Signal Enhancement Using 45° Water Flipback for 3D N-Edited ROESY and NOESY HMQC and HSQC

A novel implementation of the water flipback technique employing a 45° flip-angle water-selective pulse is presented. The use of this water flipback technique is shown to significantly enhance signal in 3D ¹⁵N-edited ROESY in a 20 kDa complex of the vnd/NK-2 homeodomain bound to DNA. The enhancement is seen relative to the same experiment using weak water presaturation during the recovery delay. This enhancement is observed for the signals from both labile and nonlabile protons. ROESY and NOESY pulse sequences with 45° water flipback are presented using both HMQC and HSQC for the ¹⁵N dimension. The 45° flipback pulse is followed by a gradient, a water selective 180° pulse, and another gradient to remove quadrature images and crosspeak phase distortion near the water frequency. Radiation damping of the water magnetization during the t₁ and t₂ evolution periods is suppressed using gradients. Water resonance planes from NOESY–HMQC and NOESY–HSQC spectra show that the HMQC version of the pulse sequences can provide stronger signal for very fast exchanging protons. The HSQC versions of the ROESY and NOESY pulse sequences are designed for the quantitative determination of protein–water crossrelaxation rates, with no water-selective pulses during the mixing time and with phase cycling and other measures for reducing axial artifacts in the water signal.     

Determination of the Splitting of the 6a0 and 6b0 Bands of C-Hexadeuterobenzene in a Supersonic Jet

By using resonance-enhanced two-photon ionization, rotationally resolved spectra of the 6¹₀ band of ¹²C₆D₆ and (¹³C¹²C₅D₆ molecules have been obtained for the first time at a rotational temperature of 0.7 K in a pulsed supersonic beam. From the former, the values of B″ = 0.1573 ± 0.0008 cm⁻¹, B′ = 0.1508 ± 0.0008 cm⁻¹, and ξ′ = −0.412 ± 0.050 have been derived for rotational and Coriolis constants in the lower and upper levels of ¹²C₆D₆. Also, the spectra corresponding to ¹²C₆H₆ and ¹³C¹²C₅H₆ have been measured and the values B″ = 0.1892 ± 0.0008 cm⁻¹, B′ = 0.1815 ± 0.0008 cm⁻¹, and ξ′ = −0.586 ± 0.050 have been obtained for ¹²C₆H₆, in agreement with previous results. Rotational constants of ¹³C labeled benzene molecules have been geometrically deduced from the constants obtained. Experimental isotopic shifts of the vibronic origins of the 6a¹₀ and 6b¹₀ bands have been determined. There is agreement with previous ¹³C-benzene-h₆ data. The present results are −0.91 ± 0.05 and 3.09 ± 0.05 cm⁻¹ for ¹³C¹²C₅D₆ and −1.64 ± 0.05 and 2.64 ± 0.05 cm⁻¹ for ¹³C¹²C₅H₆. The splittings of vibrational modes 6b and 6a in the ¹B_2u state are 4.00 ± 0.10 cm⁻¹ for ¹³C¹²C₅D₆ and 4.28 ± 0.10 cm⁻¹ for ¹³C¹²C₅H₆.     

Sensitive, quantitative carbon-13 NMR spectra by mechanical sample translation

Collecting a truly quantitative carbon-13 spectrum is a time-consuming chore. Very long relaxation delays, required between transients to allow the z-magnetization, M_z, of the spin with the longest T₁ to return to the equilibrium value, M₀, must precede each transient. These long delays also reduce sensitivity, as fewer transients per unit time can be acquired. In addition, sometimes T₁ is not known to within even a factor of two: a conservative guess for the relaxation delay then leads to very low sensitivity. We demonstrate a fresh method to bypass these problems and collect quantitative carbon-13 spectra by swapping the sample volume after each acquisition with a different portion where the magnetization is already equilibrated to M₀. Loading larger sample volumes of 10–20 mL into an unusually long (1520 mm) 5 mm OD. NMR tube and vertically sliding the tube between acquisitions accomplishes the swap. The relaxation delay can then be skipped altogether. The spectra are thus both quantitative, and far more sensitive. We demonstrate the moving tube technique on two small molecules (thymol and butylhydroxytoluene) and show good carbon-13 quantification. The gain in sensitivity can be as much as 10-fold for slowly-relaxing ¹³C resonances. These experiments show that quantitative, sensitive carbon-13 spectra are possible whenever sufficient sample volumes are available. The method is applicable to any slow-relaxing nuclear spin species, such as ²⁹Si, ¹⁵N and other low-γ nuclei.     

Complete Dipolar Decoupling ofC and Its Use in Two-Dimensional Double-Quantum Solid-State NMR for Determining Polymer Conformations

A multiple-pulse technique for complete dipolar decoupling of directly bonded¹³C-labeled sites is described. It achieves significant spectral simplifications in a recently introduced two-dimensional double-quantum solid-state NMR experiment for determining torsion angles. Both homonuclear and heteronuclear dipolar couplings are removed by combining a¹³C multiple-pulse sequence with continuous-wave irradiation on the protons. The¹³C sequence has a fundamental 10-pulse cycle which is a significantly modified magic-sandwich-echo sequence. The crucial heteronuclear decoupling is achieved by breaking the 360° “inner” pulses in the magic sandwich into 90° pulses and spacing them by¹H 360° pulse lengths. Spectral artifacts typical of multiple-pulse sequences are eliminated by phase shifts between cycles. In contrast to many other multiple-pulse decoupling sequences, the long window in the cycle is the dwell time and can be longer than the inverse dipolar coupling, which makes the sequence practical for direct detection even with long pulse ring-down times. A modification of the sequence to scale the chemical shift and increase the effective spectral width is also presented. The 1D and double-quantum 2D experiments are demonstrated on polyethylene with 4%¹³C–¹³C spin pairs. The potential of this approach for distinguishing segmental conformations is illustrated by spectral simulations of the two-dimensional ridge patterns that correlate double-quantum and single-quantum chemical-shift anisotropies.     

Control of susceptibility-related image contrast by spin-lock techniques

Macroscopic magnetic field inhomogeneities might lead to image distortions, while microscopic field inhomogeneities, due to susceptibility changes in tissues, cause spin dephasing and decreasing T₂ relaxation time. The latter effects are especially observed in the trabecular bone and in regions adjacent to air-containing cavities when gradient-echo sequences are applied. In conventional MRI, these susceptibility-related signal voids can be avoided by applying spin-echo (SE) techniques. In this study, an alternative method for the examination and control of susceptibility-related effects by spin-lock (SL) radiofrequency pulses is presented: SL pulses were applied in two different susceptibility-sensitive sequence types: (a) between the jump and return 90° pulses in a 90°_x−τ−90°_−x magnetization-prepared Fast Low Angle Shot (FLASH) sequence and (b) between the 90° pulse and the 180° pulse in an asymmetric SE sequence. The range of Larmor frequencies used for spin locking can be determined for different B₁ amplitudes of the SL pulses, allowing control of image contrast by the amplitude of the SL pulses.     

Tagging of the Magnetization with the Transition Zones of 360° Rotations Generated by a Tandem of Two Adiabatic DANTE Inversion Sequences

A new technique is presented for generating myocardial tagging using the signal intensity minima of the transition zones between the bands of 0° and 360° rotations, induced by a tandem of two adiabatic delays alternating with nutations for tailored excitation (DANTE) inversion sequences. With this approach, the underlying matrix corresponds to magnetization that has experienced 0° or 360° rotations. The DANTE sequences were implemented from adiabatic parent pulses for insensitivity of the underlying matrix to B₁ inhomogeneity. The performance of the proposed tagging technique is demonstrated theoretically with computer simulations and experimentally on phantom and on the canine heart, using a surface coil for both RF transmission and signal reception. The simulations and the experimental data demonstrated uniform grid contrast and sharp tagging profiles over a twofold variation of the B₁ field magnitude.     

Surface plasmon polaritons on square-lattice arrays of three-fold symmetric nanostructures

The influence of the geometry of three-fold symmetric rotor shaped nanostructures arranged as a two-dimensional square-lattice on the excitation of surface plasmon polaritons (SPPs) is studied numerically. We consider SPP-related extrema of the far-field reflectivity R(α) as a function of the polarization angle α of the incident light. In agreement with recent experimental work, it is observed that these extrema shift away from α=0° and α=90°, where they are found for rotationally invariant nanostructures. The polarization angle corresponding to the most efficient SPP excitation is found to be independent of the shape of the individual nanostructures. We further investigate the influence of the shape and size of the nanostructures and discuss consequences for optical near- and far-field properties.     

Improved SNR in linear reordered 2D bSSFP imaging using variable flip angles

This article presents a variable flip-angle approach for balanced steady-state free precession (bSSFP) imaging, which allows increases in signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR) while keeping specific absorption rate (SAR) constant or reduces SAR for given CNR and SNR. The gain in SNR is achieved by utilizing the higher signal in the transient phase. Flip-angle variation during the echo train is realized using a trigonometric function with M steps (ramp length). Variation is combined with a linear k-space reordering such that outer parts of k-space are sampled using a lower flip angle α_min, while the central part of k-space is acquired with a higher flip angle α_max. No additional preparation or dummy cycles are applied prior to data acquisition. Several variation schemes with different starting flip angles α_min and ramp length M are considered. For example, using α_min=1° and M=96, α_max can be set to 47° without exceeding SAR limits at 3 T and gaining up to 50% in SNR, while, conventionally, α=34° is the maximal possible flip angle. Resolution seems unaffected in volunteer imaging. In all cases, no transient artifacts due to flip-angle variation were observed. This article demonstrates the use of flip-angle variations in bSSFP to increase SNR and CNR while keeping SAR constant, which is especially important at higher field strengths. Flip-angle variation can also be combined with other methods such as parallel imaging techniques for further SAR reduction.     

Effects of nano-carbon doping and sintering temperature on microstructure and properties of MgB2

We fabricated nano-carbon (NC) doped MgB₂ bulks using an in situ process in order to improve the critical current density (J_c) under a high magnetic field and evaluated the correlated effects of the doped carbon content and sintering temperature on the phase formation, microstructure and critical properties. MgB_2−xC_x bulks with x = 0 and 0.05 were fabricated by pressing the powder into pellets and sintering at 800 °C, 900 °C, or 1000 °C for 30 min.We observed that NC was an effective dopant for MgB₂ and that part of it was incorporated into the MgB₂ while the other part remained (undoped), which reduced the grain size. The actual C content was estimated to be 68–90% of the nominal content. The NC doped samples exhibited lower T_c values and better J_c(B) behavior than the undoped samples. The doped sample sintered at 900 °C showed the highest J_c value due to its high doping level, small amount of second phase, and fine grains. On the other hand, the J_c was decreased at a sintering temperature of 1000 °C as a result of the formation of MgB₄ phase.     

N Chemical Shift Tensor Magnitude and Orientation in the Molecular Frame of Uracil Determined via MAS NMR

The potential of heteronuclear MAS NMR spectroscopy for the characterization of ¹⁵N chemical shift (CS) tensors in multiply labeled systems has been illustrated, in one of the first studies of this type, by a measurement of the chemical shift tensor magnitude and orientation in the molecular frame for the two ¹⁵N sites of uracil. Employing polycrystalline samples of ¹⁵N₂ and 2-¹³C,¹⁵N₂-labeled uracil, we have measured, via ¹⁵N–¹³C REDOR and ¹⁵N–¹H dipolar-shift experiments, the polar and azimuthal angles (θ, ψ) of orientation of the ¹⁵N–¹³C and ¹⁵N–¹H dipolar vectors in the ¹⁵N CS tensor frame. The (θ_NC, ψ_NC) angles are determined to be (92 ± 10°, 100 ± 5°) and (132 ± 3°, 88 ± 10°) for the N1 and N3 sites, respectively. Similarly, (θ_NH, ψ_NH) are found to be (15 ± 5°, −80 ± 10°) and (15 ± 5°, 90 ± 10°) for the N1 and N3 sites, respectively. These results obtained based only on MAS NMR measurements have been compared with the data reported in the literature.     

An Efficient Broadband Decoupling Sequence for Liquid Crystals

A new and efficient broadband decoupling sequence is presented. It is based on the phase cycling of two pulses with small phase angles. The pulse width is 180° ± 30°, and the phase angle is ±10°–12°. The sequence contains 16 elements, and is called SPARC-16 as an abbreviation forsmallphaseanglerapidcycling. The application of this sequence to a liquid crystalline compound, 4-n-pentyl-4′-cyanobiphenyl (5CB), is reported. The signal-to-noise ratios and the linewidths of the¹³C peaks of 5CB with SPARC-16 decoupling and with other decoupling methods are compared. The results show that the broadband decoupling efficiency of SPARC-16 is considerably better than those of other methods.     

Isoscalar quadrupole strength in Ca from the (p,p′α0) reaction at Ep = 100 MeV

The ⁴⁰Ca(p,p′ α) reaction has been studied at an incident proton energy E_p = 99.5 MeV for proton laboratory scattering angles Θ_p^lab = 17°, 23° and 27°. Emission of α particles coincident with the scattered proton has been measured for an angular range Θ_α 0° − 180° relative to the recoil axis. A multipole decomposition for the α₀-decay channel to the ³⁶Ar ground state has been performed from the angular-correlation functions. The energy distribution of the dominating E2 strength deduced in the excitation energy range E_x = 11–21 MeV agrees reasonably well with the results from electron and α-induced α₀-decay investigations. The exhaustion of the E2 energy-weighted sum rule in this channel up to an energy of 17 MeV is 16.1(4.0)%, in accord with the study of the (α, α′ α₀) reaction. However, this value is twice what is found in the (e,e′ α₀) experiment in the same energy region. Thus, the puzzling discrepancy in the E2 strengths derived from electromagnetic and hadronic probes remains unsolved.     

: A quantitative measure of NMR signal receiving efficiency

Recognizing that the sensitivity of NMR is influenced by factors such as conductance and dielectric constant of the sample, we propose the receiving efficiency to characterize how efficiently the NMR signal can be observed from a unit transverse magnetization in a sample under optimal probe tuning and matching conditions. Conveniently, the relative receiving efficiency can be defined as the ratio of the NMR signal induced by a unit transverse magnetization in a sample of interest and a reference solution. Based on the reciprocal relationship between excitation and observation in NMR, the relative receiving efficiency can be correlated with the 90° pulse length (τ₉₀). In the special case of perfect probe tuning (impedance matched to 50 Ω), is inversely proportional to τ₉₀. Application of the NMR receiving efficiency in quantitative analysis potentially enables a single external concentration reference for almost any sample, eliminating the need to know its exact chemical composition or detailed electromagnetic properties.     

Emergence of order in nanocrystalline SmFe9

Three samples consistent with 1 : 12, 2 : 17 and 1 : 7 stoichiometry, ball-milled and subsequently annealed at temperature T_a between 600 and 1200°C were studied by Rietveld analysis, coupled to Curie temperature T_c measurements and Mössbauer spectroscopy. For all samples, at 600°CT_a<900°C, the detected out-of-equilibrium phase is the hexagonal P6/mmm structure derived from TbCu₇ with the composition SmFe₉. At T_a900°C the ordered phase of Th₂Zn₁₇-type is observed. With increasing T_a the unit cell parameter small variation of the parent SmFe₉ induces a decrease of T_c and H_hf. For T_a=600°C SmFe₉ is defined by a=0.4919 nm, c=0.4162 nm, T_c=207°C and H_hf=232 kOe. The resulting ordered Sm₂Fe₁₇ is characterized by nm, c=3×0.4147 nm, T_c=144°C and H_hf=219 kOe. For T_a=750°C the SmFe₉ T_c is 171°C associated to H_hf=222 kOe.     

Echo-Planar Imaging of Porous Media with Spatial Resolution below 100 μm

A modified version of the echo-planar imaging technique incorporating a Carr–Purcell train of 180° rf pulses (PEPI) has been implemented on a standard spectrometer. It is demonstrated that artifacts in the image due to cumulative errors in the rf field can be reduced by replacing each 180° pulse by a composite sequence of three rf pulses. Artifact-free 3D images at 94 μm voxel resolution are obtained within 15 min. This technique has been applied to study the drying process in an initially water-saturated model porous medium with characteristicT^*₂of order 700 μs.     

Magnetic properties of melt-spun Sm2+Y(Co0.8Fe0.1Mn0.1)17BX alloys

Melt-spun ribbons with composition Sm_2+Y(Co_0.8Fe_0.1Mn_0.1)₁₇B_X (X=0–1.0 and Y=0–0.2) were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 500–800°C for 2.5–60 min. Our results show that all the ribbons annealed up to 800°C are composed of a TbCu₇-type phase as the main phase. The highest coercivity of 8.7 kOe is obtained in a Sm-rich sample with composition Sm_2.2(Co_0.8Fe_0.1Mn_0.1)₁₇ annealed at 750°C for 5 min. It is found that these magnets show a very promising high-temperature performance – much better than those of typical sintered 2 : 17 magnets.     

Measurement of the form-factor ratios for

The form factor ratios r_V=V(0)/A₁(0), r₂=A₂(0)/A₁(0) and r₃=A₃(0)/A₁(0) in the decay , have been measured using data from charm hadroproduction experiment E791 at Fermilab. From 3034 (595) signal (background) events in the muon channel, we obtain r_V=1.84±0.11±0.09, r₂=0.75±0.08±0.09 and, as a first measurement of r₃, we find 0.04±0.33±0.29. The values of the form factor ratios r_V and r₂ measured for the muon channel are combined with the values of r_V and r₂ that we have measured in the electron channel. The combined E791 results for the muon and electron channels are r_V=1.87±0.08±0.07 and r₂=0.73±0.06±0.08.     

Modified Michelson interferometer for probing refractive index of birefringent crystal CSBN50

Based on the modified Michelson interferometer and phase analysis method, a high-accuracy method for probing the refractive index (RI) of transparent medium is proposed. The validated test was performed on a birefringent crystal CSBN50 with the estimated accuracy being up to 10⁻⁴. The ordinary and extraordinary refractive indices of CSBN50 at 632.8 nm are determined as n₀=2.32853±0.00016 and n_e=2.27664±0.00016, respectively.     

One- and two-dimensional C–H/N–H dipolar correlation experiments under fast magic-angle spinning for determining the peptide dihedral angle φ

A recently proposed ¹³C–¹H recoupling sequence operative under fast magic-angle spinning (MAS) [K. Takegoshi, T. Terao, Solid State Nucl. Magn. Reson. 13 (1999) 203–212.] is applied to observe ¹³C–¹H and ¹⁵N–¹H dipolar powder patterns in the ¹H–¹⁵N–¹³C–¹H system of a peptide bond. Both patterns are correlated by ¹⁵N-to-¹³C cross polarization to observe one- or two-dimensional (1D or 2D) correlation spectra, which can be simulated by using a simple analytical expression to determine the H–N–C–H dihedral angle. The 1D and 2D experiments were applied to N-acetyl[1,2-¹³C,¹⁵N] -valine, and the peptide φ angle was determined with high precision by the 2D experiment to be ±155.0°±1.2°. The positive one is in good agreement with the X-ray value of 154°±5°. The 1D experiment provided the value of φ=±156.0°±0.8°.     

Separation of the ortho and para NMR signals in solid deuterium via DQ filtering

Double quantum (DQ) filtering is shown to lead to an effective separation of the NMR signals from the para (I = 1) and ortho (I = 2) molecules in solid deuterium. The separation is achieved by the pulse sequence 90_φ^°–t_pr–90_φ^°–t_ev–90_x^°–t, where the phase-cycled first two pulses create the DQ coherence. Two components are observed after the third pulse; the para signal shows the maximum at a short time t while the ortho signal reaches the maximum at a longer t. The observed signal can be expressed as ∑_I [F_I(t_pr − t) − F_I(t_pr + t)], where F_I(t) is a proper fitting function for the free induction signal of the para and ortho molecules (with I = 1 or 2, respectively). Numerical fits to experimental data at 4.2 and 2 K show that this method can be used to determine the ratio F₁(0)/F₂(0) and thus, because the initial value F_I(0) is proportional to the respective magnetization before the pulse sequence, the ortho and para concentrations in solid deuterium.