Liquid-state Nuclear Magnetic Resonance Research Articles

The role of TiO2:SnO2 heterojunction for partial oxidation of methane by photoelectrocatalytic process at room temperature

Partial Oxidation of Methane into hydrocarbons using photoelectrochemical routes is attractive from a sustainability point of view owing to the possibility of using renewable energy (i.e., solar illumination) to activate this stable molecule. However, the process demands the development of novel catalysts that can promote methane activation and oxidation in a controlled manner to increase energy conversion efficiency. Herein, we demonstrated that semiconductor heterostructures improved charge separation compared to the individual materials alone. A more effortless transfer between bands favors the separation of the electron-hole (e−/h+) pairs generated by the photoelectrocatalytic system and prevents them from recombining. This process produces reactive oxygens, essential to driving methane oxidation conversion of the C–H bond cleavage. TiO2:SnO2 semiconductor heterojunction catalysts in film shape were investigated for methane oxidation via a photoelectrocatalytic process. The methane oxidation reactions were carried out in an inflow and sealed electrochemical system for 1 h. Liquid-state nuclear magnetic resonance revealed methanol and acetic acid as the main liquid products, where the TiO2:SnO2 heterojunction exhibited better performance with values of 30 and 8 µmol.cm−2.h−1, respectively. Compared to their materials alone, the superior performance of the TiO2:SnO2 heterojunction is attributed to the formation of heterostructure type II that enables a more effortless transfer between bands, facilitating the separation of the generated e−/h+ pairs under UV-Vis irradiation. The outcomes achieved here will motivate further studies for developing semiconductor heterojunction structure catalysts in photoelectrocatalysis to partially oxidize methane into valuable chemicals.

A novel halogen-free flame-retardant fabrication for the study of smoke suppression and flame retardancy of polystyrene

A novel P–N flame-retardant (PON) was synthesized by nucleophilic substitution reaction using diphenyl phosphoryl chloride and piperazine as raw materials. Its chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR), liquid-state nuclear magnetic resonance (NMR), high resolution mass spectrometry (HEMS) and elemental analysis, and its thermal stability by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Subsequently, five char-forming agents, namely pentaerythritol (PER), chitosan (CTS), lignin (LI), graphene (GN) and expandable graphite (EG), were selected to form five intumescent flame-retardants in a 1:1 mass ratio with PON. Polystyrene (PS) composites were prepared by melt blending method. The synergistic effect of PON and different char-forming agents on thermal stability, combustion behavior and flame retardancy of PS composites were systematically investigated. The results showed that the PS/10% PON/10% EG composite had the highest limiting oxygen index (LOI) value of 25.8%, and the cone calorimetric test showed that the peak heat release rate (pHRR), total heat release rate (THR), and total smoke release (TSP) of the composite were reduced by 74.6%, 24.4% and 43.6%, respectively, compared with neat PS, and this composite exhibited the most excellent flame retardancy. Finally, the flame-retardant mechanism of PS/10% PON/10% EG composite was discussed and proposed by the results of scanning electron microscope (SEM), thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG-IR), and pyrolysis-gas chromatography-mass (PY-GC/MS) measurements in detail.

SHARPER-DOSY: Sensitivity enhanced diffusion-ordered NMR spectroscopy

Since its discovery in mid-20th century, the sensitivity of Nuclear Magnetic Resonance (NMR) has increased steadily, in part due to the design of new, sophisticated NMR experiments. Here we report on a liquid-state NMR methodology that significantly increases the sensitivity of diffusion coefficient measurements of pure compounds, allowing to estimate their sizes using a much reduced amount of material. In this method, the diffusion coefficients are being measured by analysing narrow and intense singlets, which are invariant to magnetic field inhomogeneities. The singlets are obtained through signal acquisition embedded in short (<0.5 ms) spin-echo intervals separated by non-selective 180° or 90° pulses, suppressing the chemical shift evolution of resonances and their splitting due to J couplings. The achieved 10−100 sensitivity enhancement results in a 100−10000-fold time saving. Using high field cryoprobe NMR spectrometers, this makes it possible to measure a diffusion coefficient of a medium-size organic molecule in a matter of minutes with as little as a few hundred nanograms of material.

Combined Liquid-State and Solid-State Nuclear Magnetic Resonance at Natural Abundance for Comparative Higher Order Structure Assessment in the Formulated-State of Biphasic Biopharmaceutics.

A higher-order structure (HOS) is critical to a biopharmaceutical drug as the three-dimensional structure governs its function. Even the partial perturbation in the HOS of the drug can alter the biological efficiency and efficacy. Due to current limitations in analytical technologies, it is imperative to develop a protocol to characterize the HOS of biopharmaceuticals in the native formulated state. This becomes even more challenging for the suspension formulations where solution and solid phases co-exist. Here, we have used a combinatorial approach using liquid (1D 1H) and solid-state (13C CP MAS) NMR methodology to demonstrate the HOS in the biphasic microcrystalline suspension drug in its formulated state. The data were further assessed by principal component analysis and Mahalanobis distance (DM) calculation for quantitative assessment. This approach is sufficient to provide information regarding the protein HOS and the local dynamics of the molecule when combined with orthogonal techniques such as X-ray scattering. Our method can be an elegant tool to investigate batch-to-batch variation in the process of manufacture and storage as well as a biosimilarity comparison study for biphasic/microcrystalline suspension.

Solid-Effect Dynamic Nuclear Polarization in Viscous Liquids at 9.4 T Using Narrow-Line Polarizing Agents.

Dynamic nuclear polarization (DNP) is a hyperpolarization method that is widely used for increasing the sensitivity of nuclear magnetic resonance (NMR) experiments. DNP is efficient in solid-state and liquid-state NMR, but its implementation in the intermediate state, namely, viscous media, is still less explored. Here, we show that a 1H DNP enhancement of over 50 can be obtained in viscous liquids at a magnetic field of 9.4 T and a temperature of 315 K. This was accomplished by using narrow-line polarizing agents in glycerol, both the water-soluble α,γ-bisdiphenylen-β-phenylallyl (BDPA) and triarylmethyl radicals, and a microwave/RF double-resonance probehead. We observed DNP enhancements with a field profile indicative of the solid effect and investigated the influence of microwave power, temperature, and concentration on the 1H NMR results. To demonstrate potential applications of this new DNP approach for chemistry and biology, we show hyperpolarized 1H NMR spectra of tripeptides, triglycine, and glypromate, in glycerol-d8.

Monitoring Changes in Electrolyte Composition of Commercial Li-Ion Cells after Cycling using NMR Spectroscopy and Differential Thermal Analysis

We illustrate a simple and effective electrolyte extraction methodology from commercial 18650 lithium-ion cells. This methodology is based on a liquid-liquid extraction step, which is highlighted for robustness, reproducibility, and reliability. We assess the consumption of electrolyte by tracking compositional changes using liquid-state nuclear magnetic resonance (NMR) spectroscopy, supported by differential thermal analysis (DTA) before and after cell cycling. An analysis method that monitors compositional dynamics is presented and shows the impact of these changes throughout a cell’s lifetime. Such methodology can be employed in the understanding of electrolyte degradation mechanisms to enhance the understanding of performance fade in commercial cells. Moreover, it will help build robust mathematical models that are able to predict the drive of cell degradation and ultimate failure.

Reversible Zinc Electrodeposition at -60 °C Using a Deep Eutectic Electrolyte for Low-Temperature Zinc Metal Batteries.

Rechargeable zinc (Zn) metal batteries are attractive for use as electrochemical energy storage systems on a global scale because of the low cost, high energy density, inherent safety, and strategic resource security of Zn metal. However, at low temperatures, Zn batteries typically suffer from high electrolyte viscosity and unfavorable ion transport properties. Here, we studied reversible Zn electrodeposition in mixtures of 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) ionic liquid, γ-butyrolactone (GBL) organic solvent, and Zn(TFSI)2 zinc salt. The electrolyte mixtures enabled reversible Zn electrodeposition at temperatures as low as -60 °C. An electrolyte composed of 0.1 M Zn(TFSI)2 in [EMIm]TFSI:GBL with a volume ratio of 1:3 formed a deep eutectic solvent that optimized electrolyte conductivity, viscosity, and the zinc diffusion coefficient. Liquid-state 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and molecular dynamic (MD) simulations indicate increased formation of contact ion pairs and the reduction of ion aggregates are responsible for the optimal composition.

Assessment of Aging Impact on Wax Crystallization in Selected Asphalt Binders.

For a better understanding of the changing trend in crystalline components of asphalt binders, asphalt binders originating from the SHRP Materials Reference Library with different oxidation degrees (unaged, 20 h PAV, and 60 h PAV) were prepared. The native asphalt binders and their oxidized residues were characterized by liquid-state nuclear magnetic resonance (NMR) spectroscopy and high-temperature gas chromatography (HTGC). The results showed that, compared with other carbon types, the content of internal methylene carbons of long paraffinic chains between different SHRP binders was quite different. The NMR average length of a long paraffinic internal methylene chain showed a good correlation with the wax content obtained at -20 °C using the methyl ethyl ketone (MEK) precipitation method and also the recently developed variable-temperature Fourier-transform infrared spectroscopy (VT-FTIR) method. In most cases, the average length of straight internal methylene carbons of a long paraffinic chain terminated by a methyl group increased with the oxidation of the asphalt binder. However, the difference caused by oxidation was significantly smaller than the difference caused by the source of the asphalt binder. In general, oxidation will make the n-alkanes distributed in asphalt binder fall within a narrower range. The carbon number of n-alkanes in the asphalt binder generally grew with oxidation.

Transfer of phase coherence by the dipolar field in total correlation liquid state nuclear magnetic resonance spectroscopy.

In this work, it is shown that radio-frequency pulse trains designed for total correlation nuclear magnetic resonance spectroscopy can mediate inter-molecular transfer of phase coherence from one spin species to another by the dipolar field. In contrast to previous studies (where short pulses interleaved with long free precession delays were used), here the transverse component of the dipolar field plays an important role. The transfer is so efficient that signal intensities close to those of a single pulse experiment can be achieved. The results are rationalized by numerical simulations that take into account relaxation and diffusion.

Sample illumination device facilitates in situ light-coupled NMR spectroscopy without fibre optics

In situ illumination of liquid-state nuclear magnetic resonance (NMR) samples makes it possible for a wide range of light-dependent chemical and biological phenomena to be studied by the powerful analytical technique. However, the position of an NMR sample deep within the bore of the spectrometer magnet renders such illumination challenging. Here, we demonstrate the working principles of a sample illumination device (NMRtorch) where a lighthead containing an LED array is positioned directly at the top of an NMRtorch tube which is inserted into the NMR spectrometer. The wall of the tube itself acts as a light guide, illuminating the sample from the outside. We explore how this new setup performs in a number of photo-NMR applications, including photoisomerisation and photo-chemically induced dynamic nuclear polarisation (photo-CIDNP), and demonstrate the potential for ultraviolet (UV) degradation studies with continuous online NMR assessment. This setup enables users of any typical liquid-state spectrometer to easily perform in situ photo-NMR experiments, using a wide range of wavelengths.

Enhanced Nuclear Magnetic Resonance Spectroscopy with Isotropic Mixing as a Pseudodimension.

Chemical analysis based on liquid-state nuclear magnetic resonance spectroscopy exploits numerous observables, mainly chemical shifts, relaxation rates, and internuclear coupling constants. Regarding the latter, the efficiencies of internuclear coherence transfers may be encoded in spectral peak intensities. The dependencies of these intensities on the experimental parameter that influences the transfer, for example, mixing time, are an important source of structural information. Yet, they are costly to measure and difficult to analyze. Here, we show that peak intensity build-up curves in two-dimensional total correlation spectroscopy (2D TOCSY) experiments may be quickly measured by employing nonuniform sampling and that their analysis can be effective if supported by quantum mechanical calculations. Thus, such curves can be used to form a new, third pseudodimension of the TOCSY spectrum. Similarly to the other two frequency dimensions, this one also resolves ambiguities and provides characteristic information. We show how the approach supports the analysis of a fragment of protein Tau Repeat-4 domain. Yet, its potential applications are far broader, including the analysis of complex mixtures or other polymers.

Characterization of grafting properties of ABS latexes: ATR-FTIR vs NMR spectroscopy

Acrylonitrile–Butadiene–Styrene (ABS) polymers have a complex microstructure which is formed during the grafting reaction of a polybutadiene seed latex. During the reaction, some styrene-acrylonitrile (SAN) chains are grafted onto the polybutadiene (PB) backbone chains, and this grafting is critical to achieve effective dispersion and compatibility of both phases. Therefore, accurate characterization of grafting properties helps understanding the polymerization mechanism as well as the final properties of the ABS polymer and its applications properties. In this work, the grafting properties of ABS latexes were determined by separation of the soluble and insoluble phase of the polymer, followed by the characterization of these phases using analytical techniques. Phase separation was carried out dispersing the latex in acetone followed by ultracentrifugation. The soluble and insoluble polymer phases were for the first time analysed by NMR spectroscopy to obtain the corresponding fractions of SAN and PB in each phase. The soluble fraction was analysed by liquid-state 1H Nuclear Magnetic Resonance (NMR) spectroscopy, whereas the insoluble fraction was analysed by solid-state 13C NMR spectroscopy. Moreover, both phases were analysed by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and the results obtained are compared and discussed in this article. We found that the most accurate grafting properties are achieved by analysing the composition of the soluble and insoluble fraction by NMR spectroscopy.

Tomographic entanglement indicators from NMR experiments.

In recent years, the performance of different entanglement indicators obtained directly from tomograms has been assessed in continuous-variable and hybrid quantum systems. In this paper, we carry out this task in the case of spin systems. We compute the entanglement indicators from actual experimental data obtained from three liquid-state nuclear magnetic resonance (NMR) experiments and compare them with standard entanglement measures calculated from the corresponding density matrices, both experimentally reconstructed and numerically computed. The gross features of entanglement dynamics and spin squeezing properties are found to be reproduced by these entanglement indicators. However, the extent to which these indicators and spin squeezing track the entanglement during time evolution of the multipartite systems in the NMR experiments is very sensitive to the precise nature and strength of interactions as well as the manner in which the full system is partitioned into subsystems. We also use the IBM quantum computer to implement equivalent circuits that capture the dynamics of the multipartite system in one of the NMR experiments and carry out a similar comparative assessment of the performance of tomographic indicators. This exercise shows that these indicators can estimate the degree of entanglement without necessitating detailed state reconstruction procedures, establishing the advantage of the tomographic approach.

Stable Metal–Halide Perovskite Colloids in Protic Ionic Liquid

Stable Metal–Halide Perovskite Colloids in Protic Ionic Liquid

Methoxpropamine (MXPr) in powder, urine and hair samples: Analytical characterization and metabolite identification of a new threat

Methoxpropamine (MXPr) is an arylcyclohexylamine dissociative drug with structural similarities with 3-MeO-PCE, ketamine and deschloroketamine. MXPr was identified for the first time in Europe in October 2019 in Denmark and is considered a new psychoactive substance. We undertook the molecular identification and characterization of MXPr in urine, hair and powder samples. We used a combination of several analytical methods: liquid-state nuclear magnetic resonance (NMR), infra-red spectroscopy (IR) and liquid chromatography high-resolution mass spectrometry (LC-HRMS). The second objective was to explore the metabolism of MXPr in silico and in vitro. To detect characteristic metabolites that prove MXPr consumption by urine analysis, pooled human liver microsome (pHLM) assays were performed and evaluated using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS). A software algorithm (Unifi®) was used to predict in silico biotransformations of MXPr. Three metabolites were identified in the in vitro studies including N-despropyl(nor)MXPr, O-desmethyl MXPr and dihydroMXPr. Most of these phase II metabolites were confirmed to be present in urine and hair samples collected from an MXPr consumer. This is the first report of the identification of MXPr in France with analytical findings. This study highlights the challenge of identifying new psychoactive substances (NPS) when they are missing from compound libraries and if a standard is not available. The use of various complementary analytical methods combined with HRMS offers a promising approach for the molecular characterization of NPS.

Distribution and Quantification of Diverse Functional Groups on Phosphorylated Nanocellulose Surfaces.

Phosphorylated cellulose nanofiber (CNF) is attracting attention as a newly emerged CNF with high functionality. However, many structural aspects of phosphorylated CNF remain unclear. In this study, we investigated the chemical structures and distribution of ionic functional groups on the phosphorylated CNF surfaces via liquid-state nuclear magnetic resonance measurements of colloidal dispersion. In addition to the monophosphate group, polyphosphate groups and cross-linked phosphate groups were introduced in the phosphorylated CNFs. The proportion of polyphosphate groups increased as the phosphorylation time increased, reaching ∼30% of all phosphate groups. Only a small amount of cross-linked phosphate groups existed in the phosphorylated CNF after a prolonged reaction time. Furthermore, phosphorylation of cellulose using urea and phosphoric acid was found to be regioselective at the C2 and C6 positions. There existed no significant difference between the surface degrees of substitution at the C2 and C6 positions of the phosphorylated CNFs.

Preparation of Well-Compatibilized PP/PC Blends and Foams Thereof

The performance of polypropylene-poly(ethylene brassylate) block and graft copolymers and a polypropylene-polycaprolactone graft copolymer as compatibilizers for polypropylene-rich polypropylene/bisphenol A polycarbonate (PP/PC, 80/20 wt/wt) blends was elucidated. The copolymers were synthesized either by metal-catalyzed ring-opening polymerization or transesterification of a presynthesized polyester, initiated by hydroxyl-functionalized PPs, which themselves were obtained by catalytic routes or reactive extrusion, respectively. Spectroscopic fingerprints of the copolymers from liquid-state nuclear magnetic resonance (NMR) in combination with scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic mechanical thermal analysis (DMTA), and rheology analyses of the blends indicated that the compatibilizers spontaneously organize at the interface of the two immiscible polymers leading to the formation of uniform, stable, nanophase morphologies. The effect of the compatibilizers on the performance of the PP/PC blends was evaluated, and well-compatibilized PP/PC blends showed improved melt strength and strain hardening when compared to pure PP. This was verified by the successful foam extrusion using isobutane as a blowing agent of well-compatibilized PP/PC blends to low-density PP-based foams, for which normally long-chain branched PP is required.

New insights into the use of hydroxypropyl cellulose for drug solubility enhancement: An analytical study of sub‐molecular interactions with fenofibrate in solid state and aqueous solutions

AbstractHydroxypropyl cellulose (HPC) is a solubility enhancer used for poorly soluble drugs, nano‐suspensions and amorphous solid dispersions (ASD). However, the underlying mechanism remains unclear. ASDs of a poorly soluble drug, fenofibrate (FEN), were analyzed using liquid nuclear magnetic resonance (NMR) and solid state NMR (ss‐NMR). Liquid NMR revealed interactions between the pyranose ring of the HPC molecule and the diphenylketone from FEN. The water accessibility of the CH3 groups in HPC and FEN is very low, they form a hydrophobic zone in aqueous solution that may sustain the drug nucleation. Moreover, ss‐NMR measurements confirmed very low drug crystallinity for HPC‐FEN ASDs. Cross‐polarization and direct polarization 13C spectra, 13C‐CPMAS and 13C‐PARIS, distinguished the most rigid and flexible portions in concordance with the ss‐NMR proton T1 and T1r relaxation results. Although HPC side chains (hydroxypropoxy) are the most flexible portions, their flexibility is moderate and high rigidity is the predominant. The ss‐NMR proton relaxation indicates a rather homogeneous distribution of the components (HPC and FEN) in the solid mixtures. The versatile NMR methodology proposed can be used to study other polymer‐drug systems and it may contribute to understand relevant functional aspects such as the rate of drug‐delivery and their stability.

Nuclear Magnetic Resonance Spectroscopy: A Multifaceted Toolbox to Probe Structure, Dynamics, Interactions, and Real-Time In Situ Release Kinetics in Peptide-Liposome Formulations.

Liposomal formulations represent attractive biocompatible and tunable drug delivery systems for peptide drugs. Among the tools to analyze their physicochemical properties, nuclear magnetic resonance (NMR) spectroscopy, despite being an obligatory technique to characterize molecular structure and dynamics in chemistry as well as in structural biology, yet appears to be rather sparsely used to study drug-liposome formulations. In this work, we exploited several facets of liquid-state NMR spectroscopy to characterize liposomal delivery systems for the apelin-derived K14P peptide and K14P modified by Nα-fatty acylation. Various liposome compositions and preparation modes were analyzed. Using NMR, in combination with cryo-electron microscopy and dynamic light scattering, we determined structural, dynamic, and self-association properties of these peptides in solution and probed their interactions with liposomes. Using 31P and 1H NMR, we characterized membrane fluidity and thermotropic phase transitions in empty and loaded liposomes. Based on diffusion and 1H NMR experiments, we localized and quantified peptides with respect to the interior/exterior of liposomes and changes over time and upon thermal treatments. Finally, we assessed the release kinetics of several solutes and compared various formulations. Taken together, this work shows that NMR has the potential to assist the design of peptide/liposome systems and more generally drug delivery systems.

Screening Metal-Organic Frameworks for Separation of Binary Solvent Mixtures by Compact NMR Relaxometry.

Metal–organic frameworks (MOFs) have great potential as an efficient alternative to current separation and purification procedures of a large variety of solvent mixtures—a critical process in many applications. Due to the huge number of existing MOFs, it is of key importance to identify high-throughput analytical tools, which can be used for their screening and performance ranking. In this context, the present work introduces a simple, fast, and inexpensive approach by compact low-field proton nuclear magnetic resonance (NMR) relaxometry to investigate the efficiency of MOF materials for the separation of a binary solvent mixture. The mass proportions of two solvents within a particular solvent mixture can be quantified before and after separation with the help of a priori established correlation curves relating the effective transverse relaxation times T2eff and the mass proportions of the two solvents. The new method is applied to test the separation efficiency of powdered UiO-66(Zr) for various solvent mixtures, including linear and cyclic alkanes and benzene derivate, under static conditions at room temperature. Its reliability is demonstrated by comparison with results from 1H liquid-state NMR spectroscopy.