Biselective refocusing pulses and the SERF experiment

The SERF experiment is a variant of the homonuclear J-resolved experiment, in which a single coupling constant is measured. It consists of a single chemical shift selective excitation that is followed by a biselective spin echo. Recent articles mention the existence of artefacts in SERF spectra that are supposedly related to pulse imperfections. This article presents a detailed study of the biselective refocusing pulses. It also reports a method for predicting the position and amplitude of the expected and unexpected 2D spectral peaks in SERF spectra. Artefacts can be partially eliminated by phase cycling or by the introduction of static field gradient pulses in the acquisition sequence. A procedure to obtain of pure absorption peaks in SERF spectra is proposed.     

Selective refocusing pulses in magic-angle spinning NMR: characterization and applications to multi-dimensional protein spectroscopy

Band-selective pulses are frequently used in multi-dimensional NMR in solution, but have been used relatively less often in solid-state NMR applications because of the complications imposed by magic-angle spinning. In this work, we examine the frequency profiles and the refocusing efficiency of several commonly employed selective general rotation pi pulses through experiments and numerical simulations. We demonstrate that highly efficient refocusing of transverse magnetization can be achieved, with experiments that agree well with numerical simulations. We also show that the rotational echo is shifted by a half rotor period if a selective pulse is applied over an integer number of rotor periods. Appropriately synchronizing indirect evolution periods with selective pulses ensures proper phasing of cross peaks in 2D spectra. The improved performance of selective pulses in multi-dimensional protein spectroscopy is demonstrated on the 56-residue beta1 immunoglobulin binding domain of protein G (GB1).     

LR-CAHSQC: an application of a Carr-Purcell-Meiboom-Gill-type sequence to heteronuclear multiple bond correlation spectroscopy

A new pulse sequence, long-range CPMG-adjusted heteronuclear single quantum coherence (LR-CAHSQC), is proposed for the determination of long-range JCH coupling constants from a long-range 1H-13C correlation experiment. The long-range heteronuclear coupling constants can be directly extracted from COSY-type antiphase peak patterns. The current approach utilizes CPMG-sequences for polarization transfer, and thus avoids the evolution of homonuclear JHH couplings, which normally may introduce abnormalities into the cross peak pattern. The differences between LR-CAHSQC and normal LR-HSQC are discussed.     

The generating functions formalism for the analysis of spin response to the periodic trains of RF pulses. Echo sequences with arbitrary refocusing angles and resonance offsets

The generating functions (GF) formalism was applied for calculation of spin density matrix evolution under the influence of periodic trains of RF pulses. It was shown that in a general case, closed expression for the generating function can be found that allows in many cases to derive analytical expressions for the generating function of spin density matrix (magnetization, coherences). This approach was shown to be particularly efficient for the analysis of multi-echo sequences, where one has to average over various frequency isochromats. The explicit analytical expressions for the generating function for echo amplitudes in a Carr–Purcell–Meiboom–Gill (CPMG) echo sequence, a multiecho sequence with incremental phase of refocusing pulse, a gradient echo sequence including transient period were obtained for an arbitrary flip angle and an arbitrary resonance offset. Comparison of the theory and the spin-echo experiments was done, demonstrating a good agreement.     

An analysis of phase-modulated heteronuclear dipolar decoupling sequences in solid-state nuclear magnetic resonance

The design of variants of the swept-frequency two-pulse phase modulation sequence for heteronuclear dipolar decoupling in solid-state NMR is reported, their performance evaluated, and compared with other established sequences like TPPM and SPINAL. Simulations performed to probe the role of the homonuclear (1)H-(1)H bath show that the robustness of the decoupling schemes improves with the size of the bath. In addition, these simulations reveal that the homonuclear (1)H-(1)H bath also leads to broad baselines at high MAS rates. Results from a study of the SPINAL decoupling scheme indicate that optimisation of the starting phase and phase increment improves its performance and efficiency at high MAS rates. Additionally, experiments performed on a liquid crystal display the role of the initial phase in SPINAL-64 and sequences in the SW(f)-TPPM family.     

High resolution heteronuclear correlation NMR spectroscopy between quadrupolar nuclei and protons in the solid state

A high resolution two-dimensional solid state NMR experiment is presented that correlates half-integer quadrupolar spins with protons. In this experiment the quadrupolar nuclei evolve during t1 under a split-t1, FAM-enhanced MQMAS pulse scheme. After each t1 period ending at the MQMAS echo position, single quantum magnetization is transferred, via a cross polarization process in the mixing time, from the quadrupolar nuclei to the protons. High-resolution proton signals are then detected in the t2 time domain during wPMLG5* homonuclear decoupling. The experiment has been demonstrated on a powder sample of sodium citrate and 23Na-1H 2D correlation spectra have been obtained. From the HETCOR spectra and the regular MQMAS spectrum, the three crystallographically inequivalent Na+ sites in the asymmetric unit were assigned. This MQMAS-wPMLG HETCOR pulse sequence can be used for spectral editing of half-integer quadrupolar nuclei coupled to protons.     

The influence of the molecular system on the performance of heteronuclear decoupling in solid-state NMR

The intensity of the carbon signal in a CPMAS experiment has been measured for two CH and three CH(2) moieties in four test molecules under different phase-modulated proton decoupling conditions and as a function of the spinning rate. The proton decoupling schemes investigated were the golden standard TPPM and three of the GTn family. Aim of this analysis was to better describe experimentally the impact and limitations of phase-modulated decoupling. Sizeable differences in the response to decoupling were observed in otherwise chemically identical molecular fragments, such as the CHCH(2) found in tyrosine, phenyl-succinic acid or 9-Anthrylmethyl-malonate, probably due to differences in spin-diffusion rates. In keeping with known facts, the efficiency of the decoupling was observed to decrease with the MAS rate, but with somewhat different trends for the tested systems.     

Application of optimal control to CPMG refocusing pulse design

We apply optimal control theory (OCT) to the design of refocusing pulses suitable for the CPMG sequence that are robust over a wide range of B(0) and B(1) offsets. We also introduce a model, based on recent progress in the analysis of unitary dynamics in the field of quantum information processing (QIP), that describes the multiple refocusing dynamics of the CPMG sequence as a dephasing Pauli channel. This model provides a compact characterization of the consequences and severity of residual pulse errors. We illustrate the methods by considering a specific example of designing and analyzing broadband OCT refocusing pulses of length 10t(180) that are constrained by the maximum instantaneous pulse power. We show that with this refocusing pulse, the CPMG sequence can refocus over 98% of magnetization for resonance offsets up to 3.2 times the maximum RF amplitude, even in the presence of ±10% RF inhomogeneity.     

Quantitative analysis of Earth’s field NMR spectra of strongly-coupled heteronuclear systems

In the Earth’s magnetic field, it is possible to observe spin systems consisting of unlike spins that exhibit strongly coupled second-order NMR spectra. Such spectra result when the J-coupling between two unlike spins is of the same order of magnitude as the difference in their Larmor precession frequencies. Although the analysis of second-order spectra involving only spin-½ nuclei has been discussed since the early days of NMR spectroscopy, NMR spectra involving spin-½ nuclei and quadrupolar (I > ½) nuclei have rarely been treated. Two examples are presented here, the tetrahydroborate anion, , and the ammonium cation, . For the tetrahydroborate anion, ¹J(¹¹B,¹H) = 80.9 Hz, and in an Earth’s field of 53.3 μT, ν(¹H) = 2269 Hz and ν(¹¹B) = 728 Hz. The ¹H NMR spectra exhibit features that both first- and second-order perturbation theory are unable to reproduce. On the other hand, second-order perturbation theory adequately describes ¹H NMR spectra of the ammonium anion, , where ¹J(¹⁴N,¹H) = 52.75 Hz when ν(¹H) = 2269 Hz and ν(¹⁴N) = 164 Hz. Contrary to an early report, we find that the ¹H NMR spectra are independent of the sign of ¹J(¹⁴N,¹H). Exact analysis of two-spin systems consisting of quadrupolar nuclei and spin-½ nuclei are also discussed.     

The influence of the radiofrequency excitation and conversion pulses on the lineshapes and intensities of the triple-quantum MAS NMR spectra of I = 3/2 nuclei

A rigorous examination of the various multiple-quantum magic angle spinning sequences is carried out with reference to sensitivity enhancement in the isotropic dimension and the lineshapes of the corresponding MAS peaks in the anisotropic dimension. An echo efficiency parameter is defined here, which is shown to be an indicator of the performance aspects of the various sequences. This can be used in the design of further new experiments in this field. A consequence of such a systematic analysis has been the combination of a spin-lock pulse for excitation of multiple-quantum coherences and an amplitude-modulated pulse for their conversion to observable single-quantum coherences. This approach has resulted in an improved performance over other sequences with respect to both the anisotropic lineshapes and the isotropic intensities.     

Double-quantum biased covariance spectroscopy: application to the 2D INADEQUATE experiment

A novel processing scheme is presented that converts a two-dimensional double-quantum NMR spectrum into a single-quantum correlation spectrum. The covariance-like spectrum is computed from the 2D Fourier transform spectrum by emphasizing contributions that fulfill the double-quantum condition resulting in a symmetric spectrum that is easier to analyze. The method is demonstrated for the 2D INADEQUATE experiment.     

Unusual Hindered Rotation of an Unsubstituted Phenyl Group. Variable Temperature 1H NMR Studies and Preliminary 13C Assignments in Ketazolam

An unusual hindered rotation of an unsubstituted phenyl group in the drug, ketazolam, has been found at ambient temperature. Variable temperature lH NMR has been employed to examine the two- fold rotation about the C(sp²)-C(sp³) bond. Chemical shift as- signments of the IH NMR spectra and partial assignments of the ¹³C spectra are supported by off-resonance decoupling, gated decou- pling, and low temperature 2D ^l3C-¹H heteronuclear chemical shift correlation experiments at 200.1 MHz for IH and 50.3 MHz for ¹³C.     

建筑物对微波脉冲响应仿真与实验

建立了微波脉冲在建筑物内传播、反射及透射过程的3维仿真模型,提取了空间电场时域最大值进行统计分析。分析表明：不同入射角窄带调制方波脉冲激励下,场增强区域大小与微波通过窗户和门能直接照射到的区域大小呈正比,窗户的大小对建筑物内空间场强增强区域的大小有显著影响;同时在微波脉冲的传播方向上,窗沿后的区域场强幅值明显减小;脉冲宽度对建筑物内空间场强增强区域的大小及空间场强最大值影响很小;无上升下降沿的窄带调制方波脉冲激励下,空间电场叠加增强效应更强。测量了微波脉冲辐照下,建筑物内空间功率密度分布,验证了仿真结果。     

A new method for suppressing the central transition in I=3/2 NMR spectra with a demonstration for 23Na in bovine articular cartilage

The splitting and the lineshape of the satellite transitions of 23Na are measures of the residual quadrupolar interaction and its distribution, which are related to the degrees of order and binding of sodium in biological tissues. However, these transitions are often masked by the stronger signals of the central transition and the isotropic sodium ions. A way to suppress the central signals, while preserving the lineshape and the intensity of the satellites, is suggested and tested on a liquid crystal and on bovine articular cartilage.     

Assignment of 13C Resonances in the Phencyclone-Norbornadiene Adduct Via 2D NMR. 13C Evidence for Hindered Rotation of Unsubstituted Bridgehead Phenyl Rings

¹³C NMR chemical shift assignments were obtained for the Diels-Alder adduct of phencyclone with norbornadiene in CD₂Cl₂ and in CDCl₃ solution. The ¹³C spectrum at 50.3 MHz, as well as the ¹H spectrum at 200.1 MHz, show evidence for hindered rotation of the two unsubstituted bridgehead phenyl rings of the adduct at ambient temperatures. In CD₂Cl₂ solution, all 19 of the unique ¹³C nuclei of this molecule give rise to individual ¹³C resonances. The ¹H assignments which were made earlier, together with one-bond and long-range 2D heteronuclear correlation experiments, allowed the assignment of all ¹³C chemical shifts in the molecule.     

Two-dimensional NMR correlation experiments in the gas phase

The application of common two-dimensional NMR correlation experiments to gaseous analytes for structural elucidation is reported. Standard sequences such as COSY, HSQC, and HMBC are readily applied to volatile hydrocarbons and fluorocarbons. In experiments using (19)F or (13)C as the observed nucleus, it is possible to take advantage of efficient spin-rotation relaxation to perform common experiments swiftly (a (19)F COSY acquired in 6s is shown) or to render insensitive experiments possible on a practical timescale (e.g. a gas phase INADEQUATE at natural isotopic abundance in 14h). NOE-based experiments were not successful on the gaseous systems studied.     

Classification of Raman spectra using the correlation kernel

The classification of Raman spectra can be very useful in a wide range of diagnostic applications including bacterial identification. Before any form of classification can be carried out on the Raman spectra, some form of pre‐processing is commonly applied. This pre‐processing greatly affects the accuracy of the results and introduces user bias and over‐fitting effects. In this paper, we propose using support vector machines with the correlation kernel. The use of the correlation kernel on Raman spectra has not been presented before in any published work. Our results illustrate that the correlation kernel is ‘self‐normalizing’ and produces superior classification performance with minimal pre‐processing, even on highly noisy data obtained using inexpensive equipment. Such effective classification approaches can lead to clinically valuable diagnostic applications of Raman Spectroscopy. Copyright © 2010 John Wiley & Sons, Ltd.