Nuclear Magnetic Resonance Properties Research Articles

Effects of whole wheat flour on frozen dough and steamed bread during freeze-thaw cycles

The research on Chinese steamed bread (CSB) with whole wheat flour (WWF) is limited and has not been discussed during freeze-thaw. This study investigated the effects of WWF addition on the dough and CSB quality during freeze-thaw cycles. The results of low-field nuclear magnetic resonance (LF-NMR) and dynamic rheological properties demonstrated that the WWF reduced the adverse changes of freeze-thaw treatment on the dough. Characteristics, texture, and cross section analysis of CSB showed that WWF (20%) could relatively maximize stability. To study the mechanism, arabinoxylan (AX) and water-extractable arabinoxylan (WEAX) from WWF were added to dough. Consistent with WWF, it was found that they could improve freeze-thaw tolerance of frozen dough and CSB. Meanwhile, WEAX (1.12%) could better increase quality and freeze-thaw tolerance of CSB. The results presented in the study indicate that the anti-freeze-thaw effects of WWF could be attributed to AX and WEAX.

Hyperpolarized Xenon-129 Chemical Exchange Saturation Transfer (HyperCEST) Molecular Imaging: Achievements and Future Challenges.

Molecular magnetic resonance imaging (MRI) is an emerging field that is set to revolutionize our perspective of disease diagnosis, treatment efficacy monitoring, and precision medicine in full concordance with personalized medicine. A wide range of hyperpolarized (HP) 129Xe biosensors have been recently developed, demonstrating their potential applications in molecular settings, and achieving notable success within in vitro studies. The favorable nuclear magnetic resonance properties of 129Xe, coupled with its non-toxic nature, high solubility in biological tissues, and capacity to dissolve in blood and diffuse across membranes, highlight its superior role for applications in molecular MRI settings. The incorporation of reporters that combine signal enhancement from both hyperpolarized 129Xe and chemical exchange saturation transfer holds the potential to address the primary limitation of low sensitivity observed in conventional MRI. This review provides a summary of the various applications of HP 129Xe biosensors developed over the last decade, specifically highlighting their use in MRI. Moreover, this paper addresses the evolution of in vivo applications of HP 129Xe, discussing its potential transition into clinical settings.

Multivariate modelling analysis for prediction of glycidyl esters and 3-monochloropropane-1,2-diol (3-MCPD) formation in periodically heated palm oil

Palm oil is a vegetable oil that is widely used for cooking and deep-frying because of its affordability. However, repeatedly heated palm oil is also prone to oxidation due to its significant content of unsaturated fatty acids and other chemical toxicants such as glycidyl esters and 3-monochloropropane-1,2-diol (3-MCPD). Initially, the physicochemical properties such as colour, viscosity, peroxide, p-anisidine and total oxidation (TOTOX) of periodically heated palm oil were investigated. Chemical profiling and fingerprinting of six different brands of palm cooking oil during heating cycles between 90 and 360 min were conducted using Fourier transform infrared (FTIR) and 1H Nuclear Magnetic Resonance (NMR) metabolomics. In addition, the multivariate analysis was employed to evaluate the 1H NMR spectroscopic pattern of repeatedly heated palm oil with the corresponding physicochemical properties. The FTIR metabolomics showed significant different of the chemical fingerprinting subjected to heating duration, which in agreement with the result of 1H NMR metabolomics. Partial least squares (PLS) model revealed that most of the physicochemical properties of periodically heated palm oil are positively correlated (R2 values of 0.98–0.99) to their spectroscopic pattern. Based on the findings, the color of the oils darkened with increased heating time. The peroxide value (PV), p-anisidine value (p-AnV), and total oxidation (TOTOX) values increased significantly due to degradation of unsaturated compounds and oxidation products formed. We identified targeted metabolites (probable carcinogens) such as 3-monochloropropane-1,2-diol (3-MCPD) and glycidyl ester (GE), indicating the conversion of 3-MCPD to GE in repeatedly heated oils based on PCA and OPLSDA models. Our correlation analysis of NMR and physicochemical properties has shown that the conversion of 3-MCPD to GE was significantly increased from 180 to 360 min cooking time. The combination spectroscopic techniques with physicochemical properties are a reliable and robust methods to evaluate the characteristics, stability and chemical's structure changes of periodically heated palm oil, which may contribute to probable carcinogens development. This study has proven that combination of NMR and physicochemical analysis may predict the formation of the probable carcinogens of heated cooking oil over time which emphasizing the need to avoid certain heating cycles to mitigate formation of probable carcinogens during cooking process.

Molecular insights into nuclear-magnetic-resonance properties of NaCl solution confined within calcite nanopores

Nuclear magnetic resonance (NMR) relaxation time is an important petrophysical property probing fluid dynamics within pores and providing valuable information to understand solid–fluid interactions and ion-related effects. In this study, we investigate NMR and diffusion properties of confined sodium chloride (NaCl) solutions within calcite nanopores via molecular dynamics (MD) simulations. Density profiles, self-diffusion coefficients, and NMR relaxation times were analyzed as a function of pore size, pore geometry, and NaCl concentration. MD results indicate that the presence of NaCl hinders water movement, resulting in reduced self-diffusion coefficients and relaxation times of water. Nevertheless, the influence of NaCl on water mobility is less than the effects caused by confinement and geometry. Strength of oscillations in water and ion density profiles increases when the slit pore size is reduced to 1 nm, suggesting that water-calcite interactions near pore surfaces are stronger in smaller pore sizes. Analysis of dipole–dipole correlation functions and probability distribution of correlation times shows that ions in aqueous solution have an impact on both intra- and intermolecular interactions. A comprehensive comparison of NMR relaxation times of water in both slit and spherical nanopores reveals that spherical models provide a more accurate representation of the confinement effect induced by pore networks within tight rocks. These findings provide a novel quantitative understanding of the impact of confinement, pore geometry, and ion concentration on the translational and rotational dynamics of confined fluids in calcite nanopores.

Label-Free Chemically and Molecularly Selective Magnetic Resonance Imaging.

Biomedical imaging, especially molecular imaging, has been a driving force in scientific discovery, technological innovation, and precision medicine in the past two decades. While substantial advances and discoveries in chemical biology have been made to develop molecular imaging probes and tracers, translating these exogenous agents to clinical application in precision medicine is a major challenge. Among the clinically accepted imaging modalities, magnetic resonance imaging (MRI) and magnetic resonance spectroscopy (MRS) exemplify the most effective and robust biomedical imaging tools. Both MRI and MRS enable a broad range of chemical, biological and clinical applications from determining molecular structures in biochemical analysis to imaging diagnosis and characterization of many diseases and image-guided interventions. Using chemical, biological, and nuclear magnetic resonance properties of specific endogenous metabolites and native MRI contrast-enhancing biomolecules, label-free molecular and cellular imaging with MRI can be achieved in biomedical research and clinical management of patients with various diseases. This review article outlines the chemical and biological bases of several label-free chemically and molecularly selective MRI and MRS methods that have been applied in imaging biomarker discovery, preclinical investigation, and image-guided clinical management. Examples are provided to demonstrate strategies for using endogenous probes to report the molecular, metabolic, physiological, and functional events and processes in living systems, including patients. Future perspectives on label-free molecular MRI and its challenges as well as potential solutions, including the use of rational design and engineered approaches to develop chemical and biological imaging probes to facilitate or combine with label-free molecular MRI, are discussed.

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Nuclear magnetic resonance (NMR) spectroscopy is a versatile method for studying folding in peptides, proteins, and their mimetics. In natural entities, the straightforward to obtain metric of proton chemical shift provides residue‐level insights into folded structure as well as dynamics. Rao et al. report the expansion of such methods to protein‐like chains with non‐canonical backbone compositions. Comparison of the NMR properties of a library of artificial residues in random coil and helical contexts reveals systematic chemical shift changes associated with certain residues adopting a helical folded conformation. (doi: 10.1002/pep2.24297) image

Quantifying Magnetic Resonance Effects Due to Solid–Fluid Interactions on Confined Water within Quartz-Lined Nanopores via Molecular Dynamics Simulations

Nuclear magnetic resonance (NMR) relaxation time provides valuable information about properties of fluid and solid surfaces within rocks; however, the complexity of rock samples makes it difficult to quantify the effect of solid–fluid interactions on NMR measurements. Additionally, the ability of 2 MHz NMR equipment to probe nanopores is limited, while detailed analyses of fluid NMR properties in nanopores are possible through molecular dynamics (MD) simulations. We performed atomistic MD simulations to quantify the effect of solid–fluid interactions on confined water within hydroxylated slit and cylindrical quartz-lined rock pores (slit width and cylinder radius from 1 to 9 nm). NMR properties along with density profiles and mean-squared displacements (MSD) were calculated to quantify the effect of solids on relaxation times. MD results indicate that the surface chemistry of slit and cylindrical pores causes differences in density profiles and NMR properties of water confined in silica nanopores. Structural features present in density profiles are important to interpret both MSD and NMR relaxation properties. Intramolecular correlation times are shorter than intermolecular correlation times except when water is confined inside a 1 nm slit pore. These results highlight the importance of pore size on the solid–fluid interactions at the nanoscale. Layer analysis of confined water shows that NMR relaxation times of central layers in small nanopores are not the same as bulk relaxation time. This difference originates an overestimation of pore-size distributions of tight rocks from NMR measurements via Brownstein–Tarr’s equation. Furthermore, relaxation times of water layers indicate that the effect of solid surfaces on NMR relaxation times in a 3 nm slit pore is 15.32% of those in a 9 nm slit pore.

125Te NMR study of the bulk of topological insulators Bi2Te3 and Sb2Te3

AbstractThe narrow band gap semiconductors Bi2Te3 and Sb2Te3 are well known for their room temperature thermoelectric performance. Recently, they were shown to serve as model systems of three‐dimensional topological insulators with a bulk band gap and very robust, spin‐resolved surface states due to a special band inversion in their periodic bulk. Evidently, it is of interest to investigate the special surface states with a local probe like nuclear magnetic resonance (NMR). However, especially the bulk NMR of these materials shows peculiar and rather unexpected phenomena, e. g., a magnetic field induced deformation of the local charge symmetry and excessive line broadening due to a special internuclear coupling. Here we report a comprehensive account of the room temperature NMR properties of the spin‐1/2 nucleus 125Te of single crystalline Bi2Te3 and Sb2Te3. This includes a very unusual spin‐lattice relaxation that seems not to be reflected in the NMR shift, as well as an exchange enhanced NMR line broadening.

Radiation Dosimetry by Use of Radiosensitive Hydrogels and Polymers: Mechanisms, State-of-the-Art and Perspective from 3D to 4D.

Gel dosimetry was developed in the 1990s in response to a growing need for methods to validate the radiation dose distribution delivered to cancer patients receiving high-precision radiotherapy. Three different classes of gel dosimeters were developed and extensively studied. The first class of gel dosimeters is the Fricke gel dosimeters, which consist of a hydrogel with dissolved ferrous ions that oxidize upon exposure to ionizing radiation. The oxidation results in a change in the nuclear magnetic resonance (NMR) relaxation, which makes it possible to read out Fricke gel dosimeters by use of quantitative magnetic resonance imaging (MRI). The radiation-induced oxidation in Fricke gel dosimeters can also be visualized by adding an indicator such as xylenol orange. The second class of gel dosimeters is the radiochromic gel dosimeters, which also exhibit a color change upon irradiation but do not use a metal ion. These radiochromic gel dosimeters do not demonstrate a significant radiation-induced change in NMR properties. The third class is the polymer gel dosimeters, which contain vinyl monomers that polymerize upon irradiation. Polymer gel dosimeters are predominantly read out by quantitative MRI or X-ray CT. The accuracy of the dosimeters depends on both the physico-chemical properties of the gel dosimeters and on the readout technique. Many different gel formulations have been proposed and discussed in the scientific literature in the last three decades, and scanning methods have been optimized to achieve an acceptable accuracy for clinical dosimetry. More recently, with the introduction of the MR-Linac, which combines an MRI-scanner and a clinical linear accelerator in one, it was shown possible to acquire dose maps during radiation, but new challenges arise.

Solvent Dependent Nuclear Magnetic Resonance Molecular Parameters Based on a Polarization Consistent Screened Range Separated Hybrid Density Functional Theory Framework.

Nuclear magnetic resonance (NMR) properties of solvated molecules are significantly affected by the solvent. We, therefore, employ a polarization consistent framework that efficiently addresses the solvent polarizing environment effects. Toward this goal a dielectric screened range separated hybrid (SRSH) functional is invoked with a polarizable continuum model (PCM) to properly represent the orbital gap in the condensed phase. We build on the success of range separated hybrid (RSH) functionals to address the erroneous tendency of traditional density functional theory (DFT) to collapse the orbital gap. Recently, the impact of RSH that properly opens up the orbital gap in gas-phase calculations on NMR properties has been assessed. Here, we report the use of SRSH-PCM that produces properly solute orbital gaps in calculating isotropic nuclear magnetic shielding and chemical shift parameters of molecular systems in the condensed phase. We show that in contrast to simpler DFT-PCM approaches, SRSH-PCM successfully follows expected dielectric constant trends.

Modelling complex molecular interactions in catalytic materials for energy storage and conversion in nuclear magnetic resonance

Nuclear magnetic resonance (NMR) is a non-destructive and atom-specific specific tool that has become a burgeoning analytic method for understanding the detailed molecular interactions in catalysis and energy storage materials. However, the observation of diverse chemical shifts arising from complex molecular interactions makes the interpretation of NMR spectroscopy increasingly challenging, in particular for a novel system without standards for comparison. Density functional theory-NMR (DFT-NMR) is an indispensable tool to mitigate these challenges and provide detailed 3D molecular structures that relate materials and reaction intermediate structures, and information about chemical interactions, dynamics, and reaction mechanisms. This review provides a fundamental background in DFT-NMR relating to theory development, critical parameters for calculating NMR properties, computational accuracy, and the current capabilities. A variety of practical examples from the fields of catalysis and energy storage, including CO2 capture, are summarized to illustrate the capabilities of DFT-NMR application to date. Last but not least, cautionary notes on the application of these strategies are presented for researchers modeling their own systems.

Impact of the current density on paramagnetic NMR properties.

Meta-generalized gradient approximations (meta-GGAs) and local hybrid functionals generally depend on the kinetic energy density τ. For magnetic properties, this necessitates generalizations to ensure gauge invariance. In most implementations, τ is generalized by incorporating the external magnetic field. However, this introduces artifacts in the response of the density matrix and does not satisfy the iso-orbital constraint. Here, we extend previous approaches based on the current density to paramagnetic nuclear magnetic resonance (NMR) shieldings and electron paramagnetic resonance (EPR) g-tensors. The impact is assessed for main-group compounds and transition-metal complexes considering 25 density functional approximations. It is shown that the current density leads to substantial improvements-especially for the popular Minnesota and strongly constrained and appropriately normed (SCAN) functional families. Thus, we strongly recommend to use the current density generalized τ in paramagnetic NMR and EPR calculations with meta-GGAs.

Pre-gelatinization and cellulase addition improve fermentation performance and antioxidant activity of black rice wine.

Black rice contains a variety of bioactive substances that contribute to the high nutritional value of black rice wine (BRW). However, the dense bran layer of black rice retards the fermentation rate and reduces the dissolution of active components. Hence, this study aims to investigate the effects of pre-gelatinization (PG) before cooking and cellulase (CE) addition during fermentation on the fermentation performance of BRW and its antioxidant activity. PG combined with CE treatments (PGCE) increases the alcohol content, free amino acid content, volatile flavor content and total antioxidant activity of BRW by 90.81%, 15.36%, 38.05% and 19.56%, respectively, compared with the control group. Scanning electron microscopy, low-field nuclear magnetic resonance and texture properties analysis indicate that PG treatment increases gelatinization degree of starch during cooking, decreases bound water content in cooked black rice and promotes unbound water release. CE destroys the aleurone layer structure, facilitates the release of unbound water and the exposure of rice starch, thus increasing the reaction area and extravasation content significantly, which is beneficial to microbial growth and fermentation. Incomplete aleurone layer also promotes the dissolution of anthocyanins, phenols and other active substances, increasing the antioxidant activities of BRW. PG and CE treatments reduce the fermentation time and improve the quality of BRW by destroying the black rice structure. © 2022 Society of Chemical Industry.

Understanding Redox Reaction Mechanisms of a Flavin Mononucleotide By in Situ NMR and EPR Techniques

There are many types of energy storage technologies available at present, such as batteries and supercapacitors.1,2 Common battery chemistries include lead3 and lithium-ion4; however, scaling them up to the grid level is challenging.2 Recently, redox flow batteries (RFBs) have attracted much attention, as they can overcome the intermittent nature of renewable energy sources. We have previously developed a new approach to study RFBs by using in-situ nuclear magnetic resonance (NMR) and in-situ electron paramagnetic resonance (EPR), allowing the real time tracking of the redox state of various species in a system. As a result of this work, the electrochemical processes can be better understood. Investigating and understanding the electrolyte properties is a major goal in flow battery research and this will help to develop further RFB systems.Here, we report the analysis of the redox mechanism of a flavin mononucleotide-based anolyte (FMN) in a RFB system with the in-situ NMR and EPR setups. It represents one of the safest families of organic molecules for flow battery applications as it is a molecule derived from riboflavin (vitamin B2) and commonly used as an orange-red food additive.5–7 Nevertheless, the redox properties of flavins in strongly alkaline solution have yet to be thoroughly studied. In particular, the mechanism of the redox reaction for this system is not well understood.To understand the chemistry of FMN in strongly alkaline solution, first the NMR properties were studied. It was revealed that the chemical structure of FMN changed over time, i.e., additional signals were observed to grow in, and, additionally, the existence of a paramagnetic species was confirmed. The paramagnetic species formed on dissolution and was responsible for significant line broadening in the NMR spectrum. To examine how these changes affect the redox properties of FMN, a RFB was cycled over multiple cycles. Here we observed a second charge plateau developed as we continued to cycle the battery that was not mirrored during discharge. The in-situ EPR and NMR analysis reveal that the second plateau was likely caused by a side product derived from FMN. Therefore, possible degradation mechanisms of flavins, such as hydrolysis, need to be considered. Herein we propose that the observed changes over time are caused by the hydrolysis of FMN and provide an explanation for the different redox properties.References Wang, Y. & Zhong, W. H. Development Of Electrolytes Towards Achieving Safe And High-Performance Energy-Storage Devices: A Review. ChemElectroChem 2, 22–36 (2015).Divya, K. C. & Østergaard, J. Battery Energy Storage Technology For Power Systems - An Overview. Electr. Power Syst. Res. 79, 511–520 (2009).Ruetschi, P. Review On The Lead-Acid Battery Science And Technology. J. Power Sources 2, 3–120 (1977).Goodenough, J. B. & Park, K. S. The Li-Ion Rechargeable Battery: A Perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).Orita, A., Verde, M. G., Sakai, M. & Meng, Y. S. A Biomimetic Redox Flow Battery Based On Flavin Mononucleotide. Nat. Commun. 7, 1–8 (2016).Grajek, H., Zurkowska, G., Drabent, R. & Bojarski, C. Hanna Grajek. Biochem. Biophys. Acta 881, 241–247 (1986).Grajek, H., Drabent, R., Zurkowska, G. & Bojarski, C. Absorption Of The Flavin Dimers. BBA - Gen. Subj. 801, 456–460 (1984). Figure 1

An off-the-grid approach to multi-compartment magnetic resonance fingerprinting

We propose a novel numerical approach to separate multiple tissue compartments in image voxels and to estimate quantitatively their nuclear magnetic resonance (NMR) properties and mixture fractions, given magnetic resonance fingerprinting (MRF) measurements. The number of tissues, their types or quantitative properties are not a-priori known, but the image is assumed to be composed of sparse compartments with linearly mixed Bloch magnetisation responses within voxels. Fine-grid discretisation of the multi-dimensional NMR properties creates large and highly coherent MRF dictionaries that can challenge scalability and precision of the numerical methods for (discrete) sparse approximation. To overcome these issues, we propose an off-the-grid approach equipped with an extended notion of the sparse group Lasso regularisation for sparse approximation using continuous (non-discretised) Bloch response models. Furthermore, the nonlinear and non-analytical Bloch responses are approximated by a neural network, enabling efficient back-propagation of the gradients through the proposed algorithm. Through numerical experiments on simulated and in vivo healthy brain MRF data, we demonstrate the effectiveness of the proposed scheme compared to baseline multi-compartment MRF methods.

NMR spectroscopy, excited states and relevance to problems in cell biology - transient pre-nucleation tetramerization of huntingtin and insights into Huntington's disease.

Solution nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for analyzing three-dimensional structure and dynamics of macromolecules at atomic resolution. Recent advances have exploited the unique properties of NMR in exchanging systems to detect, characterize and visualize excited sparsely populated states of biological macromolecules and their complexes, which are only transient. These states are invisible to conventional biophysical techniques, and play a key role in many processes, including molecular recognition, protein folding, enzyme catalysis, assembly and fibril formation. All the NMR techniques make use of exchange between sparsely populated NMR-invisible and highly populated NMR-visible states to transfer a magnetization property from the invisible state to the visible one where it can be easily detected and quantified. There are three classes of NMR experiments that rely on differences in distance, chemical shift or transverse relaxation (molecular mass) between the NMR-visible and -invisible species. Here, I illustrate the application of these methods to unravel the complex mechanism of sub-millisecond pre-nucleation oligomerization of the N-terminal region of huntingtin, encoded by exon-1 of the huntingtin gene, where CAG expansion leads to Huntington's disease, a fatal autosomal-dominant neurodegenerative condition. I also discuss how inhibition of tetramerization blocks the much slower (by many orders of magnitude) process of fibril formation.

DFT investigations of AgMC7H10N2 (M = Cl, Br, and I) metal organic molecules: NMR, optoelectronic, and transport properties.

The full-potential linearized augmented plane wave (FP-LAPW) method was used for the calculation of the structural, nuclear magnetic resonance (NMR), optoelectronic, and thermoelectric properties of AgMC7H10N2 (M = Cl, Br, and I) compounds. The calculated wide band gap of AgMC7H10N2 (M = Cl, Br, and I) metal organic molecules with the density of states approach were 3.32, 3.29, and 3.10eV, respectively. The NMR parameters are calculated for the Ag, Cl, Br, I, C, N, O, and H elements. It is found that by decreasing bandgap, the isotropic NMR chemical shielding values of Cl, Br, and I elements increase. The strong hybridization of Ag-4d, Cl-3p, Br-4p, and I-5p states are observed at the top of the valence band. The birefringence and anisotropic properties are observed in the optical spectra with high plasmon energies, and the figure of merit, ZT, of 0.98 for AgCl(C7H10N2) compound is found at 300K. Hence, these compounds are attractive flexible metal organic molecules for optoelectronic and transport applications.

Janus-Type Dendrimers Based on Highly Branched Fluorinated Chains with Tunable Self-Assembly and 19F Nuclear Magnetic Resonance Properties

Tuning the self-assembly of dendritic amphiphiles represents a major challenge for the design of advanced nanomaterials for biomimetic applications. The morphology of the final aggregates, in fact, critically depends on the primary structure of the dendritic building blocks as well as the environmental conditions. Here we report a new family of fluorinated Janus-type dendrimers (FJDs), based on a short-chain and branched fluorinated synthon with 27 magnetically equivalent fluorine atoms, linked to bis-MPA polyester dendrons of different generations. Increasing size, flexibility, and number of peripheral hydroxyl groups, we observed a peculiar self-assembly behavior in bulk and in aqueous media as a consequence of the subtle balance between their fluorinated and hydrophilic portions. The lowest generation FJDs formed spherical nanoparticles in water, e.g., micelles, showing a single 19F NMR peak with good signal-to-noise ratio and over time stability, making them promising as 19F-MRI traceable probes. The highest generation FJD, instead, presented an interesting morphological transition from multilamellar dendrimersomes to tubules as a consequence of a subtle balance of intra- and intermolecular forces that compete at the interface. Interestingly, a reduction of the local mobility of CF3 groups passing from dendrimersomes to tubules switches off the 19F NMR signal. The transition mechanism has been rationalized by coarse-grain simulations as well as demonstrated by using cosolvents of different nature (e.g., fluorinated) that promote conformational changes, ultimately reflected in the self-assembly behavior. Short and branched fluorinated chains have here been demonstrated as new moieties for the design of FJDs with tunable self-assembly behavior for potential applications as biocompatible 19F MRI probes in the construction of theranostic platforms.

Covalence and π-electron delocalization influence on hydrogen bonds in proton transfer process of o-hydroxy aryl Schiff bases: A combined NMR and QTAIM analysis.

Within the framework of the density functional theory approach, we studied the relationship between the chemical nature of intramolecular hydrogen bonds (HBs) and nuclear magnetic resonance (NMR) parameters, J-couplings and 1H-chemical shifts [δ(1H)], of the atoms involved in such bonds in o-hydroxyaryl Schiff bases during the proton transfer process. For the first time, the shape of the dependence of the degree of covalence in HBs on 1J(N-H), 1J(O-H), 2hJ(O-N), and δ(1H) during the proton transfer process in o-hydroxyaryl Schiff bases was analyzed. Parameters obtained from Bader's theory of atoms in molecules were used to assess the dependence of covalent character in HBs with both the NMR properties. The influence of π-electronic delocalization on 2hJ(N-O) under the proton transfer process was investigated. 2hJ(O-N) in a Mannich base was also studied in order to compare the results with an unsaturated system. In addition, substituent effects on the phenolic ring were investigated. Our results indicate that the covalent character of HBs on both sides of the transition state undergoes a smooth exponential increase as the δ(1H) moves downfield. The degree of covalence of the N⋯H (O⋯H) bond increases linearly as 1J(N-H) (1J(O-H)) becomes more negative, even after reaching the transition state. Non-vanishing values of spin dipolar (SD) and paramagnetic spin orbital terms of 2hJ(O-N) show that π-electronic delocalization has a non-negligible effect on tautomeric equilibrium and gives evidence of the presence of the resonance assisted HB.Variation of the SD term of 2hJ(O-N) follows a similar pattern as the change in the para-delocalization aromaticity index of the chelate ring.

A community-powered search of machine learning strategy space to find NMR property prediction models.

The rise of machine learning (ML) has created an explosion in the potential strategies for using data to make scientific predictions. For physical scientists wishing to apply ML strategies to a particular domain, it can be difficult to assess in advance what strategy to adopt within a vast space of possibilities. Here we outline the results of an online community-powered effort to swarm search the space of ML strategies and develop algorithms for predicting atomic-pairwise nuclear magnetic resonance (NMR) properties in molecules. Using an open-source dataset, we worked with Kaggle to design and host a 3-month competition which received 47,800 ML model predictions from 2,700 teams in 84 countries. Within 3 weeks, the Kaggle community produced models with comparable accuracy to our best previously published 'in-house' efforts. A meta-ensemble model constructed as a linear combination of the top predictions has a prediction accuracy which exceeds that of any individual model, 7-19x better than our previous state-of-the-art. The results highlight the potential of transformer architectures for predicting quantum mechanical (QM) molecular properties.