Volume 1.

ERIC Educational Resources Information Center

Edwards, Ronald

This resource book contains 20 magic tricks based on the properties of whole numbers that are intended to spark the interest and imagination of students. Following each activity, students are asked to write about their discoveries and to create their own magic tricks. A matrix of skills for all the activities and lists of the materials required…

Algebra Magic Tricks: Algecadabra! Volume 2.

ERIC Educational Resources Information Center

Edwards, Ronald

This resource book contains 15 magic tricks based on the properties of whole numbers that are intended to spark the interest and imagination of students. Following each activity, students are asked to write about their discoveries and to create their own magic tricks. A matrix of skills for all the activities and lists of the materials required…

A COAXIAL MAGIC-T

DTIC Science & Technology

Three different designs of coaxial hybrid junctions having perf ormance analogous to a wave-guide magic -T are discussed. The experimental results...loads, decoupling greater than 70 db can be obtained. An application of the magic -T in phase measurement is described which is independent of the signal amplitude and is similar to the homodyne system of phase measurement.

A CMOS VLSI IC for Real-Time Opto-Electronic Two-Dimensional Histogram Generation

DTIC Science & Technology

1993-12-01

large scale integration) design; MAGIC ; CMOS; optics; image processing; 93 16. PRICE CODE 17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATiON 19...1. Sun SPARCstation ............. .............. 6 2. Magic .................. ................... 6 a. Peg ................. .................. 7 b...38 v APPENDIX B. MAGIC CELL LAYOUTS .... ............ .. 39 APPENDIX C: SIMULATION DATA ....... ............. .. 56 A. FINITE STATE MACHINE

Magical Realist Pathways into and under the Psychotherapeutic Imaginary

ERIC Educational Resources Information Center

Speedy, Jane

2011-01-01

My experience of people's life stories from my work as a narrative therapist consistently destabilised distinctions between imagined/magical and real experiences. I came to realise that the day-to-day magical realist juxtapositions I came upon were encounters with people's daily lives, as lived, that have remained unacknowledged within the…

Glamour and Spelling: Reclaiming Magical Thinking in the Composition Classroom.

ERIC Educational Resources Information Center

Wagner, Julia

It is a good thing to demolish "magical thinking" if it refers to the view of language for which words have fixed, inevitable meanings. Words are often deprived of their meanings and reduced to verbal noises, producing involuntary responses like knee-reflexes. Various critics have discussed and written about the magical aspects of…

Garden Gnomes: Magical or Tacky?

ERIC Educational Resources Information Center

Flynt, Deborah

2012-01-01

Garden gnomes: magical or tacky? Well, art is in the eye of the beholder, and for the author's advanced seventh-grade art class, garden gnomes are magical. Gnomes have a very long history, dating back to medieval times. A fairytale describes them as brownie-like creatures that are nocturnal helpers. In this article, the author describes how her…

A framework for using magic to study the mind.

PubMed

Rensink, Ronald A; Kuhn, Gustav

2014-01-01

Over the centuries, magicians have developed extensive knowledge about the manipulation of the human mind-knowledge that has been largely ignored by psychology. It has recently been argued that this knowledge could help improve our understanding of human cognition and consciousness. But how might this be done? And how much could it ultimately contribute to the exploration of the human mind? We propose here a framework outlining how knowledge about magic can be used to help us understand the human mind. Various approaches-both old and new-are surveyed, in terms of four different levels. The first focuses on the methods in magic, using these to suggest new approaches to existing issues in psychology. The second focuses on the effects that magic can produce, such as the sense of wonder induced by seeing an apparently impossible event. Third is the consideration of magic tricks-methods and effects together-as phenomena of scientific interest in their own right. Finally, there is the organization of knowledge about magic into an informative whole, including the possibility of a science centered around the experience of wonder.

A framework for using magic to study the mind

PubMed Central

Rensink, Ronald A.; Kuhn, Gustav

2015-01-01

Over the centuries, magicians have developed extensive knowledge about the manipulation of the human mind—knowledge that has been largely ignored by psychology. It has recently been argued that this knowledge could help improve our understanding of human cognition and consciousness. But how might this be done? And how much could it ultimately contribute to the exploration of the human mind? We propose here a framework outlining how knowledge about magic can be used to help us understand the human mind. Various approaches—both old and new—are surveyed, in terms of four different levels. The first focuses on the methods in magic, using these to suggest new approaches to existing issues in psychology. The second focuses on the effects that magic can produce, such as the sense of wonder induced by seeing an apparently impossible event. Third is the consideration of magic tricks—methods and effects together—as phenomena of scientific interest in their own right. Finally, there is the organization of knowledge about magic into an informative whole, including the possibility of a science centered around the experience of wonder. PMID:25698983

Improved silicon carbide for advanced heat engines

NASA Technical Reports Server (NTRS)

Whalen, Thomas J.

1989-01-01

The development of high strength, high reliability silicon carbide parts with complex shapes suitable for use in advanced heat engines is studied. Injection molding was the forming method selected for the program because it is capable of forming complex parts adaptable for mass production on an economically sound basis. The goals were to reach a Weibull characteristic strength of 550 MPa (80 ksi) and a Weibull modulus of 16 for bars tested in four-point loading. Statistically designed experiments were performed throughout the program and a fluid mixing process employing an attritor mixer was developed. Compositional improvements in the amounts and sources of boron and carbon used and a pressureless sintering cycle were developed which provided samples of about 99 percent of theoretical density. Strengths were found to improve significantly by annealing in air. Strengths in excess of 550 MPa (80 ksi) with Weibull modulus of about 9 were obtained. Further improvements in Weibull modulus to about 16 were realized by proof testing. This is an increase of 86 percent in strength and 100 percent in Weibull modulus over the baseline data generated at the beginning of the program. Molding yields were improved and flaw distributions were observed to follow a Poisson process. Magic angle spinning nuclear magnetic resonance spectra were found to be useful in characterizing the SiC powder and the sintered samples. Turbocharger rotors were molded and examined as an indication of the moldability of the mixes which were developed in this program.

Observations of VHE γ-Ray Sources with the MAGIC Telescope

NASA Astrophysics Data System (ADS)

Bartko, H.

2008-10-01

The MAGIC telescope with its 17m diameter mirror is today the largest operating single-dish Imaging Air Cherenkov Telescope (IACT). It is located on the Canary Island La Palma, at an altitude of 2200m above sea level, as part of the Roque de los Muchachos European Northern Observatory. The MAGIC telescope detects celestial very high energy γ-radiation in the energy band between about 50 GeV and 10 TeV. Since Autumn of 2004 MAGIC has been taking data routinely, observing various objects like supernova remnants (SNRs), γ-ray binaries, Pulsars, Active Galactic Nuclei (AGN) and Gamma-ray Bursts (GRB). We briefly describe the observational strategy, the procedure implemented for the data analysis, and discuss the results for individual sources. An outlook to the construction of the second MAGIC telescope is given.

[Magical and religious healing in Byzantium].

PubMed

Józsa, László

2010-01-01

Religious and magical ways of healing have been known and practiced since the very beginning of human history. In the present article, the Byzantine philosophical, cultural, historical and "methodological" aspects of this way of healing are discussed. The article outlines the development of magic healing in Byzantium from the 4th to the 15th century. During this period magical therapy included the cult of patron saints--listed by the author--and pleading for divine intervention as well. The activity of "anargyroi" and the use of magical objects and amulets is also discussed in detail. Exorcism was also a part of religious therapy both against psychical and somatical diseases. In early Christianity, and especially in Byzantium the devil or other demons were also supposed to cause various somatical or psychical illnesses by "intrusion" or "internalisation," i.e. by possession or obsession of their victims.

Maximum nonlocality and minimum uncertainty using magic states

NASA Astrophysics Data System (ADS)

Howard, Mark

2015-04-01

We prove that magic states from the Clifford hierarchy give optimal solutions for tasks involving nonlocality and entropic uncertainty with respect to Pauli measurements. For both the nonlocality and uncertainty tasks, stabilizer states are the worst possible pure states, so our solutions have an operational interpretation as being highly nonstabilizer. The optimal strategy for a qudit version of the Clauser-Horne-Shimony-Holt game in prime dimensions is achieved by measuring maximally entangled states that are isomorphic to single-qudit magic states. These magic states have an appealingly simple form, and our proof shows that they are "balanced" with respect to all but one of the mutually unbiased stabilizer bases. Of all equatorial qudit states, magic states minimize the average entropic uncertainties for collision entropy and also, for small prime dimensions, min-entropy, a fact that may have implications for cryptography.

On an algebraic structure of dimensionally reduced magical supergravity theories

NASA Astrophysics Data System (ADS)

Fukuchi, Shin; Mizoguchi, Shun'ya

2018-06-01

We study an algebraic structure of magical supergravities in three dimensions. We show that if the commutation relations among the generators of the quasi-conformal group in the super-Ehlers decomposition are in a particular form, then one can always find a parameterization of the group element in terms of various 3d bosonic fields that reproduces the 3d reduced Lagrangian of the corresponding magical supergravity. This provides a unified treatment of all the magical supergravity theories in finding explicit relations between the 3d dimensionally reduced Lagrangians and particular coset nonlinear sigma models. We also verify that the commutation relations of E 6 (+ 2), the quasi-conformal group for A = C, indeed satisfy this property, allowing the algebraic interpretation of the structure constants and scalar field functions as was done in the F 4 (+ 4) magical supergravity.

MAGIC observations and multifrequency properties of the flat spectrum radio quasar 3C 279 in 2011

DOE PAGES

Aleksic, J.

2014-07-01

Aims. We present a study of the very high energy (VHE; E>100 GeV) γ-ray emission of the blazar PKS 1424+240 observed with the MAGIC telescopes. The primary aim of this paper is the multiwavelength spectral characterization and modeling of this blazar, which is made particularly interesting by the recent discovery of a lower limit of its redshift of z ≥ 0.6 and makes it a promising candidate to be the most distant VHE source. Methods. The source has been observed with the MAGIC telescopes in VHE rays for a total observation time of ~33.6 h from 2009 to 2011. Amore » detailed analysis of its γ-ray spectrum and time evolution has been carried out. Moreover, we have collected and analyzed simultaneous and quasi-simultaneous multiwavelength data. Results. The source was marginally detected in VHE rays during 2009 and 2010, and later, the detection was confirmed during an optical outburst in 2011. The combined significance of the stacked sample is ~7.2σ. The differential spectra measured during the different campaigns can be described by steep power laws with the indices ranging from 3.5 ± 1.2 to 5.0 ± 1.7. The MAGIC spectra corrected for the absorption due to the extragalactic background light connect smoothly, within systematic errors, with the mean spectrum in 2009-2011 observed at lower energies by the Fermi-LAT. The absorption-corrected MAGIC spectrum is flat with no apparent turn down up to 400 GeV. The multiwavelength light curve shows increasing flux in radio and optical bands that could point to a common origin from the same region of the jet. The large separation between the two peaks of the constructed non-simultaneous spectral energy distribution also requires an extremely high Doppler factor if an one zone synchrotron self-Compton model is applied. We find that a two-component synchrotron self-Compton model describes the spectral energy distribution of the source well, if the source is located at z ~ 0.6.« less

MAGIC long-term study of the distant TeV blazar PKS 1424+240 in a multiwavelength context

DOE PAGES

Aleksić, J.

2014-07-01

Aims. We present a study of the very high energy (VHE; E>100 GeV) γ-ray emission of the blazar PKS 1424+240 observed with the MAGIC telescopes. The primary aim of this paper is the multiwavelength spectral characterization and modeling of this blazar, which is made particularly interesting by the recent discovery of a lower limit of its redshift of z ≥ 0.6 and makes it a promising candidate to be the most distant VHE source. Methods. The source has been observed with the MAGIC telescopes in VHE rays for a total observation time of ~33.6 h from 2009 to 2011. Amore » detailed analysis of its γ-ray spectrum and time evolution has been carried out. Moreover, we have collected and analyzed simultaneous and quasi-simultaneous multiwavelength data. Results. The source was marginally detected in VHE rays during 2009 and 2010, and later, the detection was confirmed during an optical outburst in 2011. The combined significance of the stacked sample is ~7.2σ. The differential spectra measured during the different campaigns can be described by steep power laws with the indices ranging from 3.5 ± 1.2 to 5.0 ± 1.7. The MAGIC spectra corrected for the absorption due to the extragalactic background light connect smoothly, within systematic errors, with the mean spectrum in 2009-2011 observed at lower energies by the Fermi-LAT. The absorption-corrected MAGIC spectrum is flat with no apparent turn down up to 400 GeV. The multiwavelength light curve shows increasing flux in radio and optical bands that could point to a common origin from the same region of the jet. The large separation between the two peaks of the constructed non-simultaneous spectral energy distribution also requires an extremely high Doppler factor if an one zone synchrotron self-Compton model is applied. We find that a two-component synchrotron self-Compton model describes the spectral energy distribution of the source well, if the source is located at z ~ 0.6.« less

Logistical Support of AirLand Operations: Myth or Magic?

DTIC Science & Technology

1992-05-04

I4 May 1992 Master’s Thesis, 4 Aug 91-5 Jun 92 4. TITLE AND SUBTITLE 5. FUNDING NUMBERS .Support of AirLand Operations: Myth or Magic 6. AUTHOR(S) HA•J...SUPPORT OF AIRLAND OPERATIONS: MYTH OR MAGIC A thesis nresented to the Faculty of the U.S. Army Command and General Staff College in oartial fulfillment of...inerati,,,: Myth or Magic . Aprroved by: .Theq is Comni tt-t- fTh~airrnan; J ),I i .5 .a rria A.n . T.T! 3:•, J!. Pnwe r. M’. P. A . " ,ý) VoD" Member

Comparison of HELIX TWT Simulation Using 2-D PIC (Magic), 2-D Modal (Gator), and 1-D Modal (Christine) Methods

DTIC Science & Technology

1998-05-01

Mission Research Corporation MRC/WDC-R-424 COMPARISON OF HELIX TWT SIMULATION USING 2-D PIC ( MAGIC ), 2-D MODAL (GATOR), AND 1-D MODAL (CHRISTINE...BRILLOUIN RUN 9 3.4 OUTLIER ELECTRON EFFECT IN GATOR 12 3.5 EMISSION CONDITION AND NONLAMINAR FLOW IN MAGIC 12 3.6 RADIAL SHEAR 13 SECTION 4. PPM B...Simulation using 2-D PIC ( MAGIC ), 2-D Modal (GATOR) and 1-D Modal (CHRISTINE) methods * D.N. Smithe(a), H. Freund(b), T. M. Antonsen Jr.,(b)’(c), E

Optically guided atom interferometer tuned to magic wavelength

NASA Astrophysics Data System (ADS)

Akatsuka, Tomoya; Takahashi, Tadahiro; Katori, Hidetoshi

2017-11-01

We demonstrate an atom interferometer operating on the 1S0-3P0 clock transition of 87Sr atoms in a “magic” optical guide, where the light shift perturbations of the guiding potential are canceled. As a proof-of-principle demonstration, a Mach-Zehnder interferometer is set horizontally to map the acceleration introduced by the focused optical guide. This magic guide interferometer on the clock transition is applicable to atomic elements where magic wavelengths can be found. Possible applications of the magic guide interferometer, including a hollow-core fiber interferometer and gradiometer, are discussed.

Review of fundamental physics results with the MAGIC telescopes

NASA Astrophysics Data System (ADS)

Rico, Javier

2017-01-01

The MAGIC Cherenkov telescopes are powerful tools for the exploration of the Physics frontiers, addressing topics such as the nature of dark matter and its distribution in the Universe, or the search for quantum gravitational effects in photon propagation. Since the beginning of operations in 2004, MAGIC has studied these questions thanks to hundreds of hours of observations of different targets, and has produced several high-impact results. Those include, significantly, the most constraining limits to the WIMP annihilation cross-section for particle masses above few hundred GeV, from observations of dwarf spheroidal (dSph) satellite galaxies. More recently, we have completed a combined analysis of MAGIC and Fermi-LAT observations of dSphs, obtaining limits for dark matter particle masses between 10 GeV and 100 TeV - the widest mass range ever explored by a single gamma-ray analysis - and improving the previously published Fermi-LAT and MAGIC results by up to a factor of two at certain masses. In this talk, I present an overview of the status and results of MAGIC Fundamental Physics projects, including our latest results concerning searches for Lorentz Invariance violation (LIV), and dark matter searches. I will propose the use of the framework developed for the MAGIC/Fermi-LAT joint analysis for the combination of results from the current generation of gamma-ray and neutrino detectors.

The "Magic" String

ERIC Educational Resources Information Center

Hoover, Todd F.

2010-01-01

The "Magic" String is a discrepant event that includes a canister with what appears to be the end of two strings protruding from opposite sides of it. Due to the way the strings are attached inside the canister, it appears as if the strings can magically switch the way they are connected. When one string end is pulled, the observer's expectation…

Pulling Words Out of a Hat: Magic in ESL Lessons.

ERIC Educational Resources Information Center

Friedenberg, Randi D.

Magic motivates students to talk, and stimulates the affective domain. While watching magic, many people imagine how the effect is accomplished or how they might perform the trick if they were performing. This can be extended into an English lesson by using phrases such as, "If I were a magician, I could..." Total physical response…

The Cultural Work of Magical Realism in Three Young Adult Novels

ERIC Educational Resources Information Center

Latham, Don

2007-01-01

Magical realism as a literary mode is often subversive and transgressive, questioning the values and assumptions of the dominant society that it depicts. Young adult literature, by contrast, is typically thought to serve a socializing function, helping to integrate young readers into adult society. What then is the cultural work of magical realism…

Molecules, magic and forgetful fruit flies: the supernatural science of medical gas research.

PubMed

Mychaskiw, George

2011-09-06

Medical gas research often involves the study of molecules under extraphysiologic conditions, that is, conditions that do not exist in nature. This "supernatural" nature of medical gas research sometimes produces results that appear to be almost "magic" to those schooled in traditional physiology"Any sufficiently advanced technology is indistinguishable from magic".-Arthur C. Clarke.

Development of next-generation mapping populations: Multi-parent Advanced Generation Inter-Cross (MAGIC) and Marker-Assisted Recurrent Selection (MARS) populations in peanut

USDA-ARS?s Scientific Manuscript database

Generation Inter-Cross (MAGIC) and Marker-Assisted Recurrent Selection (MARS) have been proposed and used in many crops to dissect complex traits or QTL. MAGIC allows for dissecting genomic structure, and for improving breeding populations by integrating multiple alleles from different parents. MAR...

Elementary School Teachers' Perceptions toward ICT: The Case of Using Magic Board for Teaching Mathematics

ERIC Educational Resources Information Center

Yuan, Yuan; Lee, Chun-Yi

2012-01-01

This study aims at investigating elementary school teachers' perceptions toward to the use of ICT. Magic Board, an interactive web-based environment which provides a set of virtual manipulatives for elementary mathematics, is used as the case of ICT. After participating in Magic Board workshops, 250 elementary school teachers in Taiwan responded…

77 FR 70432 - Magic Valley Pipeline, L.P.; Notice of Filing

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-26

... Pipeline, L.P.; Notice of Filing Take notice that on November 15, 2012, Magic Valley Pipeline, L.P. (Magic...: 5:00 p.m. Eastern Time on Tuesday, November 27, 2012. Dated: November 19, 2012. Kimberly D. Bose, Secretary. [FR Doc. 2012-28544 Filed 11-23-12; 8:45 am] BILLING CODE 6717-01-P ...

Skill of ship-following large-eddy simulations in reproducing MAGIC observations across the northeast Pacific stratocumulus to cumulus transition region

DOE PAGES

McGibbon, J.; Bretherton, C. S.

2017-03-17

During the Marine ARM GPCI Investigation of Clouds (MAGIC) in October 2011 to September 2012, a container ship making periodic cruises between Los Angeles, CA, and Honolulu, HI, was instrumented with surface meteorological, aerosol and radiation instruments, a cloud radar and ceilometer, and radiosondes. Here large-eddy simulation (LES) is performed in a ship-following frame of reference for 13 four day transects from the MAGIC field campaign. The goal is to assess if LES can skillfully simulate the broad range of observed cloud characteristics and boundary layer structure across the subtropical stratocumulus to cumulus transition region sampled during different seasons andmore » meteorological conditions. Results from Leg 15A, which sampled a particularly well-defined stratocumulus to cumulus transition, demonstrate the approach. The LES reproduces the observed timing of decoupling and transition from stratocumulus to cumulus and matches the observed evolution of boundary layer structure, cloud fraction, liquid water path, and precipitation statistics remarkably well. Considering the simulations of all 13 cruises, the LES skillfully simulates the mean diurnal variation of key measured quantities, including liquid water path (LWP), cloud fraction, measures of decoupling, and cloud radar-derived precipitation. The daily mean quantities are well represented, and daily mean LWP and cloud fraction show the expected correlation with estimated inversion strength. There is a –0.6 K low bias in LES near-surface air temperature that results in a high bias of 5.6 W m –2 in sensible heat flux (SHF). Altogether, these results build confidence in the ability of LES to represent the northeast Pacific stratocumulus to trade cumulus transition region.« less

Introducing a New Interface for the Online MagIC Database by Integrating Data Uploading, Searching, and Visualization

NASA Astrophysics Data System (ADS)

Jarboe, N.; Minnett, R.; Constable, C.; Koppers, A. A.; Tauxe, L.

2013-12-01

The Magnetics Information Consortium (MagIC) is dedicated to supporting the paleomagnetic, geomagnetic, and rock magnetic communities through the development and maintenance of an online database (http://earthref.org/MAGIC/), data upload and quality control, searches, data downloads, and visualization tools. While MagIC has completed importing some of the IAGA paleomagnetic databases (TRANS, PINT, PSVRL, GPMDB) and continues to import others (ARCHEO, MAGST and SECVR), further individual data uploading from the community contributes a wealth of easily-accessible rich datasets. Previously uploading of data to the MagIC database required the use of an Excel spreadsheet using either a Mac or PC. The new method of uploading data utilizes an HTML 5 web interface where the only computer requirement is a modern browser. This web interface will highlight all errors discovered in the dataset at once instead of the iterative error checking process found in the previous Excel spreadsheet data checker. As a web service, the community will always have easy access to the most up-to-date and bug free version of the data upload software. The filtering search mechanism of the MagIC database has been changed to a more intuitive system where the data from each contribution is displayed in tables similar to how the data is uploaded (http://earthref.org/MAGIC/search/). Searches themselves can be saved as a permanent URL, if desired. The saved search URL could then be used as a citation in a publication. When appropriate, plots (equal area, Zijderveld, ARAI, demagnetization, etc.) are associated with the data to give the user a quicker understanding of the underlying dataset. The MagIC database will continue to evolve to meet the needs of the paleomagnetic, geomagnetic, and rock magnetic communities.

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.

Magical thinking and decision-making strategies among late adolescent regular gamblers: A mediation model.

PubMed

Passanisi, Alessia; Craparo, Giuseppe; Pace, Ugo

2017-08-01

In the present study, the relation between the tendency to seek supernatural connections between external events and one's own thoughts, words, and actions and gambling among late adolescents has been studied. Psychologists have called this tendency magical thinking. The principal aim of the present study was to test the fit of an explanatory model of risk that starts from magical thinking and passes through maladaptive decision-making strategies, culminating with pathological gambling. Two hundred twenty-two Italian late adolescents, regularly attending bingo halls, aged between 19 and 21 years, completed measures on magical thinking, decision-making strategies, and gambling. Results highlight that young adults adopting dysfunctional modes of thought (i.e. magical thinking) tend to engage with maladaptive styles of decision-making that predispose them to gamble. Copyright © 2017 The Foundation for Professionals in Services for Adolescents. Published by Elsevier Ltd. All rights reserved.

Are Augmented Reality Picture Books Magic or Real for Preschool Children Aged Five to Six?

ERIC Educational Resources Information Center

Yilmaz, Rabia M.; Kucuk, Sevda; Goktas, Yuksel

2017-01-01

The aim of this study is to determine preschool children's attitudes towards augmented reality picture books (ARPB), their story comprehension performance (SCP) and the relationships between these variables. The sample consisted of 92 five- and six-year-olds (49 boys, 43 girls). An attitude form, story comprehension test and interview form were…

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.

Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed.

PubMed

Chen, Ying; Fan, Huan; Meng, Fanrui

2017-03-01

The capacity of Pleurotus ostreatus to degrade lignin was investigated in the fermentation of cornstalk. Cornstalk was incubated with P. ostreatus for 30 days, and acid-soluble and acid-insoluble lignins were assessed. The microscopic structure of cornstalk samples was studied by scanning electron microscopy (SEM), and spectroscopic characteristics were measured by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance ( 13 C NMR) spectroscopy. During fermentation of cornstalk, the proportion of acid-soluble lignin did not vary significantly (P > 0.05), but that of acid-insoluble lignin decreased gradually from 17.8% on day 0 to 7.6% on day 30 (P < 0.01). SEM revealed that the surface of cornstalk was gradually damaged with cavities increasing in number and size, forming a quasi-network structure. Crystallinity decreased from 35.0 on day 0 to 15.2 on day 30. FTIR and cross-polarization magic angle spinning (CPMAS) 13 C NMR spectra showed that the intensity of the peaks corresponding to lignin, cellulose and hemicellulose also decreased gradually over 30 days. Cornstalk can be effectively degraded by P. ostreatus within 30 days. Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

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.

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

Interpreting the structural and electrochemical complexity of 0.5Li{sub 2}MnO{sub 3}{lg_bullet}.0.5LiMO{sub 2} electrodes for lithium batteries (M=Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x}, 0{le}x{le}0.5).

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

Kang, S. H.; Kempgens, P.; Greenbaum, S.

2007-01-01

The structural and electrochemical features of layered 0.5Li{sub 2}MnO{sub 3} {center_dot} 0.5LiMO{sub 2} electrodes, in which M = Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x} (0{le} x {le} 0.5), have been studied by powder X-ray diffraction, electrochemical differential-capacity measurements, {sup 7}Li magic-angle-spinning nuclear magnetic resonance, and X-ray absorption near-edge spectroscopy. Li{sub 2}MnO{sub 3}-like regions in the as-prepared samples were observed for all values of x, with transition-metal cation disorder between the LiMO{sub 2} and Li{sub 2}MnO{sub 3} components increasing with cobalt content (i.e., the value of x). The structural disorder and complexity of the electrochemical redox reactions increase when the Li{sub 2}MnO{sub 3}-likemore » regions within the electrode are activated to 4.6 V in lithium cells; interpretations of structural and electrochemical phenomena are provided.« less

NMR of thin layers using a meanderline surface coil

DOEpatents

Cowgill, Donald F.

2001-01-01

A miniature meanderline sensor coil which extends the capabilities of nuclear magnetic resonance (NMR) to provide analysis of thin planar samples and surface layer geometries. The sensor coil allows standard NMR techniques to be used to examine thin planar (or curved) layers, extending NMRs utility to many problems of modern interest. This technique can be used to examine contact layers, non-destructively depth profile into films, or image multiple layers in a 3-dimensional sense. It lends itself to high resolution NMR techniques of magic angle spinning and thus can be used to examine the bonding and electronic structure in layered materials or to observe the chemistry associated with aging coatings. Coupling this sensor coil technology with an arrangement of small magnets will produce a penetrator probe for remote in-situ chemical analysis of groundwater or contaminant sediments. Alternatively, the sensor coil can be further miniaturized to provide sub-micron depth resolution within thin films or to orthoscopically examine living tissue. This thin-layer NMR technique using a stationary meanderline coil in a series-resonant circuit has been demonstrated and it has been determined that the flat meanderline geometry has about he same detection sensitivity as a solenoidal coil, but is specifically tailored to examine planar material layers, while avoiding signals from the bulk.

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

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

Interpolation by fast Wigner transform for rapid calculations of magnetic resonance spectra from powders.

PubMed

Stevensson, Baltzar; Edén, Mattias

2011-03-28

We introduce a novel interpolation strategy, based on nonequispaced fast transforms involving spherical harmonics or Wigner functions, for efficient calculations of powder spectra in (nuclear) magnetic resonance spectroscopy. The fast Wigner transform (FWT) interpolation operates by minimizing the time-consuming calculation stages, by sampling over a small number of Gaussian spherical quadrature (GSQ) orientations that are exploited to determine the spectral frequencies and amplitudes from a 10-70 times larger GSQ set. This results in almost the same orientational averaging accuracy as if the expanded grid was utilized explicitly in an order of magnitude slower computation. FWT interpolation is applicable to spectral simulations involving any time-independent or time-dependent and noncommuting spin Hamiltonian. We further show that the merging of FWT interpolation with the well-established ASG procedure of Alderman, Solum and Grant [J. Chem. Phys. 134, 3717 (1986)] speeds up simulations by 2-7 times relative to using ASG alone (besides greatly extending its scope of application), and between 1-2 orders of magnitude compared to direct orientational averaging in the absence of interpolation. Demonstrations of efficient spectral simulations are given for several magic-angle spinning scenarios in NMR, encompassing half-integer quadrupolar spins and homonuclear dipolar-coupled (13)C systems.

Hartmann-Hahn 2D-map to optimize the RAMP-CPMAS NMR experiment for pharmaceutical materials.

PubMed

Suzuki, Kazuko; Martineau, Charlotte; Fink, Gerhard; Steuernagel, Stefan; Taulelle, Francis

2012-02-01

Cross polarization-magic angle spinning (CPMAS) is the most used experiment for solid-state NMR measurements in the pharmaceutical industry, with the well-known variant RAMP-CPMAS its dominant implementation. The experimental work presented in this contribution focuses on the entangled effects of the main parameters of such an experiment. The shape of the RAMP-CP pulse has been considered as well as the contact time duration, and a particular attention also has been devoted to the radio-frequency (RF) field inhomogeneity. (13)C CPMAS NMR spectra have been recorded with a systematic variation of (13)C and (1)H constant radiofrequency field pair values and represented as a Hartmann-Hahn matching two-dimensional map. Such a map yields a rational overview of the intricate optimal conditions necessary to achieve an efficient CP magnetization transfer. The map also highlights the effects of sweeping the RF by the RAMP-CP pulse on the number of Hartmann-Hahn matches crossed and how RF field inhomogeneity helps in increasing the CP efficiency by using a larger fraction of the sample. In the light of the results, strategies for optimal RAMP-CPMAS measurements are suggested, which lead to a much higher efficiency than constant amplitude CP experiment. Copyright © 2012 John Wiley & Sons, Ltd.

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.

Indirect detection of 10B (I = 3) overtone NMR at very fast magic angle spinning

NASA Astrophysics Data System (ADS)

Duong, Nghia Tuan; Kuprov, Ilya; Nishiyama, Yusuke

2018-06-01

The application of overtone nuclear magnetic resonance (OT NMR) to symmetric spin transitions of integer quadrupolar nuclei is of considerable interest since this transition is immune to the first-order quadrupolar interaction, thus resulting in narrow NMR lines. Owing to its roles in nature and its high natural abundance, 14N (I = 1) OT NMR has been explored, in which the indirect and/or direct acquisitions of 14N OT were experimentally demonstrated. However, other than 14N nucleus, no OT NMR observation of other integer quadrupolar nuclei has been reported in the literature. In this work, we extend the application of OT NMR to another integer quadrupolar nucleus, namely 10B (I = 3). However, this is not straightforward owing to the unfavorable characteristics of 10B isotope. Here, for the first time, we present the selective acquisition of 10B central (-1 ↔ +1) OT NMR via detection of 1H nuclei on perborate monohydrate sample. Numerical calculations are in a good agreement with the experimental results. Both show that the optimal sensitivity is achieved when the carrier frequency is applied at the second OT spinning sideband, i.e. an offset of twice of the spinning frequency from the center band.

Thermal and spectroscopic analysis of organic matter degradation and humification during composting of pig slurry in different scenarios.

PubMed

Martín-Mata, J; Lahoz-Ramos, C; Bustamante, M A; Marhuenda-Egea, F C; Moral, R; Santos, A; Sáez, J A; Bernal, M P

2016-09-01

In this work, different analytical techniques (thermal analysis, (13)C cross-polarization magic angle spinning (CPMAS) NMR and Fourier transform infrared (FT-IR) spectroscopy) have been used to study the organic matter changes during the co-composting of pig slurry with cotton gin waste. To ensure the validity of the findings, the composting process was developed in different scenarios: under experimental pilot plant conditions, using the static pile system, and under real conditions on a pig farm, using the turning pile system. Also, the thermal stability index (R1) was determined before and after an extraction with water, to evaluate the effect of eliminating water-soluble inorganic salts on the thermal analysis. The results of the thermal methods showed the degradation of the most labile organic matter during composting; R1 increased during composting in all piles, without any influence of the presence of water-soluble inorganic ions in the sample. The NMR showed a decrease in the abundance of the carbohydrate molecules and an increase in the aliphatic materials during composting, due to a concentration effect. Also, FT-IR spectroscopy was a useful technique to study the trends of polysaccharides and nitrate, as indicators of organic matter transformations during composting.

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.

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.

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

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.

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.

Molecules, magic and forgetful fruit flies: the supernatural science of medical gas research

PubMed Central

2011-01-01

Medical gas research often involves the study of molecules under extraphysiologic conditions, that is, conditions that do not exist in nature. This "supernatural" nature of medical gas research sometimes produces results that appear to be almost "magic" to those schooled in traditional physiology "Any sufficiently advanced technology is indistinguishable from magic". -Arthur C. Clarke PMID:22146602

The Magical Classroom: Exploring Science, Language, and Perception with Children.

ERIC Educational Resources Information Center

Strauss, Michael J.

The science of magic is the subject of this book which also examines how to help children experience and describe the world, how to experiment and ask questions about it, and how to make decisions about what is true and what is not. Background information about the relationship between magic and science and the nature of effects and illusions are…

Overview of MAGIC results

NASA Astrophysics Data System (ADS)

Rico, Javier; MAGIC Collaboration

2016-04-01

MAGIC is a system of two 17-m diameter Cherenkov telescopes, located at the Observatorio del Roque de los Muchachos, in the Canary island La Palma (Spain). MAGIC performs astronomical observations of gamma-ray sources in the energy range between 50 GeV and 10 TeV. The first MAGIC telescope has been operating since 2004, and in 2009 the system was completed with the second one. During 2011 and 2012 the electronics for the readout system were fully upgraded, and the camera of the first telescope replaced. After that, no major hardware interventions are foreseen in the next years, and the experiment has undertaken a final period of steady astronomical observations. MAGIC studies particle acceleration in the most violent cosmic environments, such as active galactic nuclei, gamma-ray bursts, pulsars, supernova remnants or binary systems. In addition, it addresses some fundamental questions of Physics, such as the origin of Galactic cosmic rays and the nature of dark matter. Moreover, by observing the gamma-ray emission from sources at cosmological distances, we measure the intensity and evolution of the extragalactic background radiation, and perform tests of Lorentz Invariance. In this paper I present the status and some of the latest results of the MAGIC gamma-ray telescopes.

Real time dynamics of Si magic clusters mediating phase transformation: Si(111)-(1 × 1) to (7 × 7) reconstruction revisited

NASA Astrophysics Data System (ADS)

Ong, Wei Jie; Tok, Eng Soon

2012-07-01

Using Scanning Tunneling Microscope (STM), we show that the surface undergoes phase transformation from disordered "1 × 1" to (7 × 7) reconstruction which is mediated by the formation of Si magic clusters. Mono-disperse Si magic clusters of size ~ 13.5 ± 0.5 Å can be formed by heating the Si(111) surface to 1200 °C and quenching it to room temperature at cooling rates of at least 100 °C/min. The structure consists of 3 tetra-clusters of size ~ 4.5 Ǻ similar to the Si magic clusters that were formed from Si adatoms deposited by Si solid source on Si(111)-(7 × 7) [1]. Using real time STM scanning to probe the surface at ~ 400 °C, we show that Si magic clusters pop up from the (1 × 1) surface and form spontaneously during the phase transformation. This is attributed to the difference in atomic density between "disordered 1 × 1" and (7 × 7) surface structures which lead to the release of excess Si atoms onto the surface as magic clusters.

Does magical thinking produce neutralising behaviour? An experimental investigation.

PubMed

Bocci, Laura; Gordon, P Kenneth

2007-08-01

Magical thinking is of relevance to obsessive compulsive disorder (OCD), and has been most widely investigated in relation to the cognitive bias known as thought-action fusion (TAF). This is seen as playing a role in the formation of fears about responsibility for harm. We suggest that magical thinking may also characterise some types of neutralising behaviour, which arise in response to those fears, and are a hallmark of the disorder. In an experimental study of 51 undergraduate students, we assessed whether the use of neutralising behaviours in response to an induction of fears of increasing likelihood for harm is related to a propensity for magical thinking. The 75.5% of participants demonstrated at least one form of neutralising behaviour in response to a TAF-induction task. Neutralising was associated with stronger and more persistent responses to the task, and with questionnaire measures of magical ideation. Those who neutralised did not report higher levels of OCD symptoms. It appears that neutralising is a common response in circumstances that provoke a sense of responsibility for harm. Its occurrence may be linked to magical thinking, however, the results from this experimental investigation suggested that this process may not be specific to OCD.

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.

Characterization of a novel two dimensional diode array the "magic plate" as a radiation detector for radiation therapy treatment.

PubMed

Wong, J H D; Fuduli, I; Carolan, M; Petasecca, M; Lerch, M L F; Perevertaylo, V L; Metcalfe, P; Rosenfeld, A B

2012-05-01

Intensity modulated radiation therapy (IMRT) utilizes the technology of multileaf collimators to deliver highly modulated and complex radiation treatment. Dosimetric verification of the IMRT treatment requires the verification of the delivered dose distribution. Two dimensional ion chamber or diode arrays are gaining popularity as a dosimeter of choice due to their real time feedback compared to film dosimetry. This paper describes the characterization of a novel 2D diode array, which has been named the "magic plate" (MP). It was designed to function as a 2D transmission detector as well as a planar detector for dose distribution measurements in a solid water phantom for the dosimetric verification of IMRT treatment delivery. The prototype MP is an 11 × 11 detector array based on thin (50 μm) epitaxial diode technology mounted on a 0.6 mm thick Kapton substrate using a proprietary "drop-in" technology developed by the Centre for Medical Radiation Physics, University of Wollongong. A full characterization of the detector was performed, including radiation damage study, dose per pulse effect, percent depth dose comparison with CC13 ion chamber and build up characteristics with a parallel plane ion chamber measurements, dose linearity, energy response and angular response. Postirradiated magic plate diodes showed a reproducibility of 2.1%. The MP dose per pulse response decreased at higher dose rates while at lower dose rates the MP appears to be dose rate independent. The depth dose measurement of the MP agrees with ion chamber depth dose measurements to within 0.7% while dose linearity was excellent. MP showed angular response dependency due to the anisotropy of the silicon diode with the maximum variation in angular response of 10.8% at gantry angle 180°. Angular dependence was within 3.5% for the gantry angles ± 75°. The field size dependence of the MP at isocenter agrees with ion chamber measurement to within 1.1%. In the beam perturbation study, the surface dose increased by 12.1% for a 30 × 30 cm(2) field size at the source to detector distance (SDD) of 80 cm whilst the transmission for the MP was 99%. The radiation response of the magic plate was successfully characterized. The array of epitaxial silicon based detectors with "drop-in" packaging showed properties suitable to be used as a simplified multipurpose and nonperturbing 2D radiation detector for radiation therapy dosimetric verification.

MAGIC: A Tool for Combining, Interpolating, and Processing Magnetograms

NASA Technical Reports Server (NTRS)

Allred, Joel

2012-01-01

Transients in the solar coronal magnetic field are ultimately the source of space weather. Models which seek to track the evolution of the coronal field require magnetogram images to be used as boundary conditions. These magnetograms are obtained by numerous instruments with different cadences and resolutions. A tool is required which allows modelers to fmd all available data and use them to craft accurate and physically consistent boundary conditions for their models. We have developed a software tool, MAGIC (MAGnetogram Interpolation and Composition), to perform exactly this function. MAGIC can manage the acquisition of magneto gram data, cast it into a source-independent format, and then perform the necessary spatial and temporal interpolation to provide magnetic field values as requested onto model-defined grids. MAGIC has the ability to patch magneto grams from different sources together providing a more complete picture of the Sun's field than is possible from single magneto grams. In doing this, care must be taken so as not to introduce nonphysical current densities along the seam between magnetograms. We have designed a method which minimizes these spurious current densities. MAGIC also includes a number of post-processing tools which can provide additional information to models. For example, MAGIC includes an interface to the DA VE4VM tool which derives surface flow velocities from the time evolution of surface magnetic field. MAGIC has been developed as an application of the KAMELEON data formatting toolkit which has been developed by the CCMC.

Working wonders? investigating insight with magic tricks.

PubMed

Danek, Amory H; Fraps, Thomas; von Müller, Albrecht; Grothe, Benedikt; Ollinger, Michael

2014-02-01

We propose a new approach to differentiate between insight and noninsight problem solving, by introducing magic tricks as problem solving domain. We argue that magic tricks are ideally suited to investigate representational change, the key mechanism that yields sudden insight into the solution of a problem, because in order to gain insight into the magicians' secret method, observers must overcome implicit constraints and thus change their problem representation. In Experiment 1, 50 participants were exposed to 34 different magic tricks, asking them to find out how the trick was accomplished. Upon solving a trick, participants indicated if they had reached the solution either with or without insight. Insight was reported in 41.1% of solutions. The new task domain revealed differences in solution accuracy, time course and solution confidence with insight solutions being more likely to be true, reached earlier, and obtaining higher confidence ratings. In Experiment 2, we explored which role self-imposed constraints actually play in magic tricks. 62 participants were presented with 12 magic tricks. One group received verbal cues, providing solution relevant information without giving the solution away. The control group received no informative cue. Experiment 2 showed that participants' constraints were suggestible to verbal cues, resulting in higher solution rates. Thus, magic tricks provide more detailed information about the differences between insightful and noninsightful problem solving, and the underlying mechanisms that are necessary to have an insight. Copyright © 2013 Elsevier B.V. All rights reserved.

Using Magic Board as a Teaching Aid in Third Grader Learning of Area Concepts

ERIC Educational Resources Information Center

Chang, Wen-Long; Yuan, Yuan; Lee, Chun-Yi; Chen, Min-Hui; Huang, Wen-Guu

2013-01-01

The purpose of this study was to explore the impact of incorporating Magic Board in the instruction of concepts related to area. We adopted a non-equivalent quasi-experimental design and recruited participants from two classes of third-grade students in an elementary school in Taoyuan County, Taiwan. Magic Board was used as a teaching aid in the…

CapDEM TD - Modeling and Simulation (Role and Tools) State of the Art Report

DTIC Science & Technology

2005-01-01

office/wcm1/ornclinfn/ciefilnlt rnsnx [55] http://www.idefine.com/Tutorial/TutOiial%20Sales%20Page.htm [56] Gartner , " Magic Quadrant for Business ...21 Figure 3-5: Gartner Magic Quadrant For BPA, 2004 (56...of January 2004 Niche Players Visionaries ------- Completeness of Vision ..., Figure 3-5: Gartner Magic Quadrant For BPA, 2004 [56] Gartner , Inc

Learning Activities That Combine Science Magic Activities with the 5E Instructional Model to Influence Secondary-School Students' Attitudes to Science

ERIC Educational Resources Information Center

Lin, Jang-Long; Cheng, Meng-Fei; Chang, Ying-Chi; Li, Hsiao-Wen; Chang, Jih-Yuan; Lin, Deng-Min

2014-01-01

The purpose of this study was to investigate how learning materials based on Science Magic activities affect student attitudes to science. A quasi-experimental design was conducted to explore the combination of Science Magic with the 5E Instructional Model to develop learning materials for teaching a science unit about friction. The participants…

Magical Thinking in Judgments of Causation: Can Anomalous Phenomena Affect Ontological Causal Beliefs in Children and Adults?

ERIC Educational Resources Information Center

Subbotsky, Eugene

2004-01-01

In four experiments, 4-, 5-, 6- and 9-year-old children and adults were tested on the entrenchment of their magical beliefs and their beliefs in the universal power of physical causality. In Experiment 1, even 4-year-olds showed some understanding of the difference between ordinary and anomalous (magical) causal events, but only 6-year-olds and…

The Ghost in the Machine: Why and How the Belief in Magic Survives in the Rational Mind

ERIC Educational Resources Information Center

Subbotsky, Eugene

2011-01-01

Since the time of Galileo (1564-1642), Western civilization has increasingly fallen under the spell of science. Despite this fact, anthropological and psychological research has shown that magical beliefs are present in both children and adults in modern industrial cultures. How can a belief in magic coexist with a belief in science in the mind of…

Francesca Lia Block's Use of Enchantment: Teenagers' Need for Magic in the Real World.

ERIC Educational Resources Information Center

Warner, Lois L.

2002-01-01

Considers how Francesca Lia Block's melding of the magic and the ordinary makes her work special. Suggests that magic is what makes people dream, and that the teen years is a great time to dream because there is still time to make dreams come true. Presents a nine-item annotated bibliography of titles for adolescents by Block. (SG)

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.