Nuclear Magnetic Resonance Signal Research Articles

Mechanism of Solid-State 1H Photochemically Induced Dynamic Nuclear Polarization in a Synthetic Donor-Chromophore-Acceptor at 0.3 T.

1H photochemically induced dynamic nuclear polarization (photo-CIDNP) has recently emerged as a tool to enhance bulk 1H nuclear magnetic resonance (NMR) signals in solids at magnetic fields ranging from 0.3 to 21.1 T, using synthetic donor-chromophore-acceptor (D-C-A) molecules as optically active polarizing agents (PAs). However, the mechanisms at play for the generation of spin polarization in these systems have not been determined but are essential for an in-depth understanding and further development of the process. Here, we introduce site-selective deuteration to identify the 1H photo-CIDNP mechanisms at 85 K and 0.3 T in D-C-A molecule PhotoPol. We find that the protons on the acceptor moiety are essential for the generation of polarization, establishing differential relaxation as the main mechanism. These results establish selective deuteration as a tool to identify and suppress polarization transfer mechanisms, which opens up pathways for further optimization of the optical PA at both low and high magnetic fields.

Strategic approaches to observing 39K NMR signals from potassium–graphite intercalation compounds

Abstract Solid-state nuclear magnetic resonance (NMR) is an invaluable tool for potassium–graphite intercalation compounds (K-GICs), promising anode materials of K-ion batteries, but it has not yet been applied because of several issues. We attempted 39K NMR measurements of K-GICs sealed in glass using an 18.8 T NMR spectrometer with an NMR probe adjusted to the samples. The first observed 39K NMR signal of K-GICs showed the possibility of evaluating intralayer density, which cannot be ascertained from Raman measurements.

Real‐Time Nuclear Magnetic Resonance Detection Using Maximum Likelihood Estimation with Single‐Shallow‐Nitrogen‐Vacancy Centers in Quantum Heterodyne Measurements

Single‐nitrogen‐vacancy (NV) centers in diamond are highly promising quantum nuclear magnetic resonance (NMR) sensors. However, their exposure to many sources of noise, such as surface impurities, shot noise from avalanche photodiode overlaps, and spin‐state projection errors inherent in quantum systems, limits their usefulness. Often, long measurement durations are required to accumulate sufficient data for NMR signal detection via fast Fourier transform spectrometry. For practical reasons, methods to shorten the necessary accumulation time for NMR signal detection are greatly desired. In this article, an on‐line formulation of maximum likelihood estimation (MLE) signal processing for quantum heterodyne NMR measurements is presented as a step toward this goal. This MLE method reduces the required data accumulation time by orders of magnitude and provides good estimates of target frequency locales in real time. These results are significant to practitioners of NMR detection with single‐NV centers in diamond who require a quick litmus test for potential signals when probing a wide area.

Feasibility of Surface Nuclear Magnetic Resonance With Absurdly Long Excitation Pulses

AbstractThe common understanding in surface nuclear magnetic resonance (NMR) is that the excitation pulse should be kept much shorter than the NMR relaxation times for an effective excitation. We present analytic, numerical, and experimental evidence demonstrating that this need not be so, and surface NMR signals can be retrieved even for absurdly long excitation pulses. We solve the Bloch equations in the limit of infinitely long excitation and use this result to demonstrate that a measurable magnetization can be obtained with long excitation pulses. We perform numerical simulations of the Bloch equations incorporating effects of relaxation‐during‐pulse, and our results suggest that long excitation pulses can be used to increase the depth of investigation, but that the spatial resolution of long pulse excitation is low. Data collected in Kompedal, Denmark using up to 3 s long excitation pulses provide experimental proof for the feasibility of long pulse surface NMR.

19F NMR-Based Chiral Analysis of Organoboron Compounds via Chiral Recognition of Fluorine-Labeled Boronates with Cobalt Complexes.

This study aims to develop a method for the chiral analysis of organoboron compounds using nuclear magnetic resonance (NMR) spectroscopy. It addresses the longstanding challenge associated with these chiral organoboron compounds, which often require derivatization and pretreatment prior to chromatographic analysis. Our method utilizes tridentate ligands to facilitate effective ligand exchange and incorporates fluorine labels, allowing for the precise discrimination of 19F NMR signals. This is achieved in conjunction with a chiral cationic cobalt complex, serving as the chiral solvating agent. This approach provides reliable and rapid determination of enantiomeric excess in a wide range of organoboron compounds, featuring various functional groups, and establishes a universal tool for assessing the optical purity of these substances.

Effective phase diffusion for spin phase evolution under random nonlinear magnetic field.

The general theoretical description of spin self-diffusion under a nonlinear gradient magnetic field is proposed, which extends the effective phase diffusion method for a linear gradient field. Based on the phase diffusion, the proposed method reveals the general features of phase evolutions in nonlinear gradient fields. There are three types of phase evolutions: phase diffusion, float phase evolution, and shift evolution based on the starting position. For spin diffusion near the origin of the nonlinear field, these three phase evolutions significantly affect the nuclear magnetic resonance (NMR) signal. The traditional methods have difficulties in handling these three-phase evolutions. Notably, the phase from float phase evolution is missed or misplaced in traditional methods, which leads to incorrect NMR signal attenuation or phase shift. The method here shows that the diffusing and float phase evolutions come from the first and second derivatives of the gradient field. Based on these three phase evolutions, the phase variance and corresponding NMR signal attenuation are obtained, as demonstrated by calculating the phase diffusions under both parabolic and cubic fields. The results indicate that signal attenuation obeys Gaussian attenuation for a short time, then changes to follow Lorentzian or Mittag-Leffler function attenuations as time increases, significantly different from Gaussian attenuation. For spins starting diffusion far away from the origin of the field gradient, the signal attenuation is Gaussian, but the float phase still has an important effect on the total phase shift of even-order gradient fields, which could be used to measure the diffusion coefficient directly. Random walk simulations were performed, which support the obtained theoretical results. General theoretical expressions are obtained, which can handle random order nonlinear gradient fields. The results could help develop advanced experimental techniques based on a nonlinear gradient field in NMR and magnetic resonance imaging.

Quaternary ammonium chitosan-based active packaging films incorporated with dialdehyde guar gum-proanthocyanidins conjugates: Characterization and application in the edible coating of pork

In this study, antioxidant and antibacterial proanthocyanidins (PA) were covalently conjugated with dialdehyde guar gum (DGG) to produce DGG-PA conjugates. Then DGG-PA conjugates were incorporated into quaternary ammonium chitosan (QAC)-based matrix to create QAC/DGG-PA films. The structure, physicochemical properties, and antioxidant and antibacterial effects of DGG-PA conjugates and QAC/DGG-PA films were analyzed. The active packaging potentials of QAC/DGG-PA film-forming solutions in the edible coating of pork loins were evaluated. Results showed DGG-PA conjugates had unique UV absorption peak (280 nm), infrared bands (1610 and 1521 cm−1) and proton nuclear magnetic resonance signals (6.82 ppm) of PA groups. DGG-PA conjugates showed amorphous state with sheet-like and fibrous morphology. DGG-PA conjugates had good biocompatibility and antioxidant and antibacterial effects. After adding DGG-PA conjugates, the surface of QAC-based films became smooth and the crystallographic nature of the films declined. DGG-PA conjugates elevated the light/water vapor/oxygen barrier performances, mechanical properties, and antioxidant and antibacterial effects of QAC-based films. QAC/DGG-PA edible coatings effectively prolonged the shelf life of pork loins from 4 days to 6−10 days. Results verified QAC/DGG-PA films and their film-forming solutions had good application potentials in active packaging.

A Reduced-Symmetry Pd2L4 Cage from a Heterotopic Dipyridyl Ligand.

Two dipyridyl ligands, L3,3 and L3,4, have been used in combination with palladium(II) in the construction of metallosupramolecular species that show anion-dependent behavior in solution. A rare example of a low-symmetry (C2h) lantern-type cage is formed in one instance, [Pd2(L3,3)4]4+, while the isomeric ligand yields a larger double-walled square complex, [Pd4(L3,4)8]8+. [Pd2(L3,3)4](NO3)4 was isolated in crystalline form revealing two anions within the interior of the C2h-symmetry cage. The cage itself is held together by hydrogen bonding between "head-to-tail" pairs of ligands that reinforces the symmetry generated by the ditopic ligands. In solution, the cage with NO3- has sharp 1H nuclear magnetic resonance (NMR) signals at room temperature, while the BF4- analogue has broad signals that sharpen at higher temperatures or upon addition of (Bu4N)(NO3), highlighting the importance of the anion in templating or otherwise influencing self-assembly in solution. Altering the substitution position of one of the pyridyl rings yields a more "open" complex, with [Pd4(L3,4)8](NO3)8 being isolated as a crystalline solid. The double-walled square complex has a greater Pd···Pd separation due to the increased angle that the pyridyl groups subtend at the core of the ligand. NMR spectroscopy and mass spectrometry studies suggest a single species in the presence of nitrate but multiple species with tetrafluoroborate.

Can Subsurface Oxygen Species in Oxides Participate in Catalytic Reactions? An 17O Solid-State Nuclear Magnetic Resonance Study.

The impacts of subsurface species of catalysts on reaction processes are still under debate, largely due to a lack of characterization methods for distinguishing these species from the surface species and the bulk. By using 17O solid-state nuclear magnetic resonance (NMR) spectroscopy, which can distinguish subsurface oxygen ions in CeO2 (111) nanorods, we explore the effects of subsurface species of oxides in CO oxidation reactions. The intensities of the 17O NMR signals due to surface and subsurface oxygen ions decrease after the introduction of CO into CeO2 nanorods, with a more significant decrease observed for the latter, confirming the participation of subsurface oxygen species. Density functional theory calculations show that the reaction involves subsurface oxygen ions filling the surface oxygen vacancies created by the direct contact of surface oxygen with CO. This new approach can be extended to the study of the role of oxygen species in other catalytic reactions.

Magnetic-field coils for metastability-exchange optical pumping, spectroscopy, and magnetic resonance of helium.

Optical pumping on the 23S-23P transition (1083nm) of metastable 3He or 4He atoms is used for science and applications. Gas is usually enclosed in elongated cells with lengths ranging from several centimeters to several meters for efficient absorption. Good magnetic-field homogeneity is needed for weak diffusion-induced relaxation and long nuclear magnetic resonance (NMR) signal lifetimes. A compact coil system is designed using a target-oriented numerical optimization method. It provides a suitably uniform field over cell volumes, with characteristics depending on the chosen optimization parameters. Additional pairs of coils can be used to generate transverse field components with contributions to the total field inhomogeneities that are discussed.

Tailoring solid-state DNP methods to the study of [formula omitted]-synuclein LLPS

Dynamic Nuclear Polarization (DNP) is a technique that leverages the quantum sensing capability of electron spins to enhance the sensitivity of nuclear magnetic resonance (NMR) signals, especially for insensitive samples. Glassing agents play a crucial role in the DNP process by facilitating the transfer of polarization from the unpaired electron spins to the nuclear spins along with cryoprotection of biomolecules. DNPjuice comprising of glycerol-d8/D2O/H2O has been extensively used for this purpose over the past two decades. Polyethylene glycol (PEG), also used as a cryoprotectant, is often used as a crowding agent in experimental setups to mimic cellular conditions, particularly the invitro preparation of liquid-liquid phase separated (LLPS) condensates. In this study, we investigate the efficacy of PEG as an alternative to glycerol in the DNP juice, critical for signal enhancement. The modified DNP matrix leads to high DNP enhancement which enables direct study of LLPS condensates by solid-state DNP methods without adding any external constituents. An indirect advantage of employing PEG is that the PEG signals appear at ∼72.5 ppm and are relatively well-separated from the aliphatic region of the protein spectra. Large cross-effect DNP enhancement is attained for 13C-glycine by employing the PEG-water mixture as a glassing agent and ASYMPOL-POK as the state-of-art polarizing agent, without any deuteration. The DNP enhancement and the buildup rates are similar to results obtained with DNP juice, conforming to that PEG serves as a good candidate for both inducing crowding and glassing agent in the study of LLPS.

Cryogenic and Dissolution DNP NMR on γ-Irradiated Organic Molecules.

Nuclear magnetic resonance (NMR) plays a central role in the elucidation of chemical structures but is often limited by low sensitivity. Dissolution dynamic nuclear polarization (dDNP) emerges as a transformative methodology for both solution-state NMR and metabolic NMR imaging, which could overcome this limitation. Typically, dDNP relies on combining a stable radical with the analyte within a uniform glass under cryogenic conditions. The electron polarization is then transferred through microwave irradiation to the nuclei. The present study explores the use of radicals introduced via γ-irradiation, as bearers of the electron spins that will enhance 1H or 13C nuclides. 1H solid-state NMR spectra of γ-irradiated powders at 1-5 K revealed, upon microwave irradiation, signal enhancements that, in general, were higher than those achieved through conventional glass-based DNP. Transfer of these samples to a solution-state NMR spectrometer via a rapid dissolution driven by a superheated water provided significant enhancements of solution-state 1H NMR signals. Enhancements of 13C signals in the γ-irradiated solids were more modest, as a combined consequence of a low radical concentration and of the dilute concentration of 13C in the natural abundant samples examined. Nevertheless, ca. 700-800-fold enhancements in 13C solution NMR spectra of certain sites recorded at 11.7 T could still be achieved. A total disappearance of the radicals upon performing a dDNP-like aqueous dissolution and a high stability of the samples were found. Overall, the study showcases the advantages and limitations of γ-irradiated radicals as candidates for advancing spectroscopic dDNP-enhanced NMR.

Tracking Metabolite Variations during the Degradation of Vegetables in Rice Bran Bed with Intact-State Nuclear Magnetic Resonance Spectroscopy.

Fermentation-a process of compound degradation by microorganisms-is a traditional food processing method utilized worldwide for the long-term preservation of fresh foods. In recent years, fermented foods have gained attention as health foods. Fermentation increases the nutritional value of ingredients, producing complex flavors and aromas. To identify unknown components in fermented foods, it is necessary to analyze compounds and conditions nondestructively and comprehensively. We performed intact-state nuclear magnetic resonance (NMR) spectroscopy using intermolecular single quantum coherence (iSQC) to detect the degradation of vegetables directly and nondestructively. We used two types of vegetables and a rice bran bed (nukazuke), which is used for traditional vegetable fermentation in Japan. Major metabolites such as saccharides, organic acids, and amino acids were identified in iSQC-sliced spectra. Comparing NMR signal intensities during degradation revealed the transition of metabolites characteristic of lactic acid fermentation. A pathway-based network analysis showed pathways involved in amino acid metabolism and lactic acid fermentation. Our analytical approach with intact-state NMR spectroscopy using iSQC demonstrated that it may be effective in other experimental systems, allowing for the evaluation of phenomena that have been conventionally overlooked in their true state.

Light-Induced 1H NMR Hyperpolarization in Solids at 9.4 and 21.1 T.

The inherently low sensitivity of nuclear magnetic resonance (NMR) spectroscopy is the major limiting factor for its application to elucidate structure and dynamics in solids. In the solid state, nuclear spin hyperpolarization methods based on microwave-induced dynamic nuclear polarization (DNP) provide a versatile platform to enhance the bulk NMR signal of many different sample formulations, leading to significant sensitivity improvements. Here we show that 1H NMR hyperpolarization can also be generated in solids at high magnetic fields by optical irradiation of the sample. We achieved this by exploiting a donor-chromophore-acceptor molecule with an excited state electron-electron interaction similar to the nuclear Larmor frequency, enabling solid-state 1H photochemically induced DNP (photo-CIDNP) at high magnetic fields. Through hyperpolarization relay, we obtained bulk NMR signal enhancements εH by factors of ∼100 at both 9.4 and 21.1 T for the 1H signal of o-terphenyl in magic angle spinning (MAS) NMR experiments at 100 K. These findings open a pathway toward a general light-induced hyperpolarization approach for dye-sensitized high-field NMR in solids.

Overhauser enhanced liquid state nuclear magnetic resonance spectroscopy in one and two dimensions

Nuclear magnetic resonance (NMR) is fundamental in the natural sciences, from chemical analysis and structural biology, to medicine and physics. Despite its enormous achievements, one of its most severe limitations is the low sensitivity, which arises from the small population difference of nuclear spin states. Methods such as dissolution dynamic nuclear polarization and parahydrogen induced hyperpolarization can enhance the NMR signal by several orders of magnitude, however, their intrinsic limitations render multidimensional hyperpolarized liquid-state NMR a challenge. Here, we report an instrumental design for 9.4 Tesla liquid-state dynamic nuclear polarization that enabled enhanced high-resolution NMR spectra in one and two-dimensions for small molecules, including drugs and metabolites. Achieved enhancements of up to two orders of magnitude translate to signal acquisition gains up to a factor of 10,000. We show that hyperpolarization can be transferred between nuclei, allowing DNP-enhanced two-dimensional 13C–13C correlation experiments at 13C natural abundance. The enhanced sensitivity opens up perspectives for structural determination of natural products or characterization of drugs, available in small quantities. The results provide a starting point for a broader implementation of DNP in liquid-state NMR.

EFG-CS: Predicting chemical shifts from amino acid sequences with protein structure prediction using machine learning and deep learning models.

Nuclear magnetic resonance (NMR) crystallography is one of the main methods in structural biology for analyzing protein stereochemistry and structure. The chemical shift of the resonance frequency reflects the effect of the protons in a molecule producing distinct NMR signals in different chemical environments. Apprehending chemical shifts from NMR signals can be challenging since having an NMR structure does not necessarily provide all the required chemical shift information, making predictive models essential for accurately deducing chemical shifts, either from protein structures or, more ideally, directly from amino acid sequences. Here, we present EFG-CS, a web server that specializes in chemical shift prediction. EFG-CS employs a machine learning-based transfer prediction model for backbone atom chemical shift prediction, using ESMFold-predicted protein structures. Additionally, ESG-CS incorporates a graph neural network-based model to provide comprehensive side-chain atom chemical shift predictions. Our method demonstrated reliable performance in backbone atom prediction, achieving comparable accuracy levels with root mean square errors (RMSE) of 0.30 ppm for H, 0.22 ppm for Hα, 0.89 ppm for C, 0.89 ppm for Cα, 0.84 ppm for Cβ, and 1.69 ppm for N. Moreover, our approach also showed predictive capabilities in side-chain atom chemical shift prediction achieving RMSE values of 0.71 ppm for Hβ, 0.74-1.15 ppm for Hδ, and 0.58-0.94 ppm for Hγ, solely utilizing amino acid sequences without homology or feature curation. This work shows for the first time that generative AI protein models can predict NMR shifts nearly comparable to experimental models. This web server is freely available at https://biosig.lab.uq.edu.au/efg_cs, and the chemical shift prediction results can be downloaded in tabular format and visualized in 3D format.

Characterization of shale oil and water micro-occurrence based on a novel method for fluid identification by NMR T2 spectrum

Nuclear magnetic resonance (NMR) has become a crucial technique for determining complex fluid occurrence characteristics. However, the overlap of fluid signals limits the application of the one-dimensional (1D) T2 (transverse relaxation time). Conventional methods are unable to accurately detect fluid signals that overlap entirely and cannot directly determine the petrophysical significance of each component spectrum. Leveraging the additional T1 (longitudinal relaxation time) information of two-dimensional (2D) NMR T1-T2, this study introduced a novel T2 spectra fluid identification method using the mixed Gaussian function. Six states of T2 and T1-T2 experiments were conducted on shale samples, including as-received (AR), water restoration of AR (WR-AR), water–oil restoration of AR (WOR-AR), oil-washed and dry (dry), oil-saturated (SO), and water-saturated (SW). By introducing the T2 projection spectrum, linear relationships between the 1D and 2D NMR signal amplitudes of various fluids were established to help separate the overlapping signals in the T2 spectrum. The results have demonstrated an inconsistent linear correlation between the 1D and 2D NMR signal amplitudes of various fluids, influenced by fluid composition and occurrence state. The conversion coefficient of adsorbed oil is 1.745 times higher than that of bound oil in the SO state. The adsorbed-to-bound ratio conversion coefficient was proposed as an additional input in the mixed Gaussian function to identify overlapping fluids in the oil–water coexistence state. The conversion coefficient of bound water determined by peak area analysis of 1D and 2D NMR before and after water restoration validated the identification results. The pore water altered the occurrence characteristics of oil, reducing the conversion coefficient. Furthermore, the pore-size characteristics of fluid occurrence were described. Compared with the conventional method, the proposed method bridges the gap between 1D and 2D NMR, significantly enhancing the accuracy and reliability of fluid identification by T2 spectra and providing new insights for NMR fluid evaluation in shale reservoirs.

Quantifying the water saturation degree of cement-based materials by hydrogen nuclear magnetic resonance (1H NMR)

This study investigated the T2 spectrum of hydrogen nuclear magnetic resonance (1H NMR) signals in cement paste with water-to-cement ratios (w/c) of 0.2, 0.35, and 0.5 under three different saturation methods (natural soak, vacuum saturation, and vacuum saturation with high pressure). The saturation degree and pore structure of the cement paste under different saturation methods has been calculated through the linear relationship between water absorption and increment of NMR amplitude intensity. The results showed that the saturation degree of the cement paste increased progressively with the duration of saturation until it reached a state of equilibrium. It can increase saturation degree and reduce the saturation time by increasing the saturation pressure, and vacuum saturation with high pressure is necessary for cement paste with lower w/c. It is important to noted that conditions such as unsaturation, natural soak, and vacuum saturation may result in incomplete water saturation, leading to a partial loss of the 1H NMR signal amplitude intensity and underestimation of porosity measurements. Considering the duration of saturation and the degree of saturation, it is recommended a saturation duration of at least 4 h with a vacuum pressure of 8 MPa for cement paste with w/c ratio of 0.2 and 0.35. For cement paste with w/c of 0.5, a saturation duration of at least 0.5 h with a vacuum pressure of 8 MPa is suggested.

New methods to strengthen NMR signals

Stronger alignment of atomic nuclei in Nuclear Magnetic Resonance (NMR) would enable significantly more detailed MRI scans. We spoke to Professor Malcolm Levitt, Bonifac Legrady and Mohamed Sabba about how they generated hyperpolarised nuclear states which provide a very strong NMR signal, how they plan to maintain the hyperpolarised states for a long time under ambient conditions, and the wider implications of their research.

200 GHz single chip microsystems for dynamic nuclear polarization enhanced NMR spectroscopy

Dynamic nuclear polarization (DNP) is one of the most powerful and versatile hyperpolarization methods to enhance nuclear magnetic resonance (NMR) signals. A major drawback of DNP is the cost and complexity of the required microwave hardware, especially at high magnetic fields and low temperatures. To overcome this drawback and with the focus on the study of nanoliter and subnanoliter samples, this work demonstrates 200 GHz single chip DNP microsystems where the microwave excitation/detection are performed locally on chip without the need of external microwave generators and transmission lines. The single chip integrated microsystems consist of a single or an array of microwave oscillators operating at about 200 GHz for ESR excitation/detection and an RF receiver operating at about 300 MHz for NMR detection. This work demonstrates the possibility of using the single chip approach for the realization of probes for DNP studies at high frequency, high field, and low temperature.