Pure Shift Research Articles

Downlink Multi-IRS Aided NOMA System With Second-Order Reflection

The performance of non-orthogonal multiple access (NOMA) system can be enhanced by the incorporation of intelligent reflecting surface (IRS), which has the capability of reconfiguring each user’s channel condition according to the demands. In this letter, we aim to design a transmission scheme with low power consumption for downlink multi-IRS assisted NOMA system with the consideration of second-order reflection. To this end, a joint transmit power and phase shift optimization problem is formulated. By leveraging the relationship between the phase shifts and each user’s required transmit power, the joint minimization problem is simplified as a pure phase shift optimization problem. To further address the transformed non-convex problem, a successive phase-rotation method is proposed to determine the phase shifts sequentially. Simulation results show that the proposed scheme performs better than extensive benchmarking schemes in terms of total transmit power.

Present and future of pure shift NMR in metabolomics.

NMR is one of the most powerful techniques for the analysis of biological samples in the field of metabolomics. However, the high complexity of fluids, tissues, or other biological materials taken from living organisms is still a challenge for state-of-the-art pulse sequences, thereby limiting the detection, the identification, and the quantification of metabolites. In this context, the resolution enhancement provided by broadband homonuclear decoupling methods, which allows for simplifying 1 H multiplet patterns into singlets, has placed this so-called pure shift technique as a promising approach to perform metabolic profiling with unparalleled level of detail. In recent years, the many advances achieved in the design of pure shift experiments has paved the way to the analysis of a wide range of biological samples with ultra-high resolution. This review leads the reader from the early days of the main pure shift methods that have been successfully developed over the last decades to address complex samples, to the most recent and promising applications of pure shift NMR to the field of NMR-based metabolomics.

Deep Learning Methodology for Obtaining Ultraclean Pure Shift Proton Nuclear Magnetic Resonance Spectra

Nuclear magnetic resonance (NMR) is one of the most powerful analytical techniques. In order to obtain high-quality NMR spectra, a real-time Zangger-Sterk (ZS) pulse sequence is employed to collect low-quality pure shift NMR data with high efficiency. Then, a neural network named AC-ResNet and a loss function named SM-CDMANE are developed to train a network model. The model with excellent abilities of suppressing noise, reducing line widths, discerning peaks, and removing artifacts is utilized to process the acquired NMR data. The processed spectra with noise and artifact suppression and small line widths are ultraclean and high-resolution. Peaks overlapped heavily can be resolved. Weak peaks, even hidden in the noise, can be discerned from noise. Artifacts, even as high as spectral peaks, can be removed completely while not suppressing peaks. Eliminating perfectly noise and artifacts and smoothing baseline make spectra ultraclean. The proposed methodology would greatly promote various NMR applications.

Shifted homotopy analysis of the linearized higher-spin equations in arbitrary higher-spin background

Analysis of the first-order corrections to higher-spin equations is extended to homotopy operators involving shift parameters with respect to the spinor Y variables, the argument of the higher-spin connection ω(Y) and the argument of the higher-spin zero-form C(Y). It is shown that a relaxed uniform (y + p)-shift and a shift by the argument of ω(Y) respect the proper form of the free higher-spin equations and constitute a one-parametric class of vertices that contains those resulting from the conventional (no shift) homotopy. A pure shift by the argument of ω(Y) is shown not to affect the one-form higher-spin field W in the first order and, hence, the form of the respective vertices.

Primary Structure of Glycans by NMR Spectroscopy.

Glycans, carbohydrate molecules in the realm of biology, are present as biomedically important glycoconjugates and a characteristic aspect is that their structures in many instances are branched. In determining the primary structure of a glycan, the sugar components including the absolute configuration and ring form, anomeric configuration, linkage(s), sequence, and substituents should be elucidated. Solution state NMR spectroscopy offers a unique opportunity to resolve all these aspects at atomic resolution. During the last two decades, advancement of both NMR experiments and spectrometer hardware have made it possible to unravel carbohydrate structure more efficiently. These developments applicable to glycans include, inter alia, NMR experiments that reduce spectral overlap, use selective excitations, record tilted projections of multidimensional spectra, acquire spectra by multiple receivers, utilize polarization by fast-pulsing techniques, concatenate pulse-sequence modules to acquire several spectra in a single measurement, acquire pure shift correlated spectra devoid of scalar couplings, employ stable isotope labeling to efficiently obtain homo- and/or heteronuclear correlations, as well as those that rely on dipolar cross-correlated interactions for sequential information. Refined computer programs for NMR spin simulation and chemical shift prediction aid the structural elucidation of glycans, which are notorious for their limited spectral dispersion. Hardware developments include cryogenically cold probes and dynamic nuclear polarization techniques, both resulting in enhanced sensitivity as well as ultrahigh field NMR spectrometers with a 1H NMR resonance frequency higher than 1 GHz, thus improving resolution of resonances. Taken together, the developments have made and will in the future make it possible to elucidate carbohydrate structure in great detail, thereby forming the basis for understanding of how glycans interact with other molecules.

Recovering sensitivity lost through convection in pure shift NMR.

Practical pure shift NMR experiments, especially on instruments equipped with cryoprobes, can sometimes give very disappointing results. Here we show for the first time that this is a consequence of signal loss due to sample convection, and demonstrate a simple adjustment to common pure shift NMR experiments that restores the lost signal.

Resolving the complexity in human milk oligosaccharides using pure shift NMR methods and CASPER.

Human milk oligosaccharides belong to an important class of bioactive molecules with diverse effects on the development of infants. NMR is capable of providing vital structural information about oligosaccharides which can aid in determining structure-function relationships. However, this information is often concealed by signal overlap in 1H spectra, due to the narrow chemical shift range and signal multiplicity. Signal overlap in oligosaccharide spectra can be greatly reduced, and resolution improved, by utilising pure shift methods. Here the benefits of combining pure shift methods with the CASPER computational approach to resonance assignment in oligosaccharides are demonstrated.

A COLLATERAL APPROACH ON THE 13 C NMR ANALYSIS OF PSEUDOPELLETIERINE, AN ALKALOID FROM POMEGRANATE

We reviewed a subchapter of “Natural Products, Isolation, Structure Elucidation, History” by D. Sicker et al. regarding the study of Pseudopelletierine (9-Methyl-9-azabimiccyclo[3.3.1]nonan-3-one). We boarded the NMR data in the subchapter with didactical purposes, doing an analysis of 13 C NMR chemical shifts in a spectral/structural approach. We established the structure by doing a 13 C NMR “Pure Shift” analysis if the term is worth.

Stress State of the Earth’s Crust, Seismicity, and Prospects for Long-Term Forecast of Strong Earthquakes in Uzbekistan

Abstract —The current stress state of the Earth’s crust on the territory of Uzbekistan is studied using algorithms from the cataclastic analysis of displacements (CAD) with the application of a combined catalog of earthquake source mechanisms. The axis of maximum compression is nearly horizontal and orthogonal to the strike of tectonic structures for the larger part of the area under study, and the angle of penetration of the axis of minimum compression varies greatly for different parts of the territory. The areal distribution of the Lode–Nadai coefficient indicates the predominance of a stress state close to pure shift for the area under study. Without differentiation of the seismically active bed by depth, almost the entire territory of Uzbekistan is characterized by a geodynamic stress state corresponding to horizontal compression. There are significant differences in the stress state parameters for different deep beds of the Earth’s crust. With account for the representative recording periods of seismic events of different energy levels, the earthquake recurrence parameters for the entire territory as a whole and large seismically active zones are determined. It has been established that the epicenters of strong earthquakes recorded since the historical time are grouped in compact areas with linear dimensions of 50–80 km. The tectonophysical interpretation of the selected areas is given within the framework of the CAD, in which it is noted that strong earthquakes occur mainly in areas of lower effective confining pressure and maximum tangent stresses. This is due to the fact that the values of friction forces at faults in such areas are low, which creates the most favorable conditions for large-scale destruction. According to the results of the reconstruction of the natural stresses of the CAD, such areas on the territory of Uzbekistan are identified within faults and flexural-fault zones in South Fergana and North Fergana, as well as in the Gazli region. The current seismological situation in the selected areas of long-term forecast is estimated using a set of prognostic parameters of the seismic regime, and a map of the areas of expected seismic activity is compiled. The analysis of previous forecast maps developed within the framework of the presented approach shows high value in their information.

Analysis of Small-Molecule Mixtures by Super-Resolved 1H NMR Spectroscopy.

Analysis of small molecules is essential to metabolomics, natural products, drug discovery, food technology, and many other areas of interest. Current barriers preclude from identifying the constituent molecules in a mixture as overlapping clusters of NMR lines pose a major challenge in resolving signature frequencies for individual molecules. While homonuclear decoupling techniques produce much simplified pure shift spectra, they often affect sensitivity. Conversion of typical NMR spectra to pure shift spectra by signal processing without a priori knowledge about the coupling patterns is essential for accurate analysis. We developed a super-resolved wavelet packet transform based 1H NMR spectroscopy that can be used in high-throughput studies to reliably decouple individual constituents of small molecule mixtures. We demonstrate the efficacy of the method on the model mixtures of saccharides and amino acids in the presence of significant noise.

Pure shift amide detection in conventional and TROSY-type experiments of 13C,15N-labeled proteins

Large coupling networks in uniformly 13C,15N-labeled biomolecules induce broad multiplets that even in flexible proteins are frequently not recognized as such. The reason is that given multiplets typically consist of a large number of individual resonances that result in a single broad line, in which individual components are no longer resolved. We here introduce a real-time pure shift acquisition scheme for the detection of amide protons which is based on 13C-BIRDr,X. As a result the full homo- and heteronuclear coupling network can be suppressed at low power leading to real singlets at substantially improved resolution and uncompromised sensitivity. The method is tested on a small globular and an intrinsically disordered protein (IDP) where the average spectral resolution is increased by a factor of ~ 2 and higher. Equally important, the approach works without saturation of water magnetization for solvent suppression and exchanging amide protons are not affected by saturation transfer.

Ultrahigh-Resolution Homo- and Heterodecoupled 1H and TOCSY NMR Experiments.

The original homonuclear decoupled (pure shift) experiments provide ultrahigh-resolution 1H spectra of compounds containing NMR-active heteronuclei of low natural isotopic abundance (e.g., 13C or 15N). In contrast, molecules containing highly abundant heteronuclei (like 31P or 19F) give doublets or a multiple of doublets in their homonuclear decoupled spectra, depending on the number of heteronuclear coupling partners and the magnitude of the respective coupling constants. In these cases, the complex and frequently overlapping signals may hamper the unambiguous assignment of resonances. Here, we present new heteronuclear decoupled (HD) PSYCHE 1H and TOCSY experiments, which result in simplified spectra with significantly increased resolution, allowing the reliable assessment of individual resonances. The utility of the experiments has been demonstrated on a challenging stereoisomeric mixture of a platinum-phosphine complex, where ultrahigh resolution of the obtained HD PSYCHE spectra made the structure elucidation of the chiral products feasible. HD PSYCHE methods can be potentially applied to other important 31P- or 19F-containing compounds in medicinal chemistry and metabolomics.

Direct Identification of Zeolite Beta Polymorphs by Solid-State 29Si Nuclear Magnetic Resonance Spectroscopy.

Stacking disorder and polymorphism in zeolite and zeolite-like materials hinder their structural characterization. In this work, we propose an advanced approach based on applying "pure shift" solid-state 29Si nuclear magnetic resonance (NMR) spectroscopy for the structural investigation of zeolitic materials containing intergrown polymorphs. The approach developed in the case study of zeolite beta allows for the resolution of 21 29Si signals, attributing them to non-equivalent T sites in polymorphs A, B, and C, reconstruction of individual 29Si magic angle spinning NMR spectra for each polymorph, and determination of the polymorph composition with higher accuracy than X-ray diffraction. The results reveal that two widely used synthetic routes for zeolite beta, alkaline and fluoride synthesis, lead to different polymorph compositions. These findings indicate that "pure shift" solid-state 29Si NMR can serve as a superior tool for the elucidation of polymorphism in zeolites.

Simultaneous Broadband Suppression of Homonuclear and Heteronuclear Couplings in 1 H NMR Spectroscopy.

The 1 H NMR analysis of species containing NMR-active heteronuclei can be difficult due to signal overlap caused by the combined effects of homonuclear and heteronuclear scalar (J) couplings. Here, a general pure shift method is presented for obtaining ultra-high resolution 1 H NMR spectra where spectral overlap is drastically reduced by suppressing both homonuclear and heteronuclear J-couplings, giving one single signal per 1 H chemical environment. Its usefulness is demonstrated in the analysis of fluorine- and phosphorus-containing compounds of pharmaceutical and biochemical interest.

Absolute Metabolite Quantification Using Pure Shift NMR: Toward Quantitative Metabolic Profiling of Aqueous Biological Samples.

Accurate quantification of metabolites by nuclear magnetic resonance (NMR) is of prime importance in the field of health sciences for understanding the metabolic pathways of the investigated system, to address the mechanisms of action of diseases, and improving their diagnosis, treatment, and prognosis. Unfortunately, the absolute quantitative analysis of complex samples is still limited by sensitivity and resolution issues that are intrinsic to this technique. Ultrahigh-resolution pure shift methods have especially shown to be suitable for interpreting mixtures of metabolites in biological samples. Here, we introduce a robust analytical protocol based on the use of a pure shift library of calibration reference spectra to fit the fingerprint of each metabolite of interest and determine its concentration. The approach based on the SAPPHIRE pulse sequence enhanced with a block for solvent suppression has been validated through the results of a series of model mixtures, exhibiting excellent trueness (slope values in the range of 0.93-1.02) and linearity (R2 > 0.996) in a total time (a few hours) that is fully compatible with metabolomics studies. Furthermore, we have successfully applied our method to determine the absolute metabolite concentrations in a lymphoma extracellular medium, which improves metabolomic protocols reported to date by providing a quantitative and highly resolved vision of metabolic processes at play.

Pure shift NMR and DFT methods for revealing long-range heteronuclear couplings

Determination of dihedral angles from heteronuclear nJHX couplings (where n is 2, 3 or 4 and X stands for 31P, 19F, etc.) is very useful in structure elucidation. It is a challenging task to extract these couplings from 1D 1H NMR spectra due to the presence of a large number of nJHH and nJHX. Herein, we demonstrate the utility of two different pure shift NMR methods wherein 1H–1H multiplets are collapsed into singlets, revealing only nJHX in the spectrum. The benefit of DFT calculations for prediction of these couplings and congruence with their experimental counterparts is also demonstrated.

Giving Pure Shift NMR Spectroscopy a REST─Ultrahigh-Resolution Mixture Analysis.

Most interesting problems in chemistry, biology, and pharmacy involve mixtures. However, analysis of such mixtures by NMR remains a challenge, often requiring the mixture components to be physically separated before analysis. A variety of methods have been proposed that exploit species-specific properties such as diffusion and relaxation to distinguish between the signals of different components in a mixture without the need for laborious separation. However, these methods can struggle to distinguish between components when signals overlap. Here, we exploit the relaxation properties of selected nuclei to distinguish between different components of a mixture while using pure shift methods to increase spectral resolution by up to an order of magnitude, greatly reducing signal overlap. The advantages of the new method are demonstrated in a mixture of d-xylose and l-arabinose, distinguishing unambiguously between the five major species present.

Selective Homodecoupled 1D-1H NMR Experiment for Unravelling Enantiomers.

1H NMR spectroscopy is a quick and easy tool to resolve enantiomers. However, the paradigm of resolution of enantiomers by 1H NMR is a difficult task due to the minor chemical shift differences and overlap of the resonances of the enantiomers. In the current study, we have performed the conventional selective homodecoupling 1D-1H NMR experiment to achieve chiral resolutions. The predominant features of the proposed methods are (a) high sensitivity as opposed to routinely employed pure shift NMR experiments, (b) easy optimization like conventional 1D-1H NMR, and (c) an artifact-free spectrum. The application of the method has been exhibited in the measurement of proton chemical shift differences between diastereomers and enantiomer excess (ee). The broad use of the proposed method was demonstrated by employing the six samples utilizing the chiral solvating and derivatizing agents.

Slice selective absorption-mode J-resolved NMR spectroscopy

Limited chemical shift dispersion and broad multiplet patterns limit resolution in 1H NMR spectra. J-Resolved spectroscopy overcomes this problem to a great extent. However, the phase-twist line shape in J-Resolved spectroscopy allows only the magnitude mode of the experiment to be practical, which degrades resolution. Recently, various pure shift or broadband homonuclear decoupling approaches have been integrated with J-Resolved spectroscopy to eliminate the broad dispersive contribution. In the present work, we demonstrate a broadband 1H–1H J-Resolved spectrum with a greatly reduced dispersive contribution using the concept of slice selection. We show that slice selective excitation, t1 encoding, storage, and detection of the in-phase absorptive signals can be executed, while a gradient-based suppression of the dispersive antiphase signals can be performed during the storage period. In more than two spin systems, a small part of the doubly antiphase absorptive signal may also contribute to the spectrum in addition to the inphase absorptive signals. The overall effect is a reduced multiplet pattern similar to a regular J-Resolved case as the passive spins remain unflipped due to slice selective pulses. However, the effect is broadband for a fraction of the spins when all slices are considered analogous to Zangger-Sterk (ZS) broadband homo-decoupling. Further, the fresh magnetization from neighboring slices can be accessed in different scans by frequency shifting of the slice selective pulses without a recycle delay-an elegant aspect of the ZS pulse element. This allows faster signal averaging, improving sensitivity which depends on the T1 relaxation time of the signals. This method displays sensitivity up to 4–20 percent of the regular J-RES 1H signals.

Simultaneous acquirement of pure shift 2D homonuclear correlation spectra

Two dimensional homonuclear correlation spectra like COSY, TOCSY and NOESY are classic two-dimensional spectra for analyzing coupling networks and delivering structural information of molecules. Two main challenges of the homonuclear correlation spectra are resolution and efficiency. Because of the complexity of the molecular structure and the effect of scalar coupling, spectral resolution is still difficult to meet the demand, and a higher resolution is needed to improve the quality of the homonuclear correlation spectrum. On the other hand, although some homonuclear correlation spectra are often used together (such as COSY and TOCSY), they are generally sampled separately, and as the number of sampling points in the indirect dimension increases, experiment time increases dramatically. Here, we propose a scheme that can be used to simultaneously obtain indirect dimension pure shift COSY and TOCSY or indirect dimension pure shift COSY and NOESY to improve the resolution of them, while reducing the sampling time and improving the efficiency.