Dynamic Nuclear Magnetic Resonance Research Articles

Silicon Nitride Surface Enabled Propane Dehydrogenation Catalyzed by Supported Organozirconium.

Mesoporous silicon nitride (Si3N4) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal-ligand orbital overlap. Here, tetrabenzyl zirconium (ZrBn4) was chemisorbed on Si3N4, and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C-H bond activation along the Zr-N bond, this material was found to be a highly active (1.53 molpropene molZr-1 h-1 at 450 °C) and selective (99% to propylene) catalyst for propane dehydrogenation. In contrast, the homologous silica supported complex exhibited negligible activity under these conditions.

Electronic Structures of Radical-Pair-Forming Cofactors in a Heliobacterial Reaction Center.

Photosynthetic reaction centers (RCs) are membrane proteins converting photonic excitations into electric gradients. The heliobacterial RCs (HbRCs) are assumed to be the precursors of all known RCs, making them a compelling subject for investigating structural and functional relationships. A comprehensive picture of the electronic structure of the HbRCs is still missing. In this work, the combination of selective isotope labelling of 13C and 15N nuclei and the utilization of photo-CIDNP MAS NMR (photochemically induced dynamic nuclear polarization magic-angle spinning nuclear magnetic resonance) allows for highly enhanced signals from the radical-pair-forming cofactors. The remarkable magnetic-field dependence of the solid-state photo-CIDNP effect allows for observation of positive signals of the electron donor cofactor at 4.7 T, which is interpreted in terms of a dominant contribution of the differential relaxation (DR) mechanism. Conversely, at 9.4 T, the emissive signals mainly originate from the electron acceptor, due to the strong activation of the three-spin mixing (TSM) mechanism. Consequently, we have utilized two-dimensional homonuclear photo-CIDNP MAS NMR at both 4.7 T and 9.4 T. These findings from experimental investigations are corroborated by calculations based on density functional theory (DFT). This allows us to present a comprehensive investigation of the electronic structure of the cofactors involved in electron transfer (ET).

Small Cyclic Diglycolamides: Tautomerism, Solvent Extraction and Coordination with f-Elements: One Strain to Rule Them All.

The search for new effective extractants is an important task for the management of high-level liquid waste (HLW) generated during the reprocessing of spent nuclear fuel. Here, we synthesized a series of diglycolamides with cyclic substituents for the first time. We disclosed their coordination with f-element nitrates [La(NO3)3 and UO2(NO3)2] by SC-XRD study and complexation properties toward Am(III), Ln(III), and U(VI) during solvent extraction from nitric acid solutions. Using dynamic nuclear magnetic resonance (NMR) and density functional theory (DFT) calculations, the importance of tautomerism in the extraction properties of diglycolamides was shown.

A Small Change in Structure, a Big Change in Flexibility.

Studies of the rotational barrier energy of the amide bond using quantum computing and nuclear magnetic resonance (NMR) are focused mainly on its use as a model of the peptide bond. The results of these studies are valuable not only in terms of the fundamental conformational properties of amide bonds, but also in the design of molecular machines, which have recently attracted interest. We investigate the fluxionality of the amide and enamide bonds of compound 3-[(E)-(dimethylamino)methylidene]-1,1-dimethylurea using advanced dynamic NMR experiments and a theoretical evaluation of the density functional theory (DFT) calculation. The dynamic NMR study shows restricted rotation around the amide group (16.4 kcal/mol) and a very high barrier around the enamine group (18.6 kcal/mol). In a structurally similar compound, (E)-3-(dimethylamino)-N,N-dimethylacrylamide (N atom is replaced by CH), the amide barrier is 12.4 kcal/mol and the enamine barrier is 11.7 kcal/mol. The DFT studies of both compounds reveal the electronic origin of this phenomenon. Theoretical calculations reveal the origin of the higher enamine barrier. The better delocalization of the lone pair of electrons on the end nitrogen atom into the antibonding orbital of the neighboring C-N double bond leads to the better stabilization of the ground state, and this leads to a greater increase in the enamine barrier.

Enhancing vibration damping properties of MABS/VDT blends using SEBS-g-MAH as a compatibilizer

This investigation focuses on the enhancement of the damping properties of Methyl Methacrylate Acrylonitrile Butadiene Styrene (MABS) through the formulation of a specific blend with a styrene-based elastomer referred to as VDT, and with the incorporation of Ethylene Butylene Styrene grafted Maleic Anhydride (SEBS-g-MAH) as a compatibilizer. In contrast to traditional investigations that primarily focus on the mechanical rigidity, thermal conductivity, and electrical conductivity of materials, this research explores the enhancement of damping properties via the process of melt compounding. Using a twin-screw extruder in a precise melt-mixing process, a multiphase polymer blend is generated by including three different weight ratios (10, 20, and 30 wt.%) of VDT. Furthermore, in order to enhance the compatibility between MABS and VDT, three different weight percentages of SEBS-g-MAH (2, 4, and 6 wt.%) have been used in the blend. Tensile testing, laser confocal microscopy, dynamic mechanical analysis (DMA) and nuclear magnetic resonance (NMR), are used to thoroughly assess the compatibility and effectiveness of the blends. The results indicate that the damping performance of the blend increases in direct proportion to the amount of VDT. Conversely, the addition of SEBS-g-MAH has a non-monotonic effect: the inclusion of 4 wt.% SEBS-g-MAH leads to the most substantial improvements in both damping performance and tensile strength, exceeding the results obtained with 2 wt.% and 6 wt.% compatibilizer. The study highlights the need for carefully choosing the right wt.% of compatibilizers when aiming to formulate polymer blends with enhanced vibration dampening properties.

Water behavior at PEMFC triple phase boundary: Exploring ionomer and catalytic layer effects via molecular dynamic simulations and NMR experiments

Polymer electrolyte membrane fuel cells (PEMFCs) offer a clean and efficient energy generation technology. However, optimizing their performance in terms of water transport through the electrolyte membrane remains a challenge. In this study, we employ molecular dynamics simulation and nuclear magnetic resonance (NMR) experiments to investigate the influence of carbon materials and membrane thickness on water diffusion within the triple phase boundary of a PEMFC. Our theoretical investigation highlights the significant impact of Nafion content on water morphology within the system. The structural analysis reveals the intricate interplay between material properties and water behavior in confined environments. The formation of water channels facilitated by the ionomer enhances water mobility, while excessive ionomer content leads to reduced diffusion coefficients. Experimental measurements using NMR diffusion validate the correlation between our simulation results and real-world observations. Furthermore, our Molecular Dynamic (MD) and NMR studies identify the optimal performance range for ionomer content, with systems containing 12 to 24 oligomers (20–30 % w/w) exhibiting superior water diffusion within Vulcan Carbon (VC) structures. By shedding light on water transport phenomena in PEMFCs, our findings contribute to a better understanding of fuel cell performance and provide valuable insights for the design and optimization of fuel cell systems.

NMR Self-Diffusion and Transverse Relaxation Time in Bitumen: The Effect of Aging.

In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T2 . The translational diffusion at T> of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T2 data could be described as a continuous unimodal distributions of relaxation times determined both at T< and T> .

Polarization Amplification in Dynamic Nuclear Polarization Magic-Angle Spinning Solid-State Nuclear Magnetic Resonance by Solubilizing Traditional Ionic Salts.

Dynamic nuclear polarization can improve the sensitivity of magic-angle spinning solid-state NMR experiments by 1-2 orders of magnitude. In aqueous media, experiments are usually performed using the so-called DNP juice, a glycerol-d8/D2O/H2O mixture (60/30/10, v/v/v) that can form a homogeneous glass at cryogenic temperatures. This acts as a cryoprotectant and prevents phase separation of the paramagnetic polarizing agents (PAs) that are added to the mixture to provide the source of electron spin polarization required for DNP. Here, we show that relatively high 1H DNP enhancements (∼60) can also be obtained in water without glycerol (or other glass forming agents) simply by dissolving high concentrations of electrolytes (such as NaCl or LiCl), which perturb the otherwise unavoidable ice crystallization observed upon cooling, thereby reducing PA phase separation and restoring DNP efficiency.

The Effect of Disorder on Endogenous MAS-DNP: Study of Silicate Glasses and Crystals.

In dynamic nuclear polarization nuclear magnetic resonance (DNP-NMR) experiments, the large Boltzmann polarization of unpaired electrons is transferred to surrounding nuclei, leading to a significant increase in the sensitivity of the NMR signal. In order to obtain large polarization gains in the bulk of inorganic samples, paramagnetic metal ions are introduced as minor dopants acting as polarizing agents. While this approach has been shown to be very efficient in crystalline inorganic oxides, significantly lower enhancements have been reported when applying this approach to oxide glasses. In order to rationalize the origin of the difference in the efficiency of DNP in amorphous and crystalline inorganic matrices, we performed a detailed comparison in terms of their magnetic resonance properties. To diminish differences in the DNP performance arising from distinct nuclear interactions, glass and crystal systems of similar compositions were chosen, Li2OCaO·2SiO2 and Li2CaSiO4, respectively. Using Gd(III) as polarizing agent, DNP provided signal enhancements in the range of 100 for the crystalline sample, while only up to around factor 5 in the glass, for both 6Li and 29Si nuclei. We find that the drop in enhancement in glasses can be attributed to three main factors: shorter nuclear and electron relaxation times as well as the dielectric properties of glass and crystal. The amorphous nature of the glass sample is responsible for a high dielectric loss, leading to efficient microwave absorption and consequently lower effective microwave power and an increase in sample temperature which leads to further reduction of the electron relaxation time. These results help rationalize the observed sensitivity enhancements and provide guidance in identifying materials that could benefit from the DNP approach.

Enhanced piroctone olamine retention from shampoo for superior anti-dandruff efficacy.

Dandruff is a pervasive chronic condition which negatively impacts quality of life. Effective treatment requires efficient delivery of scalp benefit agents that control commensal scalp Malassezia levels. Delivery of benefit agents from shampoos requires balancing many technical parameters to achieve the desired outcome without sacrificing secondary parameters, such as cosmetic attributes. To develop formulation technologies that increase the shampoo delivery efficiency of the scalp benefit agent piroctone olamine (PO). Increased delivery should result in increased anti-dandruff efficacy. Micellar Stability and Association parameters were quantified via dynamic surface tension and nuclear magnetic resonance (NMR) diffusion parameters, respectively. PO delivery has been assessed in vivo both on the scalp surface and follicular infindibula using extraction procedures and analytical analysis. Clinical anti-dandruff efficacy was assessed for an advanced delivery technology prototype in comparison to standard delivery technology. Shampoo prototypes have been developed that increase the delivery efficiency of PO. Both surfactant and polymer coacervate-based approaches have been developed. Decreased micellar stability results in weaker association between PO and micelles, resulting in more efficient PO retention on the scalp surface and delivery to the infundibula. Increased charge density of cationic polymers optimizes coacervation enabling improved PO delivery as well. Increased PO delivery has been shown clinically to result in higher anti-dandruff efficacy as measured by both visible flakes and underlying biomarkers. Increased efficiency PO delivery shampoos have been developed by optimization of both surfactant and coacervate parameters. The increased deposition efficiency results in significantly more products with significantly greater anti-dandruff efficacy.

Acrylamide derivatives: A dynamic nuclear magnetic resonance study.

Substituted acrylamides have found an extensive application in organic and medical chemistry; therefore, it is very important to get insight into their features such as electronic structure, spectral properties, and stereochemical transformations. A correct interpretation of the chemical behavior and biological activity of these heteroatomic systems is impossible without knowledge of the structure of stereodynamic forms and factors determining their relative stability. The structure and peculiarities of stereodynamic behavior of substituted acrylamides and their model compounds were studied by dynamic and multinuclear 1 H, 13 C, and 15 N nuclear magnetic resonance (NMR) spectroscopy in CDCl3 and DMSO-d6 solution. It has been established that acrylamides in solution are realized as Z- and E-isomers, with the E-rotamer being somewhat predominant. The obtained experimental values of the free activation energy of rotamers vary within 15-17 kcal/mol, depending on the stereochemical structure of the molecule. 15 N NMR spectroscopy is the most reliable and fastest method for determining the structural and stereochemical features of nitrogen-containing compounds.

A focus on detection of polymorphs by dynamic nuclear polarization solid-state nuclear magnetic resonance spectroscopy.

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy has found increasing application as a method for quantification and structure determination of solid forms (polymorphs) of organic solids and active pharmaceutical ingredients (APIs). However, ssNMR spectroscopy suffers from low sensitivity and resolution, making it challenging to detect dilute solid forms that may be present after recrystallization or reaction with co-formers. Cousin et al. (S. F. Cousin et al., Chem. Sci., 2023, https://doi.org/10.1039/D3SC02063K) have demonstrated that dynamic nuclear polarization (DNP) enhanced 13C cross-polarization (CP) saturation recovery experiments can be used to detect dilute polymorphic forms that are present within a mixture of solid forms. Enhancement of the NMR signal by DNP and differences in signal build-up rates for different polymorphs provide the sensitivity and contrast needed to resolve NMR signals from minor polymorphic forms. This method demonstrated by Cousin et al. should aid the discovery of solid drug forms.

Structure and properties of cerium phosphate and silicophosphate glasses

AbstractWe report on the fabrication, properties, and structure of cerium pyrophosphate glasses and partially substituted cerium silicophosphates. In those glasses, cerium occurs predominantly as Ce(III). A combination of dynamic nuclear magnetic resonance and electrical impedance spectroscopy is used to overcome the problem of assessing cerium speciation. While optical spectroscopy is unable to quantify the ratio of Ce(III)/Ce(IV) due to spectral overlap, proxy observations of the effect of silica‐for‐cerium substitution on optical extinction and the shape and width of the UV band gap corroborate vibrational spectroscopic data of the structural roles of cerium and silica. While silica bonding to phosphate units appears to stabilize Ce(IV), it also impedes the polaron transport, leading to higher polaron activation energy and lower electronic conductivity. On the other hand, Ce(III) is stabilized by coordinating to P = O.

Dynamic NMR Relaxometry as a Simple Tool for Measuring Liquid Transfers and Characterizing Surface and Structure Evolution in Porous Media.

Porous media containing voids which can be filled with gas and/or liquids are ubiquitous in our everyday life: soils, wood, bricks, concrete, sponges, and textiles. It is of major interest to identify how a liquid, pushing another fluid or transporting particles, ions, or nutriments, can penetrate or be extracted from the porous medium. High-resolution X-ray microtomography, neutron imaging, and magnetic resonance imaging are techniques allowing us to obtain, in a nondestructive way, a view of the internal processes in nontransparent porous media. Here we review the possibilities of a simple though powerful technique which provides various direct quantitative information on the liquid distribution inside the porous structure and its variations over time due to fluid transport and/or phase changes. It relies on the analysis of the details of the NMR (nuclear magnetic resonance) relaxation of the proton spins of the liquid molecules and its evolution during some process such as the imbibition, drying, or phase change of the sample. This rather cheap technique then allows us to distinguish how the liquid is distributed in the different pore sizes or pore types and how this evolves over time; since the NMR relaxation time depends on the fraction of time spent by the molecule along the solid surface, this technique can also be used to determine the specific surface of some pore classes in the material. The principles of the technique and its contribution to the physical understanding of the processes are illustrated through examples: imbibition, drying or fluid transfers in a nanoporous silica glass, large pores dispersed in a fine polymeric porous matrix, a pile of cellulose fibers partially saturated with bound water, a softwood, and a simple porous inclusion in a cement paste. We thus show the efficiency of the technique to quantify the transfers with a good temporal resolution.

Combining NMR and molecular dynamics simulations for revealing the alkali-ion transport in solid-state battery materials

Understanding the microscopic transport of alkali-ion in rechargeable battery materials is vital. Although nuclear magnetic resonance (NMR) is a powerful and versatile technique for probing ion transport, it alone can hardly obtain the explicit atomic picture. Provided that a proper theoretical method has been applied, molecular dynamic (MD) simulations could be used to explicitly predict atomic motions, and thus become a complementary tool to NMR. However, the combination of NMR and MD for studying the dynamic processes of battery materials are not widely used because of the mismatch of the spatial and time scales of dynamic process accessible by them. This article presents a brief conjunct view of them on alkali-ion transport in the bulk of solid-state battery materials. Moreover, we outlook the challenges of studying alkali-ion transport on battery interfaces with NMR and MD simulations.

Enzymatic processing and MHC loading 3Molecular mechanisms of chaperone-mediated MHC-I peptide loading

Peptide loading of MHC-I molecules occurs as a result of dynamic protein folding and assembly processes involving not only the MHC-I heavy chain, the light chain, beta 2-m, and antigenic peptide, but also the components of the peptide loading complex (PLC), including tapasin, as well as the PLC-independent chaperone, TAP binding protein, related (TAPBPR). Structural studies of tapasin and TAPBPR reveal that these, like many other proteins, contain both well-ordered domains as well as regions of disorder. To examine the contributions of disordered regions of both MHC-I molecules and of TAPBPR, we have examined X-ray structures of MHC-I molecules assembled with disulfide linked truncated peptides, of TAPBPR/MHC-I complexes containing truncated peptides, and of nanobody/TAPBPR complexes. Different disordered regions of TAPBPR rigidify on interaction with MHC-I or with specific nanobodies. Conversely, the peptide binding groove of MHC-I structurally rearranges on interaction with TAPBPR. These observations are consistent with solution nuclear magnetic resonance (NMR) spectroscopy data examining the interaction of TAPBPR with isotope-labeled peptide-MHC-I complexes. The dynamic NMR data reveal a transient pMHC-I/TAPBPR intermediate that controls the selection of high-affinity peptides. We propose a model of negative allosteric coupling that involves the entire peptide binding groove. Such a model, based primarily on observations of TAPBPR should be applicable to tapasin in the PLC as well.

Design and Simulation Studies of a Continuously Tunable Sub-THz Gyrotron Using Magnetic and Thermal Tuning Schemes

In this article, the frequency tunability of a sub-Terahertz (THz) gyrotron has been investigated using both magnetic and thermal tuning schemes. A triode-type magnetron injection gun (MIG) has been designed using an electron optics tool, which predicted an annular electron beam with a < 4% velocity spread. Furthermore, the cavity has been modeled to operate in the TE11,2 mode at 527 GHz for dynamic nuclear polarization-nuclear magnetic resonance (DNP/NMR) applications. The transient behavior of the present gyrotron has been studied using a time-dependent self-consistent multimode code. A maximum continuous wave (CW) power of ~14 W was obtained at 527.20 GHz with 16.75 kV, 90 mA, and 1.85 pitch of e-beam. The tunable bandwidth has been obtained as ~0.31 GHz (527.20–527.51 GHz) by using a magnetic tuning scheme and ~0.31 GHz (526.90–527.20 GHz) by using the thermal tuning scheme by taking advantage of gyrotron sensitivity on cavity structural parameters and cavity shape.

Physical aging of PC:PS blends: Dynamic mechanical analysis and nuclear magnetic resonance studies

AbstractThe effect of physical aging of the partially miscible blend of polycarbonate:polystyrene (PC:PS) at temperatures near the glass transition temperature (Tg) of the PS was studied as a function of time. For this purpose, blends of PC and PS with different ratios were elaborated and characterized using SEM, FTIR, DSC, and DMA techniques. The results indicated the presence of weak interaction upon blending with a maximum of interaction for the 50:50 blend. The effect of physical aging on the latter was then investigated via DMA, DSC, and NMR analyses. The DMA results showed that both phases were sensitive to aging. The effect was found to be strongly dependent on both the temperature and time. The aging of PC:PS blend was also found to trap stress during the process which induced an instability in the viscoelastic behavior. The latter was found to be associated with a phase‐separation morphology of the blend and influenced by its composition. The NMR analysis also showed a pronounced distortion of the conformation combined with increasing molecular motion. These effects were found to be important for aging below the PS's Tg.

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex.

Dynamic solution nuclear magnetic resonance (NMR) spectroscopy is the typical method of characterizing the dynamic rearrangements of atoms within the coordination sphere for transition metal polyhydride complexes. Line shape fitting of the dynamic NMR spectra can lead to estimates for the activation parameters of the dynamic rearrangement processes. A combination of dynamic 31P-{1H} NMR spectroscopy of metal-bound phosphorus atoms with dynamic 1H-{31P} NMR spectroscopy of hydride ligands may identify hydride ligand rearrangements that occur in conjunction with a phosphorus atom rearrangement. For molecules that exhibit such a coupled pair of rearrangements, dynamic NMR spectroscopy can be used to test theoretical models for the ligand rearrangements. Dynamic 1H-{31P} NMR spectroscopy and line shape fitting can also identify the presence of an exchange process that moves a specific hydride ligand beyond the metal's inner coordination sphere through a proton exchange with a solvent molecule such as adventitious water. The preparation of a new compound, ReH5(PPh3)2(sec-butyl amine), that exemplifies multiple dynamic rearrangement processes is presented along with line shape fitting of dynamic NMR spectra of the complex. Line shape fitting results can be analyzed by the Eyring equation to estimate the activation parameters for the identified dynamic processes.

S-Palmitoylation and Sterol Interactions Mediate Antiviral Specificity of IFITMs.

Interferon-induced transmembrane proteins (IFITM1, 2, and 3) are important antiviral proteins that are active against many viruses, including influenza A virus (IAV), dengue virus (DENV), Ebola virus (EBOV), Zika virus (ZIKV), and severe acute respiratory syndrome coronavirus (SARS-CoV). IFITM proteins exhibit specificity in activity, but their distinct mechanisms of action and regulation are unclear. Since S-palmitoylation and cholesterol homeostasis are crucial for viral infections, we investigated IFITM interactions with cholesterol by photoaffinity cross-linking in mammalian cells along with molecular dynamic simulations and nuclear magnetic resonance analysis in vitro. These studies suggest that cholesterol can directly interact with S-palmitoylated IFITMs in cells and alter the conformation of IFITMs in membrane bilayers. Notably, we discovered that the S-palmitoylation levels regulate differential IFITM protein interactions with cholesterol in mammalian cells and specificity of antiviral activity toward IAV, SARS-CoV-2, and EBOV. Our studies suggest that modulation of IFITM S-palmitoylation levels and cholesterol interaction influence host susceptibility to different viruses.