Liquid-state Nuclear Magnetic Resonance Research Articles

Cosolvent-free sol–gel synthesis of macroporous silica gels from tetramethoxysilane–tetraethoxysilane mixtures

Abstract Tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and their mixtures were used for the cosolvent-free synthesis of macroporous silica gels as precursors for monolithic silica glasses. The liquid-state 29Si nuclear magnetic resonance (NMR) spectroscopy of precursor solutions indicated that cross-transesterification between TMOS and TEOS was completed in a few hours at 20 °C in the presence of an acid catalyst, whereas it was negligible when the catalyst was absent. In the precursor solutions prepared from TMOS, phase separation occurred after gelation, resulting in translucent gels. In contrast, in the solutions prepared from TEOS or a mixture of TMOS and TEOS at a TMOS mole fraction of 0.8, the phase separation can be induced before gelation, and opaque xerogels were easily obtained without fracture. The average size of macroscopic particles and macroporous structures were uniform over opaque xerogels prepared from TEOS. In contrast, in opaque xerogels prepared from the TMOS-rich mixture of TMOS and TEOS, the average particle size and macroscopic porosity inside them were notably smaller than those of the subsurface, probably because of a large exotherm upon gelation and the resulting temperature gradient in the gelling solutions. Such spatial morphology distribution made the sintering of the opaque gels into clear silica glasses difficult. Opaque gels prepared from TEOS and translucent gels prepared from solutions containing TMOS were transformed to clear silica glasses in high yields of ~99% by sintering in a helium atmosphere at 1050–1350 °C. Graphical abstract

Identification and quantification of phosphate turnover indicators after long-term compost application – long-term and single season effects

Abstract Background and aims Soil organic phosphorus (Porg) is of interest for plant nutrition because it can comprise between 20 and 80% of total soil phosphate (P). This study aims to examine the effect of compost application on soil phosphatases and microbial biomass, which influence the P turnover and, furthermore, to examine the speciation of Porg. Methods Soil from a long-term field experiment (since 1997) which compares compost application with inorganic fertilization was analyzed for calcium-acetate-lactate extractable P (CAL-P), Olsen-P, acid (Acid-Pase) and alkaline (Alk-Pase) phosphatase activity and microbial biomass P. Porg speciation was additionally analyzed with liquid-state 31P nuclear magnetic resonance spectroscopy (31P-NMR). Results We found a significant increasing long-term effect of high compost application (equivalent to 400 kg ha−1 N (400)) on Acid-Pase (45%) and Alk-Pase (58%). After compost application, Acid-Pase increased by 41% in treatment 400 (3 days after compost application (DAA)). The 31P-NMR analysis showed a significant increase of inorganic orthophosphate (55%) after high compost application. Furthermore, the total phosphomonoester region was significantly decreased in the treatment 400 (8%). Conclusions We demonstrated that long-term compost application increases phosphatase activity which plays a key role in the mineralization of soil Porg. In particular, the decrease of the concentration of Porg species in the phosphomonoester region in the treatment 400 with high compost application highlights that an increased turnover affects this soil P pool and may provide P to plants. This knowledge provides a better understanding of how the P cycle responds to long-term compost fertilization.

Insoluble Network Skeleton and Soluble Components of Nylon 6,6-Sputtered Nanoparticles: Insights from Liquid-State and Solid-State NMR Analysis.

In this study, we performed a detailed analysis of -sputtered-nylon 6,6 plasma polymer nanoparticles (NPs). Following a previous study using standard techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, we employed unconventional approaches, specifically solid- and liquid-state high-resolution nuclear magnetic resonance (NMR) spectroscopy, supplemented by gel permeation chromatography (GPC). Scanning electron microscopy (SEM) was also used to examine changes in the size of the NPs after contact with solvents and after heating. Our investigations revealed suspected strong binding and networking of the NPs, and a soluble monomer/oligomer phase was identified and characterised. This fraction is removable using solvent or heat treatment without significantly affecting the size of the NPs. Additionally, we suggested the chemical structure of this soluble phase. Our findings support the proposed rubber-like character of plasma polymer NPs and explain their strong tendency to reflect from substrates upon high-speed impact.

Structural insights into the binding mechanism of Clr4 methyltransferase to H3K9 methylated nucleosome

The establishment and maintenance of heterochromatin, a specific chromatin structure essential for genomic stability and regulation, rely on intricate interactions between chromatin-modifying enzymes and nucleosomal histone proteins. However, the precise trigger for these modifications remains unclear, thus highlighting the need for a deeper understanding of how methyltransferases facilitate histone methylation among others. Here, we investigate the molecular mechanisms underlying heterochromatin assembly by studying the interaction between the H3K9 methyltransferase Clr4 and H3K9-methylated nucleosomes. Using a combination of liquid-state nuclear magnetic resonance spectroscopy and cryo-electron microscopy, we elucidate the structural basis of Clr4 binding to H3K9-methylated nucleosomes. Our results reveal that Clr4 engages with nucleosomes through its chromodomain and disordered regions to promote de novo methylation. This study provides crucial insights into the molecular mechanisms governing heterochromatin formation by highlighting the significance of chromatin-modifying enzymes in genome regulation and disease pathology.

Water-Enhanced Direct Air Capture of Carbon Dioxide in Metal-Organic Frameworks.

We have developed two series of amine-functionalized zirconium (Zr) metal-organic framework-808 (MOF-808), which were produced by postsynthetic modifications to have either amino acids coordinated to Zr ions (MOF-808-AAs) or polyamines covalently bound to the chloro-functionalized structure (MOF-808-PAs). These MOF variants were comprehensively characterized by liquid-state 1H nuclear magnetic resonance (NMR) measurements and potentiometric acid-base titration to determine the amounts of amines, energy-dispersive X-ray spectroscopy to assess the extent of covalent substitution by polyamines, powder X-ray diffraction analysis to verify the maintenance of the MOF crystallinity and structure after postsynthetic modifications, nitrogen sorption isotherm measurements to confirm retention of the porosity, and water sorption isotherm measurements to find the water uptake in the pores of each member of the series. Evaluation and testing of these compounds in direct air capture (DAC) of CO2 showed improved CO2 capture performance for the functionalized forms, especially under humid conditions: In dry conditions, the l-lysine- and tris(3-aminopropyl)amine-functionalized variants, termed as MOF-808-Lys and MOF-808-TAPA, exhibited the highest CO2 uptakes at 400 ppm, measuring 0.612 and 0.498 mmol g-1, and further capacity enhancement was achieved by introducing 50% relative humidity, resulting in remarkable uptakes of 1.205 and 0.872 mmol g-1 corresponding to 97 and 75% increase compared to the dry uptakes, respectively. The mechanism underlying the enhanced uptake efficiency was revealed by 13C solid-state NMR and temperature-programmed desorption measurements, indicating the formation of bicarbonate species, and therefore a stoichiometry of 1:1 CO2 to each amine site.

Ray Freeman. 6 January 1932—1 May 2022

Ray Freeman pioneered many of the important advances in the technique of liquid-state nuclear magnetic resonance spectroscopy: he changed fundamentally the ways in which chemists and structural biologists use NMR. Born in Nottingham, he was an undergraduate chemistry student at Oxford after National Service working with radar, and completed his Part II and doctoral research with Rex Richards (FRS 1959). After brief spells with Anatole Abragam (ForMemRS 1983) in Saclay, France, and at the National Physical Laboratory in Teddington, he worked for 10 years in the research department of Varian Associates, Palo Alto, USA. He was appointed as lecturer in physical chemistry and tutorial fellow of Magdalen College, Oxford, in 1973, and subsequently promoted to Aldrichian praelector. In 1987 he was appointed to the John Humphrey Plummer chair at the University of Cambridge, where he remained active in research long after his retirement in 1999, publishing his last paper at the age of 84.

Characterization of crude extracts from willow barks and their performance as proanthocyanidin -based coagulants in water treatment

This work investigates the proanthocyanidin profile of willow bark crude extracts and these materials were cationized and preliminarily tested as biocoagulants for water treatment. The characteristics of crude extracts proanthocyanidin were investigated using size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). XPS analysis indicates that the crude extracts contain significant amounts of sugars. Furthermore, SEC and liquid-state NMR spectroscopy showed that crude extract contains roughly 3–4 flavan-3-ol units with procyanidin (PC)/ prodelphinidin (PD) ratio of roughly 3–5. Thus, the modified form of tannin (proanthocyanidin-enriched) coagulants obtained the higher cationic charge density. The coagulation experiments with kaolin-river water mixture suggested that all the selected willow hybrids’ tannin coagulants were effective in settling the particles down. This study indicates that the value of willow bark can be significantly improved by the usage of crude extracts for water treatment.

Novel Operando Nuclear Magnetic Resonance Approach for Tracking the Electrode State of Charge in Li/Na-Ion Batteries

Lithium and sodium-ion batteries have become the focal point of interest for the energy transition due to their promising applications for electric cars and energy grid storage. Operando characterization of batteries is critical to understand the degradation processes and increasing their electrochemical performance, especially in abusive conditions like during fast charges. Knowledge of the redox state of each electrode is essential to identify the origins of capacity loss in full batteries. Among the methods used for these investigations, operando Nuclear Magnetic Resonance (NMR) methods are promising since, without destroying the battery, they enable monitoring in real-time the electrochemical processes and the formation of short-lived metastable or reactive phases [1,2].Up to now, most operando NMR studies have focused on 7Li NMR spectroscopy to follow the lithiation and degradation processes in the solid electrodes of lithium-ion batteries. However, the large shifts and broadenings of the NMR spectra, which result from the redox-active paramagnetic ions (Ni2/3+, Co4+, Mn3/4+) or from the metallicity of the electrodes [3], complicate operando NMR spectra acquisition and interpretation for full batteries.Herein, we demonstrate that the 1H operando NMR signal of the liquid electrolyte solvent can be used to spy on the positive electrode evolution while benefitting from the high sensitivity of 1H liquid-state NMR compared to 7Li NMR. So far, operando NMR using the liquid electrolyte signal was mainly exploited to follow electrolyte decomposition [4] or to image indirectly dendrite formation [5]. Contrary to the lithium or sodium atoms composing the electrodes, hydrogen atoms in the electrolyte solvent are not a direct probe of the state of charge of the electrode. We demonstrate that the 1H NMR signal of the electrolyte molecules in the battery is, however, highly sensitive to the magnetic susceptibility (and therefore the redox state) of the neighboring particles of positive electrode active material.The state-of-charge (SOC) of the positive electrodes in the charging battery can be tracked indirectly through distortion in the spectrum of the dimethyl carbonate (DMC) solvent near the positive electrode. The effect of the other battery components such as current collectors, separators, or even negative electrodes is shown to be negligible compared to the perturbations induced by the positive electrode. We define specific descriptors to track the changes in the distorted 1H NMR spectrum of the battery and we correlate these changes with the state-of-charge of the positive electrode inside the battery as it is charged and discharged. This approach will enable measuring, operando, the redox state of positive electrodes in batteries, even when their 7Li signals cannot be detected by NMR. Exact knowledge of the redox state will contribute to a better exploitation of the electrochemical curves in full batteries.[1] Bagheri, K.; Deschamps, M.; Salager, E. Nuclear Magnetic Resonance for Interfaces in Rechargeable Batteries. Current Opinion in Colloid & Interface Science 2023, 64, 101675. https://doi.org/10.1016/j.cocis.2022.101675.[2] Liu, X.; Liang, Z.; Xiang, Y.; Lin, M.; Li, Q.; Liu, Z.; Zhong, G.; Fu, R.; Yang, Y. Solid‐State NMR and MRI Spectroscopy for Li/Na Batteries: Materials, Interface, and in Situ Characterization. Advanced Materials 2021, 33 (50), 2005878. https://doi.org/10.1002/adma.202005878.[3] Grey, C. P.; Dupré, N. NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries. Chemical Reviews 2004, 104 (10), 4493–4512. https://doi.org/10.1021/cr020734p.[4] Wiemers-Meyer, S.; Winter, M.; Nowak, S. NMR as a Powerful Tool to Study Lithium Ion Battery Electrolytes. Annual Reports on NMR Spectroscopy 2019, 121–162. https://doi.org/10.1016/bs.arnmr.2018.12.003.[5] Ilott, A. J.; Mohammadi, M.; Chang, H. J.; Grey, C. P.; Jerschow, A. Real-Time 3D Imaging of Microstructure Growth in Battery Cells Using Indirect MRI. Proceedings of the National Academy of Sciences 2016, 113 (39), 10779–10784. https://doi.org/10.1073/pnas.1607903113.

Controllable Topological Transformations of 818 Molecular Metalla-knots by Oxidation of Thiazole-Based Ligands.

By exploiting coordination-driven self-assembly, high yields of two 818 molecular metalla-knots could be obtained using a thiazole-moiety-containing asymmetric dipyridyl ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole (L1 ), as confirmed using X-ray crystallographic analysis, electrospray ionization-time-of-flight/mass spectrometry (ESI-TOF/MS), and detailed liquid-state nuclear magnetic resonance (NMR) spectroscopy. To modulate the self-assembled structures, m-chloroperbenzoic acid (m-CPBA) was utilized to oxidize thiazole-based ligand L1 to N-thiazole-oxide-based ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole 3-oxide (L2 ), which enabled the selective construction of the corresponding tetranuclear macrocycles. Notably, two molecular metalla-knots could be topologically transformed from 818 knots to simple monocycles because the L1 alkyne bond was inert toward m-CPBA, as confirmed by liquid-state NMR spectroscopy, ESI-TOF/MS, and elemental analysis.

Biphasic NMR of Hyperpolarized Suspensions-Real-Time Monitoring of Solute-to-Solid Conversion to Watch Materials Grow.

Nuclear magnetic resonance (NMR) spectroscopy is a key method for the determination of molecular structures. Due to its intrinsically high (i.e., atomistic) resolution and versatility, it has found numerous applications for investigating gases, liquids, and solids. However, liquid-state NMR has found little application for suspensions of solid particles as the resonances of such systems are excessively broadened, typically beyond the detection threshold. Herein, we propose a route to overcoming this critical limitation by enhancing the signals of particle suspensions by >3.000-fold using dissolution dynamic nuclear polarization (d-DNP) coupled with rapid solid precipitation. For the proof-of-concept series of experiments, we employed calcium phosphate (CaP) as a model system. By d-DNP, we boosted the signals of phosphate 31P spins before rapid CaP precipitation inside the NMR spectrometer, leading to the inclusion of the hyperpolarized phosphate into CaP-nucleated solid particles within milliseconds. With our approach, within only 1 s of acquisition time, we obtained spectra of biphasic systems, i.e., micrometer-sized dilute solid CaP particles coexisting with their solution-state precursors. Thus, this work is a step toward real-time characterization of the solid-solution equilibrium. Finally, integrating the hyperpolarized data with molecular dynamics simulations and electron microscopy enabled us to shed light on the CaP formation mechanism in atomistic detail.

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.