Reference deconvolution. Elimination of distortions arising from reference line truncation

Reference deconvolution (G. A. Morris; J. Magn. Reson. 80, 547 (1988)) or reference lineshape adjustment (J. M. Wouters and G. A. Petersson, J. Magn. Reson. 28,81 (1977); J. M. Wouters, G. A. Petersson, W. C. Agosta, F. H. Field, W. A. Gibbons, H. Wyssbrod, and D. Cowburn, J. Magn. Reson. 28, 93 (1977)) relies on extracting the signal of a known reference material from an experimental spectrum and using a comparison between the experimental reference signal and that predicted by theory to correct instrumental contributions to the full experimental spectrum. Truncation of the reference line can produce unwanted artifacts and distortions in the final spectrum. The source of these anomalies usually lies in the dispersion-mode rather than in the absorption-mode data, as discontinuities are formed when the dispersion “wings” are truncated. These discontinuities can be reduced by a numerical extrapolation covering the lost region; this is sufficient to provide adequate results in most cases, but fails where spectra have baseline errors. A method of recreating the full dispersion signal directly from the corresponding adsorption data, based on the Hilbert transform relationship between the real and imaginary parts of a Fourier transform, is demonstrated here. This method results in the removal of truncation distortions from the deconvoluted spectrum, thus extending the range of application of the reference deconvolution technique.     

Comparative Studies of Phase-Cycling Schemes for Multiple π-Pulse Sequences

Recently, a new phase cycling scheme was introduced by this laboratory for use in biological solid-state NMR experiments involving multiple π-pulses with characteristics that suggested it may enhance the sensitivity of these kind of experiments (Y. Li and J. N. S. Evans, 1995,Chem. Phys. Lett.241,79 and Erratum, 1995,ibid.246,527; Y. Li and J. N. S. Evans, 1996,J. Magn. Reson. B111,296). The new sequence followed the supercycled concept proposed a decade ago for heteronuclear decoupling experiments. In this paper, more detailed experiments demonstrate that the claim of enhanced sensitivity was unfounded, and in fact the supercycle proposed differs little from the established XY-8 and XY-16 based supercycles.     

Application to Rat Lung of the Extended Rorschach–Hazlewood Model of Spin–Lattice Relaxation

The spin–lattice relaxation timeT₁was measured in excised degassed (airless) rat lungs over the frequency range 6.7 to 80.5 MHz. The observed frequency dependence was fitted successfully to the water–biopolymer cross-relaxation theory proposed by H. E. Rorschach and C. F. Hazlewood (RH) [J. Magn. Reson.70,79 (1986)]. The rotating frame spin–lattice relaxation timeT_1ρwas also measured in rat lung fragments over the frequency range 0.56 to 5.6 kHz, and the observed frequency dependence was explained with an extension of the RH model. The agreement between the theory and the experimental data in both cases is good.     

Projection Presaturation. III. Accurate Selective Excitation or Presaturation of the Regions of Tailored Shape in the Presence of Short-T1 Species

A new method is described which further increases the accuracy of localization by projection presaturation (PP), a technique for multidimensional spatial localization of contoured regions of interest (ROIs), whose shape, size, position, and number can be chosen arbitrarily (J. Magn. Reson.90, 313, 1990). By applying a nonselective radiofrequency inversion pulse after the PP saturation cycle and nulling the residual longitudinal magnetization of the region outside the ROI, the outer-volume signal is suppressed to the "noise" level, thus improving the accuracy of the basic PP localization, even when saturating a large exterior volume of short-T₁ species. The ability of the method to perform spatial and spectral localization simultaneously is also described. Alternatively, the single-shot methods for selective saturation (instead of selective excitation) of single or multiple contoured regions at arbitrary positions in an extended volume are presented. In particular, the results of selective excitation and saturation of a region of conformal geometric shape in two and three dimensions in a phantom as well as in vivo (healthy volunteers) are presented to demonstrate the efficacy of the method. Applications of these methods include flow- and motion-artifact suppression in body MRI, accurate conformal localization for in vivo spectroscopy in the presence of chemical shift, outer-volume suppression for resolution or speed enhancement in ultrafast imaging (Magn. Reson. Med.13, 77, 1990; J. Phys. C10, L55, 1977), and spin tagging by selective excitation/saturation of flowing spins for flow studies and angiography.     

Iterative analysis of strong coupling effects in semiselective J spectroscopy

A computer program for the iterative analysis of semiselective J spectra (A. Bax, J. Magn. Reson.52, 330 (1983)) is described, and experimental and calculated f₁ cross sections through semiselective 2D J spectra for the three-spin system of fumaric acid monoethyl ester and the five-spin system of thiophene are compared.     

MAG-PGSTE: a new STE-based PGSE NMR sequence for the determination of diffusion in magnetically inhomogeneous samples

A new stimulated echo based pulsed gradient spin-echo sequence, MAG-PGSTE, has been developed for the determination of self-diffusion in magnetically inhomogeneous samples. The sequence was tested on two glass bead samples (i.e., 212-300 and <106 microm glass bead packs). The MAG-PGSTE sequence was compared to the MAGSTE (or MPFG) (P.Z. Sun, J.G. Seland, D. Cory, Background gradient suppression in pulsed gradient stimulated echo measurements, J. Magn. Reson. 161 (2003) 168-173; P.Z. Sun, S.A. Smith, J. Zhou, Analysis of the magic asymmetric gradient stimulated echo sequence with shaped gradients, J. Magn. Reson. 171 (2004) 324-329; P.Z. Sun, Improved diffusion measurement in heterogeneous systems using the magic asymmetric gradient stimulated echo (MAGSTE) technique, J. Magn. Reson. 187 (2007) 177-183; P. Galvosas, F. Stallmach, J. K?rger, Background gradient suppression in stimulated echo NMR diffusion studies using magic pulsed field gradient ratios, J. Magn. Reson. 166 (2004) 164-173, P. Galvosas, PFG NMR-Diffusionsuntersuchungen mit ultra-hohen gepulsten magnetischen Feldgradienten an mikropor?sen Materialien, Ph.D. Thesis, Universit?t Leipzig, 2003, P.Z. Sun, Nuclear Magnetic Resonance Microscopy and Diffusion, Ph.D. Thesis, Massachusetts Institute of Technology, 2003] sequence and Cotts 13-interval [R.M. Cotts, M.J.R. Hoch, T. Sun, J.T. Marker, Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems, J. Magn. Reson. 83 (1989) 252-266] sequence using both glass bead samples. The MAG-PGSTE and MAGSTE (or MPFG) sequences outperformed the Cotts 13-interval sequence in the measurement of diffusion coefficients; more interestingly, for the sample with higher background gradients (i.e., the <106 microm glass bead sample), the MAG-PGSTE sequence provided higher signal-to-noise ratios and thus better diffusion measurements than the MAGSTE and Cotts 13-interval sequences. In addition, the MAG-PGSTE sequence provided good characterization of the surface-to-volume ratio for the glass bead samples.     

Spectral simulations incorporating gradient coherence selection.

Computer-aided methods can considerably simplify the use of the product operator formalism for theoretical analysis of NMR phenomena, which otherwise becomes unwieldy for anything but simple spin systems and pulse sequences. In this report, two previously available programming approaches using symbolic algebra (J. Shriver, Concepts Magn. Reson. 4, 1-33, 1992) and numerical simulation using object-oriented programming (S. A. Smith, T. O. Levante, B. H. Meier, and R. R. Ernst, J. Magn. Reson. A 106, 75-105, 1994) have been extended to include the use of gradient operators for simulation of spatially localized NMR spectroscopy and gradient coherence selection. These methods are demonstrated using an analysis of the response of an AX(3) spin system to the STEAM pulse sequence and verified with experimental measurements on lactate.     

NMR investigation of the organic conductor λ-(BETS)2FeCl4

The two-dimensional organic conductor λ-(BETS)₂FeCl₄ has an unusual phase diagram as a function of temperature and magnetic field that includes a paramagnetic metal (PM) phase, an antiferromagnetic insulating (AFI) phase, and a field-induced superconducting phase (S. Uji, H. Kobayashi, L. Balicas, J. S. Brooks: Adv. Mater. 14: 243, 2002). Here, we report a preliminary investigation of the PM and AFI phases at 9 T over the temperature range of 2.0–180 K that uses proton nuclear magnetic resonance measurements of the spectrum, the spin-lattice relaxation rate 1/T ₁, and the spin echo decay rate 1/T ₂. The sample is a small single crystal whose mass is about 3 μg (approximately 2·10¹⁶ protons). Its small size creates several challenges that include detecting small signals and excluding parasitic proton signals that are not from the sample (H. N. Bachman, I. F. Silvera: J. Magn. Reson. 162: 417, 2003). These strategies and other techniques used to obtain viable signals are described.     

A short note on orientation selection in the DEER experiments on a native cofactor and a spin label in the reaction center ofRhodobacter sphaeroides

The analysis of the two-frequency pulsed electron paramagnetic resonance (EPR) (double electron-electron spin resonance, DEER) investigation on the coupling between the semiquinone anion state of the primary acceptor (Q_A) and the spin label at the cysteine 156 in the H-subunit in the photosynthetic reaction center (RC) fromRhodobacter sphaerodes (R26) (I. V. Borovykh, S. Ceola, P. Gajula, P. Gast, H. J. Steinhoff, M. Huber: J. Magn. Reson. 180, 178–185, 2006) is reinvestigated to include orientation selection. The combination of the EPR properties of the two radicals and the pump and observer frequencies suggests that such an effect could play a role even at the X-band (9 GHz) EPR fields and frequencies employed. The magnitude of the effect is estimated from the structures obtained from the molecular-dynamics (MD) simulations from the previous study: the distance change is small (around 2%) and the distance of 3.05 nm obtained then is possibly underestimated by 0.06 nm. Thus, the difference of at least 0.2 nm between the measured distance and the average distance of 2.8 nm found by the MD simulation remains, suggesting a significant difference between the measurement and the X-ray structure of the RC, as discussed previously.     

Comparative Studies of Phase-Cycling Schemes for Multiple π-Pulse Sequences

Recently, a new phase cycling scheme was introduced by this laboratory for use in biological solid-state NMR experiments involving multiple π-pulses with characteristics that suggested it may enhance the sensitivity of these kind of experiments (Y. Li and J. N. S. Evans, 1995,Chem. Phys. Lett.241,79 and Erratum, 1995,ibid.246,527; Y. Li and J. N. S. Evans, 1996,J. Magn. Reson. B111,296). The new sequence followed the supercycled concept proposed a decade ago for heteronuclear decoupling experiments. In this paper, more detailed experiments demonstrate that the claim of enhanced sensitivity was unfounded, and in fact the supercycle proposed differs little from the established XY-8 and XY-16 based supercycles.     

Conformational Equilibria in Polypeptides. II. Dihedral-Angle Distribution in Antamanide Based on Three-Bond Coupling Information

The use of³Jcoupling information in deriving dihedral-angle restraints for polypeptide-structure determination in the presence of conformational equilibria is illustrated withantamanide,cyclo(–Val¹–Pro²– Pro³– Ala⁴– Phe⁵– Phe⁶– Pro⁷– Pro⁸– Phe⁹– Phe¹⁰–). The experimental basis comprises accurate three-bond coupling constants as obtained from both homonuclear [C. Griesinger, O. W. Sørensen, and R. R. Ernst,J. Magn. Reson.75,474 (1987)] and heteronuclear [J. M. Schmidt,J. Magn. Reson.124,298 (1997)] exclusive correlation spectroscopy (E.COSY). For the backbone and side-chain dihedral angles in the nonproline residues, φ and χ₁, respectively, probability-distribution functions are derived and evaluated on the basis of χ²statistics and significance estimates. Various motional models are considered in the quantitative compilation of molecular-geometry parameters from spin-system parameters. From the³Jcoupling analysis, antamanide is found to possess a very flexible structure which is consistent with the results previously obtained in homonuclear NOE and¹³C–T₁relaxation studies. To fully agree with experiment, rotamer equilibria must be assumed for almost all of the torsions investigated in the peptide.     

Comment on “A new model of charge transfer during ice–ice collisions”: [C. R. Physique 3 (2002) 1293–1303]

A model which proposes modifications of a theory of collisional charging of ice is criticized. To cite this article: J.G. Dash, J.S. Wettlaufer, C. R. Physique 4 (2003).     

Magnetic resonance imaging of rigid polymers at elevated temperatures with SPRITE

Magnetic resonance imaging has rarely been applied to rigid polymeric materials, due primarily to the strong dipolar coupling and short signal lifetimes inherent in these materials. SPRITE (single point ramped imaging withT ₁ enhancement) (B. J. Balcom, R. P. MacGregor, S. D. Beyea, D. P. Green, R. L. Armstrong, T. W. Bremner: J. Magn. Reson. A123, 131–134, 1996) is particularly well suited to imaging solid materials. With SPRITE, the only requirement is thatT ₂^* be long enough so that the signal can be phase-encoded. The minimum phase encoding time is limited by the maximum gradient strength available and by the instrument deadtime. At present this is usually tens of microseconds and will only improve with refinements in technology. We have used the SPRITE sequence in conjunction with raising the sample temperature to obtain images of rigid polymers that have largely frustrated conventional imaging methods. This approach provides a straightforward and reliable method for imaging a class of samples that, up until now, have been very difficult to image.     

Random packing models for amorphous binary alloys

Arthur Nowick's research on amorphous alloys, with S. R. Mader and others at the IBM Thomas J. Watson Research Center, during the period 1963–1967, was important in motivating research in this field during the following three decades. This paper illustrates the development of random packing models for binary amorphous alloys following the 1965 paper by A. S. Nowick and S. R. Mader, “A hard-sphere model to simulate alloy thin films” [IBM J. Res. Dev.9, 358 (1965)].     

Accurate Measurements of Multiple-Bond C–H Coupling Constants from Phase-Sensitive 2D INEPT Spectra

Measurements of multiple-bond ¹³C–¹H coupling constants are of great interest for the assignment of nonprotonated ¹³C resonances and the elucidation of molecular conformation in solution. Usually, the heteronuclear multiple-bond coupling constants were measured either by the J_CH splittings mostly in selective 2D spectra or in 3D spectra, which are time consuming, or by the cross peak intensity analysis in 2D quantitative heteronuclear J correlation spectra (1994, G. Zhu, A. Renwick, and A. Bax, J. Magn. Reson. A 110, 257; 1994, A. Bax, G. W. Vuister, S. Grzesiek, F. Delaglio, A. C. Wang, R. Tschudin, and G. Zhu, Methods Enzymol. 239, 79.), which suffer from the accuracy problem caused by the signal-to-noise ratio and the nonpure absorptive peak patterns. Concerted incrementation of the duration for developing proton antiphase magnetization with respect to carbon-13 and the evolution time for proton chemical shift in different steps in a modified INEPT pulse sequence provides a new method for accurate measurements of heteronuclear multiple-bond coupling constants in a single 2D experiment.     

Multidimensional optimization of structural changes of molecules upon lonization in Franck-Condon factor calculations

Two different iterative methods, namely, the conjugate gradients method and the pattern search method, are applied to Franck-Condon factor calculations using the Coon et al. method (J. B. Coon, R. E. DeWames, and C. M. Loyd, J. Mol. Spectrosc.8, 235–299 (1962)) and the generating function method (T. E. Sharp and H. M. Rosenstock, J. Chem. Phys.41, 3453–3463 (1964); R. Botter, V. H. Dibeler, J. A. Walker, and H. M. Rosenstock, J. Chem. Phys.44, 1271–1278 (1966)). In such treatment, either the changes in normal coordinates or the changes in internal symmetry displacement coordinates are refined automatically until the weighted sum of square deviation between the calculated and the observed Franck-Condon factors is minimized. Some properties of the methods used are given and their applications to several cases are discussed in detail.     

HD structural isotope effect in hydrogen-bonded 2-aminoethanol

The microwave spectra of the d₃ species of intramolecularly hydrogen-bonded 2-aminoethanol (ODCH₂CH₂ND₂) as well as the d₃-O¹⁸, d₃-N¹⁵ and three d₂ isotopic forms have been studied. The r_s O-(D)?N distance of 2.8027(5) Å in the d₃ species is 0.0058(7) Å shorter than the O-(H)?N distance found earlier for the d₀ species (R. E. Penn and R. F. Curl, Jr., J. Chem. Phys.55, 651–658 (1971)). The anomalous r_s structural parameters $\text{r}\text{OH = 1.14}\text{A}\text{?}$ and ∠COH = 103.7°, when corrected for the systematic error caused by the O?N “shrinkage” upon deuteration, become 1.00 Å and 108°, respectively.     

Spin Echo Analysis of Restricted Diffusion under Generalized Gradient Waveforms: Planar, Cylindrical, and Spherical Pores with Wall Relaxivity

A simple matrix formalism presented by Callaghan [J. Magn. Reson.129, 74–84 (1997)], and based on the multiple propagator approach of Caprihanet al.[J. Magn. Reson. A118, 94–102 (1996)], allows for the calculation of the echo attenuation,E(q), in spin echo diffusion experiments, for practically all gradient waveforms. We have extended the method to the treatment of restricted diffusion in parallel plate, cylindrical, and spherical geometries, including the effects of fluid–surface interactions. In particular, theq-space coherence curves are presented for the finite-width gradient pulse PGSE experiment and the results of the matrix calculations compare precisely with published computer simulations. It is shown that the use of long gradient pulses (δ a²/D) create the illusion of smaller pores if a narrow pulse approximation is assumed, while ignoring the presence of significant wall relaxation can lead to both an underestimation of the pore dimensions and a misidentification of the pore geometry.