Liangjie Lin

Partial homogeneity based high-resolution nuclear magnetic resonance spectra under inhomogeneous magnetic fields

In nuclear magnetic resonance (NMR) technique, it is of great necessity and importance to obtain high-resolution spectra, especially under inhomogeneous magnetic fields. In this study, a method based on partial homogeneity is proposed for retrieving high-resolution one-dimensional NMR spectra under inhomogeneous fields. Signals from series of small voxels, which characterize high resolution due to small sizes, are recorded simultaneously. Then, an inhomogeneity correction algorithm is developed based on pattern recognition to correct the influence brought by field inhomogeneity automatically, thus yielding high-resolution information. Experiments on chemical solutions and fish spawn were carried out to demonstrate the performance of the proposed method. The proposed method serves as a single radiofrequency pulse high-resolution NMR spectroscopy under inhomogeneous fields and may provide an alternative of obtaining high-resolution spectra of in vivo living systems or chemical-reaction systems, where performances of conventional techniques are usually degenerated by field inhomogeneity.

Measuring JHH values with a selective constant-time 2D NMR protocol

Proton-proton scalar couplings play important roles in molecule structure elucidation. However, measurements of JHH values in complex coupled spin systems remain challenging. In this study, we develop a selective constant-time (SECT) 2D NMR protocol with which scalar coupling networks involving chosen protons can be revealed, and corresponding JHH values can be measured through doublets along the F1 dimension. All JHH values within a network of n fully coupled protons can be separately determined with (n-1) SECT experiments. Additionally, the proposed pulse sequence possesses satisfactory sensitivity and handy implementation. Therefore, it will interest scientists who intend to address structural analyzes of molecules with overcrowded spectra, and may greatly facilitate the applications of scalar-coupling constants in molecule structure studies.

A simultaneous multi-slice selective J-resolved experiment for fully resolved scalar coupling information

Proton-proton scalar coupling plays an important role in molecular structure elucidation. Many methods have been proposed for revealing scalar coupling networks involving chosen protons. However, determining all JHH values within a fully coupled network remains as a tedious process. Here, we propose a method termed as simultaneous multi-slice selective J-resolved spectroscopy (SMS-SEJRES) for simultaneously measuring JHH values out of all coupling networks in a sample within one experiment. In this work, gradient-encoded selective refocusing, PSYCHE decoupling and echo planar spectroscopic imaging (EPSI) detection module are adopted, resulting in different selective J-edited spectra extracted from different spatial positions. The proposed pulse sequence can facilitate the analysis of molecular structures. Therefore, it will interest scientists who would like to efficiently address the structural analysis of molecules.

Discrete decoding based ultrafast multidimensional nuclear magnetic resonance spectroscopy.

The three-dimensional (3D) nuclear magnetic resonance (NMR) spectroscopy constitutes an important and powerful tool in analyzing chemical and biological systems. However, the abundant 3D information arrives at the expense of long acquisition times lasting hours or even days. Therefore, there has been a continuous interest in developing techniques to accelerate recordings of 3D NMR spectra, among which the ultrafast spatiotemporal encoding technique supplies impressive acquisition speed by compressing a multidimensional spectrum in a single scan. However, it tends to suffer from tradeoffs among spectral widths in different dimensions, which deteriorates in cases of NMR spectroscopy with more dimensions. In this study, the discrete decoding is proposed to liberate the ultrafast technique from tradeoffs among spectral widths in different dimensions by focusing decoding on signal-bearing sites. For verifying its feasibility and effectiveness, we utilized the method to generate two different types of 3D spectra. The proposed method is also applicable to cases with more than three dimensions, which, based on the experimental results, may widen applications of the ultrafast technique.

Ultrahigh-Resolution NMR Spectroscopy for Rapid Chemical and Biological Applications in Inhomogeneous Magnetic Fields

NMR spectroscopy is a commonly used analytical technique in practical applications, and its applicability is further promoted by pure chemical shift techniques based on spectral simplification for analyses. Unfortunately, magnetic field inhomogeneity caused by adverse experimental conditions remains an obstacle restricting NMR applications. In this study, we introduce a new NMR method for high-resolution pure shift proton (1H) NMR measurements in inhomogeneous magnetic fields. We demonstrate that the method allows one to perform chemical analyses on complex solutions in deshimmed magnetic fields, to obtain metabolite information on intact biological tissues with intrinsic field inhomogeneities and to achieve in situ electrochemical detection under externally adverse field conditions. This approach is readily implemented on common commercial NMR instruments without field shimming and locking procedures, specialized hardware requirements as well as complicated sample pretreatments. It provides an effective tool for NMR applications to high-resolution chemical and biological measurements under inhomogeneous magnetic field conditions.

High-resolution localized spatiotemporal encoding correlated spectra under inhomogeneous magnetic fields via asymmetrical gradient encoding/decoding.

Applications of conventional localized nuclear magnetic resonance correlated spectroscopy are restrained by long acquisition times and poor performance under inhomogeneous magnetic fields. Here, a method that combines the spatiotemporal encoding technique with the localization technique and implements the encoding and decoding in unison with suitable asymmetrical gradients is proposed to obtain high‐resolution localized correlated spectra under inhomogeneous fields in greatly reduced times. Experiments on phantom solutions prove its insensitivity to linear field inhomogeneities along three orthogonal axes. Moreover, this method is applied to adipose study of marrow tissue with resolution improvements. The proposed method may offer promising perspectives for fast analyses of biological tissues. Copyright

Reverse detection for spectral width improvements in spatially encoded dimensions of ultrafast two‐dimensional NMR spectra

Recently, the spatially encoded technique has been broadly used in the fast analyses of chemical systems and real‐time detections of chemical reactions. In spatially encoded ultrafast 2D spectra, spectral widths and resolution in spatially encoded dimensions are contradictive, leading to the risk of insufficient spectral widths when providing satisfactory resolution values for all resonances. Here, a method named as reverse detection is proposed to improve the spectral width in the spatially encoded dimension. Experimental results show that spectral width improvements are at least twofold with reverse detection solely, and more improvements can be expected along with the gradient‐controlled folding method. The proposed method can be applied to almost any spatially encoded scheme with echo planar spectroscopic imaging—like detection module and may promote wide applications of ultrafast 2D spectroscopy techniques in chemical analyses. Copyright

Accelerating two-dimensional nuclear magnetic resonance correlation spectroscopy via selective coherence transfer

Nuclear magnetic resonance (NMR) spectroscopy serves as an important tool for both qualitative and quantitative analyses of various systems in chemistry, biology, and medicine. However, applications of one-dimensional 1H NMR are often restrained by the presence of severe overlap among different resonances. The advent of two-dimensional (2D) 1H NMR constitutes a promising alternative by extending the crowded resonances into a plane and thereby alleviating the spectral congestions. However, the enhanced ability in discriminating resonances is achieved at the cost of extended experimental duration due to necessity of various scans with progressive delays to construct the indirect dimension. Therefore, in this study, we propose a selective coherence transfer (SECOT) method to accelerate acquisitions of 2D correlation spectroscopy by converting chemical shifts into spatial positions within the effective sample length and then performing an echo planar spectroscopic imaging module to record the spatial and spectral information, which generates 2D correlation spectrum after 2D Fourier transformation. The feasibility and effectiveness of SECOT have been verified by a set of experiments under both homogeneous and inhomogeneous magnetic fields. Moreover, evaluations of SECOT for quantitative analyses are carried out on samples with a series of different concentrations. Based on these experimental results, the SECOT may open important perspectives for fast, accurate, and stable investigations of various chemical systems both qualitatively and quantitatively.

In Situ Monitoring Potential-Dependent Electrochemical Process by Liquid NMR Spectroelectrochemical Determination: A Proof-of-Concept Study

We report the design and the performance of a two-chamber thin-layer electrochemical device for in situ potential-dependent liquid NMR measurement. Liquid NMR spectra, simultaneously recorded with cyclic voltammetry (CV), have been obtained to reveal molecular changes with potentials scanning. As a proof of concept, redox properties of 1,4-benzoquinone based systems have been investigated, and a π dimerization has been identified by combining both in situ and ex situ NMR analyses. This work provides a new approach for spectroelectrochemistry, which will contribute to developing electrochemical NMR (EC-NMR) as an important tool for the analysis of electrochemical process at a molecular level.

Improving spectral resolution in spatial encoding dimension of single-scan nuclear magnetic resonance 2D spin echo correlated spectroscopy

The spatial encoding technique can be used to accelerate the acquisition of multi-dimensional nuclear magnetic resonance spectra. However, with this technique, we have to make trade-offs between the spectral width and the resolution in the spatial encoding dimension (F1 dimension), resulting in the difficulty of covering large spectral widths while preserving acceptable resolutions for spatial encoding spectra. In this study, a selective shifting method is proposed to overcome the aforementioned drawback. This method is capable of narrowing spectral widths and improving spectral resolutions in spatial encoding dimensions by selectively shifting certain peaks in spectra of the ultrafast version of spin echo correlated spectroscopy (UFSECSY). This method can also serve as a powerful tool to obtain high-resolution correlated spectra in inhomogeneous magnetic fields for its resistance to any inhomogeneity in the F1 dimension inherited from UFSECSY. Theoretical derivations and experiments have been carried out to demonstrate performances of the proposed method. Results show that the spectral width in spatial encoding dimension can be reduced by shortening distances between cross peaks and axial peaks with the proposed method and the expected resolution improvement can be achieved. Finally, the shifting-absent spectrum can be recovered readily by post-processing.