利用对称位移脉冲改善分辨率-IMPRESS HMBC

众所周知异核二维实验在中、小分子的结构确定中非常重要. 例如¹H与¹³C/¹⁵N异核远程相关无疑是连接分子中孤立结构碎片及季碳的最有利的工具. 然而，在间接检测的异核二维实验中，间接检测域-异核维的太低分辨率一直是困扰着化学家的主要问题. 过去在有限的采样时间内提高分辨率的方法主要有线性预测、带选择脉冲和控制好的折叠3种方法. 文中介绍一种最新开发出的利用Hadamard激发雕刻的方法. 借助Varian核磁共振系统的高品质射频系统和灵活的软件工具, 用户可以方便的实施新的激发雕 刻方案，极大地改善gHMBC实验的F₁分辨率.     

Improved resolution using symmetrically shifted pulses.

An approach to Hadamard phase encode the two halves of the F(1) dimension of a gHSQC experiment is presented. The phase encoding is achieved by excitation sculpting of the F(1) dimension using symmetrically shifted pulses. This approach (IMPRESS-improved resolution using symmetrically shifted pulses) increases the resolution of the F(1) dimension by exploiting spectral folding, but the folding is coded in the fashion of a Hadamard H(2) matrix. Editing of the IMPRESS spectra during processing sorts out spectral crowding which is a typical consequence of F(1) spectral folding. It is shown that for the same total experiment time, the IMPRESS-gHSQC experiment provides narrower peaks along the F(1) dimension compared to the normal gHSQC experiment. As a consequence of decreased linewidth, the peak height (sensitivity) is also increased.     

Localised two-dimensional correlated spectroscopy based on Hadamard encoding technique

A new pulse sequence based on Hadamard encoding technique, dubbed as Hadamard encoded localised correlation spectroscopy (HLCOSY) was devised to speed up the acquisition of localised two-dimensional (2D) nuclear magnetic resonance (NMR) correlation spectroscopy (LCOSY). Direct frequency-domain (F2) excitation with an array of different radiofrequencies has been used to speed up 2D NMR experiments by a large factor. Multiplex excitation in the indirect frequency (F1) dimension is restricted to the signal-bearing regions and is encoded according to a Hadamard matrix of order N, where N is a relatively small number. The detected signals are decoded by reference to the same Hadamard matrix. An HLCOSY spectrum of a two-compartment phantom was obtained with a total acquisition time of 32 s, with its volume localisation confirmed. The success in achieving 2D LCOSY spectrum of pig marrow within 40 s shows the feasibility of HLCOSY for the detection of biological tissues. It may provide a promising way for in vivo and in vitro NMRs.     

Extending the excitation sculpting concept for selective excitation

Nowadays, excitation sculpting is probably the most efficient way to achieve selectivity in an NMR experiment, since it associates very clean frequency selection with "user-friendliness." In the present report, it is shown that the excitation sculpting concept, originally based on a double pulse field gradient echo acting on a selected transverse magnetization, can be extended through new experiments designed to act on longitudinal magnetization. This leads to outstanding performances, especially when the transverse relaxation rate is a limiting factor as, for example, in the case of biological macromolecules. Several new sequences are proposed, aiming at the selection of magnetization aligned either/both on a transverse axis or/and on the z-axis. Their potentialities are illustrated in light of different applications including multiplet-selective excitation, band-selective excitation, and water suppression.     

中国南海海绵中19-methoxy-scalarin立体构型的确定

对中国南海海绵中的新化合物19-methoxy-scalarin进行¹H和¹³C NMR谱的全归属, 并运用“激发雕刻”技术,利用1D GOESY实验确定该化合物立体构型。实验结果亦表明1D GOESY实验选择性好,提供的信息更加直观、清晰,是化合物立体结构确定的好方法。     

Hadamard NMR spectroscopy in solids

The duration of 2D and 3D NMR experiments in solids can be reduced by several orders of magnitude by using frequency domain Hadamard encoding with long selective pulses. We demonstrate Hadamard encoded experiments in (13)C enriched solids samples. To avoid multiple quantum interferences, the Hadamard encoding pulses are applied sequentially rather than simultaneously in this study. Among other possible applications, dipolar assisted rotational resonance experiments and measurement of NOESY type build-up rates in proton driven spin diffusion are demonstrated.     

阿达玛变换在核磁共振成象中的应用

阿达玛变换应用到核磁共振成象技术中,能提高成象技术的灵敏度。本文阐述了阿达玛变换在线扫描核磁共振成象中应用原理,推出了合成的激发信号相位与阿达玛编码关系。得到频率合成的激发信号相位表,据该表合成的激发信号产生多个自旋回波,能使核磁共振成象技术速度快、灵敏度高。文中还对该方法作了深入的讨论。     

Two-dimensional Hadamard spectroscopy

Direct frequency-domain excitation of NMR with an array of different radiofrequencies has been used to speed up two-dimensional NMR experiments by a large factor. Multiplex excitation in the F(1) frequency dimension is restricted to the signal-bearing regions and is encoded according to a Hadamard matrix of dimension N by N, where N is a relatively small number. The detected signals are decoded by reference to the same Hadamard matrix. Alternatively a phase-encoding scheme can be employed. Two-dimensional correlation experiments (COSY and TOCSY) and cross-relaxation measurements (NOESY) implemented on proton systems can be completed in less than a minute in cases where the intrinsic sensitivity is sufficiently high that prolonged multiscan averaging is not required. The results are presented in the form of a high-resolution contour diagram similar to the familiar two-dimensional spectra obtained by Fourier transform methods. Experiments on strychnine demonstrate more than two orders of magnitude improvement in speed compared with the traditional methods.     

SOGGY: solvent-optimized double gradient spectroscopy for water suppression. A comparison with some existing techniques

Excitation sculpting, a general method to suppress unwanted magnetization while controlling the phase of the retained signal [T.L. Hwang, A.J. Shaka, Water suppression that works. Excitation sculpting using arbitrary waveforms and pulsed field gradients, J. Magn. Reson. Ser. A 112 (1995) 275-279] is a highly effective method of water suppression for both biological and small molecule NMR spectroscopy. In excitation sculpting, a double pulsed field gradient spin echo forms the core of the sequence and pairing a low-power soft 180 degrees (-x) pulse with a high-power 180 degrees (x) all resonances except the water are flipped and retained, while the water peak is attenuated. By replacing the hard 180 degrees pulse in the double echo with a new phase-alternating composite pulse, broadband and adjustable excitation of large bandwidths with simultaneous high water suppression is obtained. This "Solvent-Optimized Gradient-Gradient Spectroscopy" (SOGGY) sequence is a reliable workhorse method for a wide range of practical situations in NMR spectroscopy, optimizing both solute sensitivity and water suppression.     

Methods of reconstruction of spectra in multidimensional NMR spectroscopy

In this review, some methods for speeding up the performance of multidimensional nuclear magnetic resonance (NMR) experiments are discussed. It is shown that, at a sufficiently high spectral sensitivity, which does not require multiple scanning with averaging, two-dimensional proton-correlation experiments (COSY and TOCSY) can be performed in less than one minute. A multifold decrease in the time of multidimensional experiments can be achieved by various methods, for example, by the direct excitation of resonance signals with a set of different frequencies obtained using the Hadamard matrix. Methods for reconstructing multidimensional NMR spectra based on the inverse Radon transform and a number of other promising methods are also considered     

Spectral unraveling by space-selective Hadamard spectroscopy

Spectral unraveling by space-selective Hadamard spectroscopy (SUSHY) enables recording of NMR spectra of multiple samples loaded in multiple sample tubes in a modified spinner turbine and a regular 5mm liquids NMR probe equipped with a tri-axis pulsed field gradient coil. The individual spectrum from each sample is extracted by adding and subtracting data that are simultaneously obtained from all the tubes based on the principles of spatially resolved Hadamard spectroscopy. The well-known Hadamard spectroscopy has been applied for spatial selection and the method utilizes standard configuration of NMR instrument hardware. The SUSHY method can be easily incorporated in multi-dimensional multi-tube NMR experiments. This method combines the excitation multiplexing, natural advantage of FTNMR, and sample multiplexing and offers high-throughput by reducing the total experimental time by up to a factor of four in a 4-tube mode.     

Band-Selective HSQC and HMBC Experiments Using Excitation Sculpting and PFGSE

Variants of the HSQC and HMBC experiments are described. They allow the restriction of the heteronuclear chemical shift domain without causing spectral folding. Selectivity is introduced in the HSQC experiment by means of excitation sculpting. The selective element of the pulse sequence is a double pulsed field gradient spin echo. It may be used either split by the t(1) evolution period, or not. The selectivity profile depends on the scheme used as well as on the number of protons attached to the heteronucleus. The selective HMBC experiment requires only a single echo sequence as no strict control of the signal phase is required. A complex glycoconjugate is used as a test compound for the new pulse sequences.     

Features of temporal noise spatial localization while indexing in accordance with the 2D hadamard transform

It is shown that the 2D indexation of a communication channel 1D noise with the help of the 2D Hadamard transform makes it possible to represent the distribution of this noise in the restored image space in the form of a 2D distribution of its variance. The width of noise variance distribution depends on the extent of preservation of correlation between elements of communication channel 1D noise. It is shown that the degree of 2D spatial localization of noise in this case exceeds the degree of noise localization in the case when 1D Hadamard transform is used.     

A simple scheme for the design of solvent-suppression pulses

Excitation sculpting was first introduced as a way to efficiently suppress solvent signals. It requires a pulse sequence that acts as a null pulse at the solvent-resonance frequency and as an inversion pulse everywhere else. In this article, it is shown that such a goal can be achieved starting with "top-hat" inversion shaped pulses such as I-BURP-2 or gaussian cascade G3. The result is a Globally Antisymmetric Selective Pulse, or GASP. Numerical optimization was used to extend the performance of such pulses. Multifrequency signal suppression was shown to be possible through application of successive excitation sculpting modules.     

Stochastic excitation and Hadamard correlation spectroscopy with bandwidth extension in RF FT-EPR

The application of correlation spectroscopy employing stochastic excitation and the Hadamard transform to time-domain Fourier transform electron paramagnetic resonance (FT-EPR) spectroscopy in the radiofrequency (RF) band is described. An existing, time-domain FT-EPR spectrometer system with a Larmor frequency (L(f)) of 300 MHz was used to develop this technique by incorporating a pseudo-random pulse sequence generator to output the maximum length binary sequence (MLBS, 10- and 11-bit). Software developed to control the EPR system setup, acquire the signals, and post process the data, is outlined. The software incorporates the Hadamard transform algorithm to perform the required cross-correlation of the acquired signal and the MLBS after stochastic excitation. To accommodate the EPR signals, bandwidth extension was accomplished by sampling at a rate many times faster than the RF pulse repetition rate, and subsequent digital signal processing of the data. The results of these experiments showed that there was a decrease in the total acquisition time, and an improved free induction decay (FID) signal-to-noise (S/N) ratio compared to the conventional coherent averaging approach. These techniques have the potential to reduce the RF pulse power to the levels used in continuous wave (CW) EPR while retaining the advantage of time-domain EPR methods. These methods have the potential to facilitate the progression to in vivo FT-EPR imaging of larger volumes.     

Gradient-Enhanced One-Dimensional Proton Chemical-Shift Correlation with Full Sensitivity

High-quality spectra were obtained by implementing pulsed field gradients (PFGs) as part of 1D selective experiments. The use of PFGs for coherence rejection rather than coherence selection ensures that there is no loss of signal and the sensitivity of these experiments is the same as that of their phase-cycled predecessors. The excitation scheme chosen ensures that these experiments are highly resistant to spin–spin relaxation. The following techniques are described: 1D ge-TOCSY, 1D ge-NOESY, 1D ge-TOCSY–TOCSY, 1D ge-NOESY–NOESY, 1D ge-TOCSY–NOESY, and 1D ge-NOESY–TOCSY. Their applications, for the separation of overlapping spin systems, tracing spin-diffusion signals, and extending the transfer of magnetization beyond an individual spin system, are illustrated using oligo- and polysaccharide samples.     

Unwanted signal leakage in excitation sculpting with single axis gradients

Excitation sculpting (T-L. Hwang and A. J. Shaka, J. Magn. Reson. A 112, 275-279 (1995)) used for solvent suppression and selective excitation in NMR bases its success on the ability to remove baseline and phase errors created by the application of selective rf pulses. This is achieved by the application of two pulsed field gradient (PFG) echoes in sequence. It is essential that the two pairs of PFGs select the coherence transfer steps independently of each other, which is conveniently achieved if they are applied along orthogonal spatial axes. Here, the much more common case where both PFG pairs must be applied along a single axis is investigated. This is shown to lead to complications for certain ratios of PFG strengths. The original theory of excitation sculpting is restated in the spherical basis for convenience. Some of the effects can only be explained by invoking the dipolar demagnetizing field.     

Hadamard NMR spectroscopy for two-dimensional quantum information processing and parallel search algorithms

Hadamard spectroscopy has earlier been used to speed-up multi-dimensional NMR experiments. In this work, we speed-up the two-dimensional quantum computing scheme, by using Hadamard spectroscopy in the indirect dimension, resulting in a scheme which is faster and requires the Fourier transformation only in the direct dimension. Two and three qubit quantum gates are implemented with an extra observer qubit. We also use one-dimensional Hadamard spectroscopy for binary information storage by spatial encoding and implementation of a parallel search algorithm.     

The 'DANTE' experiment

The selective excitation scheme known as ‘DANTE’ emerged from a confluence of several ideas for new NMR experiments, some more fanciful than others. DANTE offers a simple and effective way to restrict excitation to a very narrow frequency band, usually that of a single resonance line. Initially applied to the study of individual proton-coupled carbon-13 spin multiplets, the method has been extended to water presaturation, relaxation measurements, and chemical exchange studies. Through the imposition of a magnetic field gradient it offers a simple method to enhance resolution by restricting the effective volume of the sample. Multiple DANTE excitation (with Hadamard encoding) can speed up multidimensional spectroscopy by orders of magnitude. Applied to magnetic resonance imaging, the DANTE sequence has been used to superimpose a rectangular grid onto a cardiac image, permitting motional distortions to be monitored in real time.     

B1-insensitive Hadamard spectroscopic imaging technique

A B₁-insensitive Hadamard spectroscopic imaging technique for multivolume localization is presented and tested experimentally. This technique can give localized spectroscopic information from n regions of interest by n scans using homogeneous or inhomogeneous coils, such as surface coils. The B₁ insensitivity is achieved by using RF pulses which invert spins adiabatically at several well-defined slices simultaneously. We show how any adiabatic pulse can be modified such that it can invert spins at one or several desired frequency bands simultaneously. With the modified adiabatic pulses, B₁-insensitive Hadamard spectroscopic imaging experiments of any order can be performed.