Nuclear Magnetic Resonance Signal Research Articles

Cumulative Data of 1H and 13C NMR Signals and Specific Rotations of Eremophilane Sesquiterpenoids. 4. 10H-3-O-Furanoeremophilanes

1H and 13C nuclear magnetic resonance (NMR) data and specific rotations of eremophilane sesquiterpenoids are cumulated as a series of review articles. This fourth chapter focuses on furanoeremophilanes bearing 10H with C-3 oxygen functionality, and 175 10H-furanoeremophilanes with 3-O functionality are listed in 38 tables. Those with 15,6-lactones and 6,15-ethers are included in this chapter. Dihydrofurans, lactols, dimers, nor- and seco-compounds, and other related compounds, are not included in this chapter. These data may help chemists working in the area of natural products chemistry and synthetic scientists as well as computational chemists.

Rician Noise Removal in Low-noise Condition via a Deep Unfolding Network

Nuclear magnetic resonance (NMR) signals as the key role of research on denoising, are mainly influenced by Rician noise. Restoring clean Rician medical images from signal-related Rician noise is a challenging task with great practical significance. In this paper, an energy function based on MAP estimation is proposed, mainly for conditions of low noise, where the noise distribution is approximately Gaussian. Then the mathematical model is embedded into the network structure to realize the knot of knowledge-driven and network learning. The experiment shows that the proposed model only uses simple and lightweight network modules and a small amount of training data, which has a better denoising effect and has achieved satisfactory results under the two evaluation indexes.

In-cell dehydration of sodium manganese hexacyanoferrate cathode revealed by solid-state NMR

The hard-to-remove lattice water has been regarded as a significant obstacle impeding the practical use of Prussian blue analogue cathodes for sodium-ion batteries. This work monitored the electrochemical evolution of a hydrated monoclinic sodium manganese hexacyanoferrate cathode by solid-state nuclear magnetic resonance (NMR). For the first time, we established a correlation between the chemical shifts of 23Na NMR signals and the presence or absence of lattice water within this cathode. Through this method, we verified the electrochemical dehydration process that coincides with the merging of two redox platforms and a phase transformation in the initial cycles. Furthermore, we discovered that the lattice water is completely removed after several-day cell rest following a single activation cycle.

Spontaneous increasing of sensitivity and resolution in parahydrogen-induced hyperpolarization by RASER

Enhancing the sensitivity of nuclear magnetic resonance (NMR) technology has been the focus of NMR research for decades, which offers the potential to significantly expand its applications in chemistry, biology, and medical imaging. Parahydrogen-induced polarization (PHIP) emerges as a cost-effective approach to substantially enhance the sensitivity of NMR. Nevertheless, the amplification of the 1H signal in PHIP is susceptible to interference from the thermal polarization state 1H NMR signal. Employing RASER (radiofrequency amplification by stimulated emission of radiation) proves effective in mitigating such interference, which can reduce the linewidth and increase the sensitivity at the same time. In this work, we utilized PHIP and RASER to enhance the signal-to-noise ratio (SNR) of a series of biocompatible alkynyl organic acid molecules. The alkynyl acid with the highest enhancement factor was first identified through PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) experiments. Subsequently, RASER experiments were carried out through hyperpolarization of 5-hexynoic acid, exploring its signal characteristics under varying flow rates and pressures. The SNR of proton signals of 5-hexynoic acid surpassed 150,000, an 18.62-fold improvement compared with traditional hyperpolarized signals in PASADENA, and a markedly narrowed linewidth of 0.06 Hz.

Capillary Imbibition Laws of Fresh–Brackish Waters in Sandstone

Understanding the capillary imbibition laws of brackish water in rocks is necessary to reveal the mechanism of fluid, salt, and ion transport. In this study, we investigated the capillary imbibition laws of a Na2SO4 solution of different concentrations in sandstone by measuring the parameters of water absorption mass, water migration front height, nuclear magnetic resonance (NMR) T2 spectra, and stratified moisture distribution. The results indicate the following: (1) With an increase in the salt solution concentration, the water absorption rate of samples increases, specifically manifested in an increase in the rate of absorption mass and a rising rate of the absorption front. (2) With an increase in the salt solution concentration, the total NMR signals in samples measured at the end of water absorption decreases; that is, the total amount of water absorption decreases. (3) When the solution concentration exceeds 0.50 g/L, variations in the NMR signal of samples and the absorbed water mass over time are not synchronic and are even opposite at some stages. Based on the capillary dynamic theories of liquid, the influence of salts on solution properties and the modification of the pore structure by crystallization are considered when discussing the underlying mechanism of capillary imbibition in sandstone. By calculating the physical properties such as the density, viscosity, surface tension, and contact angle of solutions with different concentrations, the imbibition process does not exhibit any significant variation with the difference in the properties of the liquid. The equivalent capillary radii of the samples at varying salt concentrations are obtained by fitting the capillary dynamics curves with the theoretically calculated values. The equivalent capillary radii of samples in higher salt concentrations are larger, i.e., the difference in capillary imbibition laws introduced by the salt concentration should be attributed to modifications to the pore structure caused by salt crystallization.

NMR diffusion in restricted environment approached by a fractional Langevin model

The diffusion motion of spin-bearing molecules is considerably affected in confined environments. In Nuclear Magnetic Resonance (NMR) experiments, under the presence of magnetic field gradients, this movement can be encoded in spin phase and the NMR signal attenuation due to diffusion can be evaluated. This paper considered this effect in both normal and anomalous diffusion by means of the Langevin stochastic model within the Gaussian phase approximation (GPA) for a constant gradient temporal profile. The phenomenological approach illustrates the emergence of fractional order exponential decay in the NMR signal and retrieves the classical result from Hanh echo.

TECHNOLOGY FOR CONTROL AND MANAGEMENT OF MILK QUALITY USING MAGNETIC FIELD

In production, various methods are used to control the quality of manufactured products due to physical and chemical effects. In recent years, the principle of the phenomenon of nuclear magnetic resonance (NMR) has been increasingly used in the management and control of technological processes in food production. This paper examines the possibility of using the phenomenon of nuclear magnetic resonance for the purpose of automated control of milk quality by a magnetic field. By studying the isotopes of the NMR spectra of the specified product, it is possible to determine whether the product is natural or artificial, that is, its cost and quality. This work also provides a block diagram of the technological process and explains the expressions for receiving NMR signals and processing them with the creation of a magnetic field using electromagnets in an automated control system. This method allows not only to control the process, but also to determine the physical properties of milk and dairy products, contributing to changes in quality. To do this, it is necessary to maintain the optimal value of the generated magnetic field with very high accuracy.

Stereochemical and Computational NMR Survey of 1,2,3-Triazoles: in Search of the Original Tauto-Conformers.

The conformational analysis of nine functionalized 1,2,3-triazoles was carried out by the correlation of calculated and experimental high-level nuclear magnetic resonance (NMR) chemical shifts. In solution, the studied triazoles are in exchange dynamic equilibrium caused by their prototropic tautomerism of the NH-proton. The experimentally unresolved NMR signals were assigned for most of the compounds. A more thorough survey was conducted for 4-t-butyl-1,2,3-triazole-5-carbaldehyde oxime. The analysis performed within the framework of the DP4+ formalism completely confirmed the hypothesis of the predominance of the 2H-tautomer. Thus, the methodology for estimating stereochemical structures in the absence of some experimental data allowed the most stable conformations for dynamic systems with different tautomeric ratios to be reliably identified.

Gradient-based surface nuclear magnetic resonance for groundwater investigation

In medical magnetic resonance imaging, spatial localization (imaging) is based upon the application of controlled magnetic field gradients on top of the main magnetic field to spatially modulate the frequency and/or phase of the nuclear magnetic resonance (NMR) signal across the volume of investigation. In this work, we have applied similar physical principles to produce controlled magnetic field gradients during surface NMR-based groundwater investigations. In this approach, a gradient pulse of variable amplitude or duration is applied immediately after the excitation pulse to cause predictable phase encoding of the NMR signal as a function of depth. This approach is also applicable to emerging surface NMR detection methods that use a prepolarization field with fast nonadiabatic turn-off to generate detectable NMR signals from the shallow subsurface. In this case, the gradient pulse is applied after terminating the prepolarization field and provides a heretofore unavailable means of localizing the NMR response as a function of depth. The application of gradients can also be combined with tip-angle-based modulation to yield higher imaging resolution than can be achieved through either gradient- or tip-angle-based imaging alone. We implemented this new gradient-based capability into a surface NMR gradient generation accessory that is compatible with the GMR-Flex instrument and developed surface NMR-specific forward modeling and linear inverse models. We validated the accuracy of this novel gradient-based sNMR technology using computer simulations, experiments using a small pool filled with a discrete layer of bulk water, and field experiments at well-characterized groundwater test sites along Ebey Island, WA, and Larned, KS. The gradient-based sNMR imaging observations were compared with high-resolution direct push NMR results observed at these sites. The results of computer simulations and field experiments indicate improvements in both the detection (signal-to-noise ratio) and spatial resolution of shallow subsurface water content using gradient-based surface NMR, compared with traditional surface NMR imaging methods.

Systematic QM/MM Study for Predicting 31P NMR Chemical Shifts of Adenosine Nucleotides in Solution and Stages of ATP Hydrolysis in a Protein Environment.

NMR (nuclear magnetic resonance) spectroscopy allows for important atomistic insights into the structure and dynamics of biological macromolecules; however, reliable assignments of experimental spectra are often difficult. Herein, quantum mechanical/molecular mechanical (QM/MM) calculations can provide crucial support. A major problem for the simulations is that experimental NMR signals are time-averaged over much longer time scales, and since computed chemical shifts are highly sensitive to local changes in the electronic and structural environment, sufficiently large averages over representative structural ensembles are essential. This entails high computational demands for reliable simulations. For NMR measurements in biological systems, a nucleus of major interest is 31P since it is both highly present (e.g., in nucleic acids) and easily observable. The focus of our present study is to develop a robust and computationally cost-efficient framework for simulating 31P NMR chemical shifts of nucleotides. We apply this scheme to study the different stages of the ATP hydrolysis reaction catalyzed by p97. Our methodology is based on MM molecular dynamics (MM-MD) sampling, followed by QM/MM structure optimizations and NMR calculations. Overall, our study is one of the most comprehensive QM-based 31P studies in a protein environment and the first to provide computed NMR chemical shifts for multiple nucleotide states in a protein environment. This study sheds light on a process that is challenging to probe experimentally and aims to bridge the gap between measured and calculated NMR spectroscopic properties.

Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49Ti Solid-State Nuclear Magnetic Resonance Spectroscopy.

Treatment of Ziegler-Natta (ZN) catalysts with BCl3 improves their activity by increasing the number of active sites. Here we show how 47/49Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of 47/49Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit 49Ti NMR signatures (δiso,exp = -170 ppm; CQ,exp = 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl2 support, formed upon post-treatment with BCl3 and removal of the alkoxo ligands, paralleling the increased polymerization activity.

Time-frequency analysis reveals an association between the specific nuclear magnetic resonance (NMR) signal properties of serum samples and arteriosclerotic lesion progression in a diabetes mouse model.

Diabetes causes arteriosclerosis, primarily due to persistent hyperglycemia, subsequently leading to various cardiovascular events. No method has been established for directly detecting and evaluating arteriosclerotic lesions from blood samples of diabetic patients, as the mechanism of arteriosclerotic lesion formation, which involves complex molecular biological processes, has not been elucidated. "NMR modal analysis" is a technology that enables visualization of specific nuclear magnetic resonance (NMR) signal properties of blood samples. We hypothesized that this technique could be used to identify changes in blood status associated with the progression of arteriosclerotic lesions in the context of diabetes. The study aimed to assess the possibility of early detection and evaluation of arteriosclerotic lesions by NMR modal analysis of serum samples from diabetes model mice. Diabetes model mice (BKS.Cg db/db) were bred in a clean room and fed a normal diet. Blood samples were collected and centrifuged. Carotid arteries were collected for histological examination by hematoxylin and eosin staining on weeks 10, 14, 18, 22, and 26. The serum was separated and subjected to NMR modal analysis and biochemical examination. Mice typically show hyperglycemia at an early stage (8 weeks old), and pathological findings of a previous study showed that more than half of mice had atheromatous plaques at 18 weeks old, and severe arteriosclerotic lesions were observed in almost all mice after 22 weeks. Partial least squares regression analysis was performed, which showed that the mice were clearly classified into two groups with positive and negative score values within 18 weeks of age. The findings of this study revealed that NMR modal properties of serum are associated with arteriosclerotic lesions. Thus, it may be worth exploring the possibility that the risk of cardiovascular events in diabetic patients could be assessed using serum samples.

Qudit-Based Spectroscopy for Measurement and Control of Nuclear-Spin Qubits in Silicon Carbide.

Nuclear spins with hyperfine coupling to single electron spins are highly valuable quantum bits. Here we probe and characterize the particularly rich nuclear-spin environment around single silicon vacancy color centers (V2) in 4H-SiC. By using the electron spin-3/2 qudit as a four level sensor, we identify several sets of ^{29}Si and ^{13}C nuclear spins through their hyperfine interaction. We extract the major components of their hyperfine coupling via optical detected nuclear magnetic resonance, and assign them to shells in the crystal via the density function theory simulations. We utilize the ground-state level anticrossing of the electron spin for dynamic nuclear polarization and achieve a nuclear-spin polarization of up to 98±6%. We show that this scheme can be used to detect the nuclear magnetic resonance signal of individual spins and demonstrate their coherent control. Our work provides a detailed set of parameters and first steps for future use of SiC as a multiqubit memory and quantum computing platform.

Multivariate Machine Learning Models of Nanoscale Porosity from Ultrafast NMR Relaxometry.

Nanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well-established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal-organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high-throughput, non-destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.

Multivariate Machine Learning Models of Nanoscale Porosity from Ultrafast NMR Relaxometry

AbstractNanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well‐established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal‐organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high‐throughput, non‐destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.

A Straightforward Method for the Generation of Hyperpolarized Orthohydrogen with a Partially Negative Line.

The hydrogen molecule, which exists in two spin isomers (ortho- and parahydrogen), is a highly studied system due to its fundamental properties and practical applications. Parahydrogen is used for Nuclear Magnetic Resonance signal enhancement, which is hyperpolarization of other molecules, including biorelevant ones. Hyperpolarization can be achieved by using Signal Amplification by Reversible Exchange (SABRE). SABRE can also convert parahydrogen into orthohydrogen, and surprisingly, in some cases, it has been discovered that orthohydrogen's resonance has the Partially Negative Line (PNL) pattern. Here, an approach for obtaining orthohydrogen with a PNL signal is presented for two catalysts: Ir-IMes, and Ir-IMesBn. The type of solvent in which SABRE is conducted is crucial for the observation of PNL. Specifically, a PNL signal can be easily generated in benzene using both catalysts, but it is more intense for Ir-IMesBn. In acetone, PNL is observed only for Ir-IMesBn. In methanol, no PNL is detected. The PNL effect is only detectable during the initial steps of pre-catalyst activation, and disappears as the activation process progresses. We have proposed a working hypothesis that explains our results. The presented data may facilitate the further investigation of PNL and its applications in material science and catalysis.

A Straightforward Method for the Generation of Hyperpolarized Orthohydrogen with a Partially Negative Line

AbstractThe hydrogen molecule, which exists in two spin isomers (ortho‐ and parahydrogen), is a highly studied system due to its fundamental properties and practical applications. Parahydrogen is used for Nuclear Magnetic Resonance signal enhancement, which is hyperpolarization of other molecules, including biorelevant ones. Hyperpolarization can be achieved by using Signal Amplification by Reversible Exchange (SABRE). SABRE can also convert parahydrogen into orthohydrogen, and surprisingly, in some cases, it has been discovered that orthohydrogen's resonance has the Partially Negative Line (PNL) pattern. Here, an approach for obtaining orthohydrogen with a PNL signal is presented for two catalysts: Ir−IMes, and Ir−IMesBn. The type of solvent in which SABRE is conducted is crucial for the observation of PNL. Specifically, a PNL signal can be easily generated in benzene using both catalysts, but it is more intense for Ir−IMesBn. In acetone, PNL is observed only for Ir−IMesBn. In methanol, no PNL is detected. The PNL effect is only detectable during the initial steps of pre‐catalyst activation, and disappears as the activation process progresses. We have proposed a working hypothesis that explains our results. The presented data may facilitate the further investigation of PNL and its applications in material science and catalysis.

Intrinsically disordered Pseudomonas chaperone FapA slows down the fibrillation of major biofilm-forming functional amyloid FapC.

Functional bacterial amyloids play a crucial role in the formation of biofilms, which mediate chronic infections and contribute to antimicrobial resistance. This study focuses on the FapC amyloid fibrillar protein from Pseudomonas, a major contributor to biofilm formation. We investigate the initial steps of FapC amyloid formation and the impact of the chaperone-like protein FapA on this process. Using solution nuclear magnetic resonance (NMR), we recently showed that both FapC and FapA are intrinsically disordered proteins (IDPs). Here, the secondary structure propensities (SSPs) are compared to alphafold (DeepMind, protein structure prediction tool/algorithm: https://alphafold.ebi.ac.uk/) models. We further demonstrate that the FapA chaperone interacts with FapC and significantly slows down the formation of FapC fibrils. Our NMR titrations reveal ~ 18% of the resonances show FapA-induced chemical shift perturbations (CSPs), which has not been previously observed, the largest being for A82, N201, C237, C240, A241, and G245. These sites may suggest a specific interaction site and/or hotspots of fibrillation inhibition/control interface at the repeat-1 (R1)/loop-2 (L2) and L2/R3 transition areas and at the C-terminus of FapC. Remarkably, ~ 90% of FapA NMR signals exhibit substantial CSPs upon titration with FapC, the largest being for S63, A69, A80, and I92. A temperature-dependent effect of FapA was observed on FapC by thioflavin T (ThT) and NMR experiments. This study provides a detailed understanding of the interaction between the FapA and FapC, shedding light on the regulation and slowing down of amyloid formation, and has important implications for the development of therapeutic strategies targeting biofilms and associated infections.

Efficient Scavenging of TEMPOL Radical by Ascorbic Acid in Solution and Related Prolongation of 13C and 1H Nuclear Spin Relaxation Times of the Solute

Dynamic nuclear polarization for nuclear magnetic resonance (NMR) spectroscopy and imaging uses free radicals to strongly enhance the NMR signal of a compound under investigation. At the same time, the radicals shorten significantly its nuclear spin relaxation times which reduces the time window available for the experiments. Radical scavenging can overcome this drawback. Our work presents a detailed study of the reduction of the TEMPOL radical by ascorbic acid in solution by high-resolution NMR. Carbon-13 and hydrogen-1 nuclear spin relaxations are confirmed to be restored to their values without TEMPOL. Reaction mechanism, kinetics, and the influence of pD and viscosity are thoroughly discussed. The detailed investigation conducted in this work should help with choosing suitable concentrations in the samples for dynamic nuclear polarization and optimizing the measurement protocols.

Determination of application boundaries to Giulotto method to during measuring of longitudinal relaxation time in nuclear magnetic flowmeters-relaxometers

The method of nuclear magnetic resonance, which is currently the most common in research and control of parameters of condensed matter, and the nuclear magnetic flowmeters-relaxometers that implement this method are described. The features of determining the times of longitudinal and transverse relaxation in nuclear magnetic flowmeters-relaxometers under different flow regimes of the medium in the process of monitoring its parameters have been established. The advantages of using a modulation technique for recording nuclear magnetic signals in flowmeters-relaxometers in comparison with other registration methods are noted. Using various approximations by the Giulotto method from the Bloch equations, a relation was obtained to determine the longitudinal relaxation time from the results of two measurements of the amplitudes of the nuclear magnetic resonance signal or resonant frequencies at different modulation frequencies. It has been experimentally proven that this relationship has a number of restrictions on its application for flowing liquid. These limitations are associated both with the technique of recording nuclear magnetic resonance signals and with the ability to generate such signals at different modulation frequencies of a constant magnetic field, the amplitudes of which differ from each other beyond the measurement error. The reasons that led to this discrepancy in the ratio for determining the time of longitudinal relaxation have been established. The limits of applicability of the obtained relation are found and it is experimentally proven that within these limits this relation can be used for reliable measurements of relaxation constants. Using experimental data, the relationship for determining the longitudinal relaxation time was studied. It has been proven that in a number of cases it is impossible to determine the desired value using the indicated relationship, although nuclear magnetic resonance signals of the current medium are recorded, and the medium has relaxation times. The results obtained make it possible to eliminate errors when using the nuclear magnetic resonance method to study flowing media and solve a number of complex problems in the energy, oil, chemical and pharmaceutical industries.