Advanced Nuclear Magnetic Resonance Research Articles

The role of Nuclear Magnetic Resonance (NMR) spectroscopy in cattle metabolism

Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful analytical tool that has significantly advanced the understanding of cattle metabolism. Nuclear Magnetic Resonance (NMR) spectroscopy plays a pivotal role in the study of cattle metabolism, offering distinct advantages over other spectrometric methods. NMR spectroscopy is a powerful analytical tool that provides detailed molecular insights by exploiting the magnetic properties of atomic nuclei. Unlike mass spectrometry and infrared spectroscopy, NMR does not require extensive sample preparation or destruction, preserving the integrity of biological samples. This non-invasive nature is particularly beneficial for longitudinal studies in cattle, where metabolic changes over time are of interest. One of the key strengths of NMR spectroscopy is its ability to simultaneously detect and quantify a broad range of metabolites in complex biological matrices, such as blood, urine, and tissue extracts. This comprehensive metabolic profiling is crucial for understanding the biochemical pathways and physiological states in cattle. NMR's high reproducibility and quantitative accuracy further enhance its suitability for metabolic studies, enabling precise monitoring of metabolic fluctuations in response to dietary changes, environmental stressors, or disease conditions. NMR spectroscopy also offers unique advantages in elucidating structural information about metabolites. Through multidimensional NMR techniques, researchers can determine the molecular structure and conformation of metabolites, providing deeper insights into metabolic functions and interactions. This structural elucidation is often challenging with other spectrometric methods, which may lack the resolution or require derivatization of samples. Moreover, NMR spectroscopy's non-destructive nature allows for the analysis of living tissues and in vivo studies, facilitating real-time monitoring of metabolic processes. This capability is instrumental in studying dynamic metabolic responses and adaptations in cattle under different physiological states. Additionally, the development of advanced NMR techniques, such as high-resolution magic angle spinning (HR-MAS) and hyperpolarization, has further expanded the scope of NMR applications in metabolic research. NMR spectroscopy stands out as a superior method for studying cattle metabolism due to its non-destructive approach, comprehensive metabolic profiling, structural elucidation capabilities, and potential for in vivo analysis. These advantages make NMR an indispensable tool in advancing our understanding of cattle metabolism and improving livestock health and productivity. Keywords: Nuclear Magnetic Resonance (NMR), Cattles, Metabolomics.

Exploring the corrosion mechanism of oxide glasses using advanced solid-state nuclear magnetic resonance spectroscopy

Despite over 70 years of study, the mechanism of glass corrosion, particularly the formation of the amorphous alteration layer known as the gel layer, remains a subject of controversy. A critical debate revolves around the origin of the abrupt change in chemical concentration near the interface between the gel layer and the glass phase. The prevailing concept attributes this shift to the dissolution of glass compositions, followed by their precipitation onto the glass surface, ultimately forming the gel layer. In this study, we utilized state-of-the-art solid-state nuclear magnetic resonance (SSNMR) techniques to track the atomic-scale network evolution of phosphate glass and borosilicate glass during corrosion. The SSNMR results demonstrate that water partially disrupts the glass network at the surface but hardly disrupts the glass network of the hydrated glass phase. This distinct interaction leads to different structures at the surface compared to the hydrated glass phase. A significant exchange of alkali metal ions in the glass occurs with H species (H+ or H3O+) in the surrounding water. Our findings demonstrate that the ion-selective diffusion, combined with the structural difference between the gel layer and hydrated glass phase, rather than the dissolution-reprecipitation of glass compositions, is responsible for the formation of a gel layer on the glass surface and the abrupt change in chemical concentration near the interface between the gel layer and the hydrated glass phase. These new findings provide valuable and novel insights into the corrosion mechanism of oxide glasses.

Flow Characterization in Fractured Shale Oil Matrices Using Advanced Nuclear Magnetic Resonance Techniques

The evaluation of flow dynamics in fractured shale oil reservoirs presents significant challenges due to the complex pore configurations and high organic material concentration. Conventional methods for petrophysical and fluid dynamic evaluations are insufficient in addressing these complexities. However, nuclear magnetic resonance (NMR) technology is an effective technique for quantitatively delineating fluid micro-transport properties across the reservoir core. This study presents an experimental methodology rooted in NMR technology to quantify the flow capabilities within the shale oil matrix. This approach incorporates high-pressure saturation flow experiments across seven distinct core samples to gauge the micro-transport phenomena of fluids across various pore dimensions. The results revealed that under high-pressure saturation, shale cores devoid of fractures demonstrated an average crude oil saturation rate of merely 19.44%. Cores with evident stratification exhibited a 16.18% increase in flow capacity compared to their non-stratified counterparts. The flow dynamics within these shale reservoirs exhibited a range of behaviors, from non-linear to linear. In lower-permeability zones, non-linear patterns became increasingly apparent. An NMR T2 spectrum analysis was used to identify the minimum effective pore size conducive to shale oil flow within the matrix, which was between 8 and 10 nanometers. These insights provide a foundation for a deeper understanding of the mechanisms behind oil and gas migration in fractured shale oil matrices, offering valuable insight into their extractive potential.

Chemical composition of soil humin in an organic soil profile

Humin is identified as the most recalcitrant fraction of soil organic matter, but its synthesis and depth variability in the soil profile are unknown. Here, we suggest that carboxyl-rich alicyclic structures (CRAM) and fused aromatic ring structures (FAR) can process significant components of the humin structure. We conducted molecular-level characterization of humin using advanced solid-state nuclear magnetic resonance spectroscopy (SSNMR) experiments and calculated the proportion of FAR and functionalities of CRAM (OCq, –C(CH)n, –CH3) structures. Dipolar dephased (dd) direct polarization magic angle spinning (DPMAS) NMR experiments provided insights into non-protonated carbon and mobile quaternary carbons. We calculated the proportions of non-protonated aromatic carbon and non-polar aliphatic C in the organic layers of the topsoil (Oa), mid-soil (Om), and mineral subsoil (Cg). It was evident that the total aliphatic carbon constitutes a significant proportion of humin, as is the non-protonated C attached to CH3. The 13C dd/DPMAS NMR spectrum of Cg humin clearly showed the formation and preservation of hydrophobic OCq, which is indicative of CRAM structures. CRAM structures could be attached to FAR, which makes the whole structure relatively more hydrophobic, a critical humin functionality in deeper soil. The findings from our research can be successfully utilized in terrestrial carbon sequestration studies to amplify the potential of humin as a recalcitrant carbon reservoir.

Deciphering Cholesterol's Role in PD-L2 Stability: A Distinct Regulatory Mechanism From PD-L1

Programmed cell death 1 ligand 2 (PD-L2), a member of the B7 immune checkpoint protein family, emerges as a crucial player in immune modulation. Despite its functional overlap with programmed cell death 1 ligand 1 (PD-L1) in binding to the programmed cell death protein 1 (PD-1) on T cells, PD-L2 exhibits a divergent expression pattern and a higher affinity for PD-1. However, the regulatory mechanisms of PD-L2 remain under-explored. Here, our investigations illustrate the pivotal role of cholesterol in modulating PD-L2 stability. Using advanced nuclear magnetic resonance (NMR) and biochemical analyses, we demonstrate a direct and specific binding between cholesterol and PD-L2, mediated by an F-xxx-V-xx-LR motif in its transmembrane domain, distinct from that in PD-L1. This interaction stabilizes PD-L2 and prevents its downstream degradation. Disruption of this binding motif compromises PD-L2′s cellular stability, underscoring its potential significance in cancer biology. These findings not only deepen our understanding of PD-L2 regulation in the context of tumors, but also open avenues for potential therapeutic interventions.

SAND: Automated Time-Domain Modeling of NMR Spectra Applied to Metabolite Quantification.

Developments in untargeted nuclear magnetic resonance (NMR) metabolomics enable the profiling of thousands of biological samples. The exploitation of this rich source of information requires a detailed quantification of spectral features. However, the development of a consistent and automatic workflow has been challenging because of extensive signal overlap. To address this challenge, we introduce the software Spectral Automated NMR Decomposition (SAND). SAND follows on from the previous success of time-domain modeling and automatically quantifies entire spectra without manual interaction. The SAND approach uses hybrid optimization with Markov chain Monte Carlo methods, employing subsampling in both time and frequency domains. In particular, SAND randomly divides the time-domain data into training and validation sets to help avoid overfitting. We demonstrate the accuracy of SAND, which provides a correlation of ∼0.9 with ground truth on cases including highly overlapped simulated data sets, a two-compound mixture, and a urine sample spiked with different amounts of a four-compound mixture. We further demonstrate an automated annotation using correlation networks derived from SAND decomposed peaks, and on average, 74% of peaks for each compound can be recovered in single clusters. SAND is available in NMRbox, the cloud computing environment for NMR software hosted by the Network for Advanced NMR (NAN). Since the SAND method uses time-domain subsampling (i.e., random subset of time-domain points), it has the potential to be extended to a higher dimensionality and nonuniformly sampled data.

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.

Peculiar Phosphonate Modifications of Velvet Worm Slime Revealed by Advanced Nuclear Magnetic Resonance and Mass Spectrometry.

Nature is rich with examples of highly specialized biological materials produced by organisms for functions, including defense, hunting, and protection. Along these lines, velvet worms (Onychophora) expel a protein-based slime used for hunting and defense that upon shearing and dehydration forms fibers as stiff as thermoplastics. These fibers can dissolve back into their precursor proteins in water, after which they can be drawn into new fibers, providing biological inspiration to design recyclable materials. Elevated phosphorus content in velvet worm slime was previously observed and putatively ascribed to protein phosphorylation. Here, we show instead that phosphorus is primarily present as phosphonate moieties in the slime of distantly related velvet worm species. Using high-resolution nuclear magnetic resonance (NMR), natural abundance dynamic nuclear polarization (DNP), and mass spectrometry (MS), we demonstrate that 2-aminoethyl phosphonate (2-AEP) is associated with glycans linked to large slime proteins, while transcriptomic analyses confirm the expression of 2-AEP synthesizing enzymes in slime glands. The evolutionary conservation of this rare protein modification suggests an essential functional role of phosphonates in velvet worm slime and should stimulate further study of the function of this unusual chemical modification in nature.

Assessing the Acute Toxicological Effects of Annona muricata Leaf Ethanol Extract on Rats: Biochemical, Histopathological, and Metabolomics Analyses.

Annona muricata is a common plant used in Africa and South America to manage various types of disease. However, there is insufficient toxicological information or published standard available regarding repeated dose animal toxicity data. As part of the safety assessment, we exposed Sprague Dawley rats to an acute oral toxicity of A. muricata. The intent of the current study was to use advanced proton nuclear magnetic resonance (1H NMR) in serum and urinary metabolomics evaluation techniques to provide the in vivo acute toxicological profile of A. muricata leaf ethanol extract in accordance with the Organization for Economic Co-operation and Development's (OECD) 423 guidelines. A single 2000 mg/kg dose of A. muricata leaf ethanol extract was administered to Sprague Dawley rats over an observational period of 14 days. The toxicity evaluation (physical and behavior observation, body weight, renal function test, liver function test and 1H NMR analysis) showed no abnormal toxicity. Histopathological analysis manifested mild changes, i.e., the treated kidney manifested mild hypercellularity of mesangial cells and mild red blood cell congestion. In addition, there was mild hemorrhage into tissue with scattered inflammatory cells and mild dilated central vein with fibrosis in the liver. However, the changes were very mild and not significant which correlate with other analyses conducted in this study (biochemical test and 1H NMR metabolomic analysis). On the other hand, urinary 1H NMR analysis collected on day 15 revealed high similarity on the metabolite variations for both untreated and treated groups. Importantly, the outcomes suggest that A. muricata leaf ethanol extract can be safely consumed at a dose of 2000 mg/kg and the LD50 must be more than 2000 mg/kg.

The impact of maize straw incorporation on arsenic and cadmium availability, transformation and microbial communities in alkaline-contaminated soils

Increasing evidence of the uncertainty of crop straw returning in heavy metal-contaminated soil is a significant concern. The present study investigated the influence of 1 and 2% maize straws (MS) amendment on As and Cd bioavailability in two different alkaline soils (A-industrial and B-irrigation) after 56 days of ageing. Adding MS to the two soils decreased the pH by 1.28 (A soil) and 1.13 (B soil) and increased the concentration of dissolved organic carbon (DOC) by 54.40 mg/kg (A soil) and 100.00 mg/kg (B soil) during the study period. After 56 days of ageing, the overall NaHCO3–As and DTPA-Cd increased by 40% and 33% (A) and 39% and 41% (B) soils, respectively. The MS additions increased the alteration of As and Cd exchangeable and residual fractions, whereas advanced solid-state 13C nuclear magnetic resonance (NMR) revealed that alkyl C and alkyl O–C–O in A soil and alkyl C, Methoxy C/N-alkyl, and alkyl O–C–O in B soil significantly contributed to the As and Cd mobilisation. Collectively, 16 S rRNA analyses revealed Acidobacteria, Firmicutes, Chloroflexi, Actinobacteria and Bacillus promoted the As and Cd mobilisation following the MS addition, while principle component analysis (PCA) demonstrated that bacterial proliferation significantly influenced MS decomposition, resulting in As and Cd mobilisation in the two soils. Overall, the study highlights the implications of applying MS to As- and Cd-contaminated alkaline soil and offers the framework for conditions to be considered during As- and Cd-remediation efforts, especially when MS is the sole remediation component.

Structural impact of niobium oxide on lithium silicate glasses: Results from advanced interaction-selective solid-state nuclear magnetic resonance and Raman spectroscopy

While niobium-containing oxide glasses are used in many technological applications, especially optical glasses, the exact structural role of Nb and its impact on the structure of covalent/ionic oxide glasses remain incompletely understood. In the present study, this issue is addressed for Nb2O5-containing lithium silicate glasses using 7Li, 29Si, and 93Nb magic-angle-spinning (MAS) and advanced NMR methods sensitive to 7Li–7Li and 7Li–93Nb magnetic dipole-dipole interactions, accompanied by molecular dynamics (MD) and Monte-Carlo (MC) simulations. In glasses along the compositional line (1–y)Li2Si2O5–yNb2O5, 29Si MAS-NMR spectra reveal a gradual silica network repolymerization with increasing y, indicating that the accommodation of the niobium oxide component into the glassy network requires on average about 0.7 equivalents of lithium oxide. Significant 7Li–93Nb interactions were also detected and quantified by Rotational Echo Saturation Pulse Double Resonance (RESPDOR) experiments. Consistent with this finding, profound changes in the local environments of the lithium ions and their spatial distributions are observed in 7Li satellite transition (SATRAS) spectra and 7Li dipolar spin echo decays, whereas 93Nb NMR and Raman spectra suggest the formation of six-coordinated NbO6 polyhedra with both, corner- and edge-sharing connectivity. Results obtained on glasses along a second composition line, SiO2–[(Li2O)1.4(Nb2O5)], confirm the above-described structural concepts. The average homo- and heteronuclear dipolar interaction strengths as expressed by the second moments M2(Li-Li) and M2(Li-Nb) are consistent with random spatial distributions of the lithium and niobium species, with a tendency towards Nb clustering at higher concentrations. All of these results suggest that niobium oxide adopts a network former role in these glasses. The current study defines a comprehensive general strategy for elucidating the structural impact of NMR active intermediate oxides incorporated into silicate glasses.

Production of isotopically enriched high molecular weight hyaluronic acid and characterization by solid-state NMR

Hyaluronic acid (HA) is a naturally occurring polysaccharide that is abundant in the extracellular matrix (ECM) of all vertebrate cells. HA-based hydrogels have attracted great interest for biomedical applications due to their high viscoelasticity and biocompatibility. In both ECM and hydrogel applications, high molecular weight (HMW)-HA can absorb a large amount of water to yield matrices with a high level of structural integrity. To understand the molecular underpinnings of structural and functional properties of HA-containing hydrogels, few techniques are available. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for such studies, e.g. 13C NMR measurements can reveal the structural and dynamical features of (HMW) HA. However, a major obstacle to 13C NMR is the low natural abundance of 13C, necessitating the generation of HMW-HA that is enriched with 13C isotopes. Here we present a convenient method to obtain 13C- and 15N-enriched HMW-HA in good yield from Streptococcus equi subsp. zooepidemicus. The labeled HMW-HA has been characterized by solution and magic angle spinning (MAS) solid-state NMR spectroscopy, as well as other methods. These results will open new ways to study the structure and dynamics of HMW-HA-based hydrogels, and interactions of HMW-HA with proteins and other ECM components, using advanced NMR techniques.

Approaching Molecular Definition on Oxide-Supported Single-Atom Catalysts.

ConspectusSingle-atom catalysts (SACs) offer unique advantages such as high (noble) metal utilization through maximum possible dispersion, large metal-support contact areas, and oxidation states usually unattainable in classic nanoparticle catalysis. In addition, SACs can serve as models for determining active sites, a simultaneously desired as well as elusive target in the field of heterogeneous catalysis. Due to the complexity of heterogeneous catalysts bearing a variety of different sites on metal particles and the respective support as well as at their interface, studies of intrinsic activities and selectivities remain largely inconclusive. While SACs could close this gap, many supported SACs remain intrinsically ill-defined due to complexities arising from the variety of different adsorption sites for atomically dispersed metals, hampering the establishment of meaningful structure-activity correlations. In addition to overcoming this limitation, well-defined SACs could even be utilized to shed light on fundamental phenomena in catalysis that remain ambiguous when studies are obscured by the complexity of heterogeneous catalysts.In this Account, we describe approaches to break down the complexity of supported single-atom catalysts through the careful choice of oxide supports with specific binding motives as well as the adsorption of well-defined ligands such as ionic liquids on single metal sites. An example of molecularly defined oxide supports is polyoxometalates (POMs), which are metal oxo clusters with precisely known composition and structure. POMs exhibit a limited number of sites to anchor atomically dispersed metals such as Pt, Pd, and Rh. Polyoxometalate-supported single-atom catalysts (POM-SACs) thus represent ideal systems for the in situ spectroscopic study of single atom sites during reactions as, in principle, all sites are identical and thus equally active in catalytic reactions. We have utilized this benefit in studies of the mechanism of CO and alcohol oxidation reactions as well as the hydro(deoxy)genation of various biomass-derived compounds. More so, the redox properties of polyoxometalates can be finely tuned by changing the composition of the support while keeping the geometry of the single-atom active site largely constant. We further developed soluble analogues of heterogeneous POM-SACs, opening the door to advanced liquid-phase nuclear magnetic resonance (NMR) and UV-vis techniques but, in particular, to electrospray ionization mass spectrometry (ESI-MS) which proves powerful in determining catalytic intermediates as well as their gas-phase reactivity. Employing this technique, we were able to resolve some of the long-standing questions about hydrogen spillover, demonstrating the broad utility of studies on defined model catalysts.

NMR log response prediction from conventional petrophysical logs with XGBoost-PSO framework

A combined approach that exploits both the eXtreme Gradient Boosting (XGBoost) method and the Particle Swarm Optimization (PSO) method was used here to predict the nuclear magnetic resonance (NMR) log parameters such as porosity and permeability from field measurements. Data obtained by NMR are extremely critical for modeling the reservoir behavior and are among the most vital inputs for reservoir simulations. Therefore, developing an intelligent framework that can accurately predict NMR logging response by using conventional, low-cost logging data can be a valuable tool for field development. A number of conventional well logs, such as neutron, density, sonic, caliper, gamma-ray, and resistivity logs, recorded from sixteen wells in an offshore oilfield in Persian Gulf were used in the XGBoost-PSO framework to predict NMR log response. The outputs are the free fluid porosity (CMFF), bound fluid porosity (BFV), permeability (KTIM), and total porosity (TCMR). Based on the results, in terms of prediction accuracy, comparing correlation coefficients, the XGBoost-PSO model performs in the range of 88.5–91.4%. Moreover, the application of PSO in hyperparameter optimization of predicted parameters confirmed at least five percent improvement. Overall, we were able to demonstrate that ordinary conventional logging data can be utilized to obtain more advanced NMR data without performing expensive, time-consuming, and high-risk logging operations to decrease operational costs without compromising the benefits.

One-dimensional alignment of defects in a flexible metal-organic framework.

Crystalline materials are often considered to have rigid periodic lattices, while soft materials are associated with flexibility and nonperiodicity. The continuous evolution of metal-organic frameworks (MOFs) has erased the boundaries between these two distinct conceptions. Flexibility, disorder, and defects have been found to be abundant in MOF materials with imperfect crystallinity, and their intricate interplay is poorly understood because of the limited strategies for characterizing disordered structures. Here, we apply advanced nuclear magnetic resonance spectroscopy to elucidate the mesoscale structures in a defective MOF with a semicrystalline lattice. We show that engineered defects can tune the degree of lattice flexibility by combining both ordered and disordered compartments. The one-dimensional alignment of correlated defects is the key for the reversible topological transition. The unique matrix is featured with both rigid framework of nanoporosity and flexible linkage of high swellability.

Three-Component Betti Condensation for Synthesis of Aminomethylnaphthols Incorporating Deoxy-isoequilenine Scaffold-Absolute Configuration and Application

Chiral aminomethylnaphthols have been prepared highly diastereoselective by means of three-component “Betti condensation”, using steroidal 2-naphthol analogue, synthesized from estrone. The use of 2-methoxybenzaldehyde or 2-pyridinecarboxaldehyde as aldehyde component and (S)-(–)-1-phenylethan-1-amine or (S)-(–)-1-(naphthalen-2-yl)ethan-1-amine, as chiral non-racemic amine component providing the diastereoselectivity, allowed the synthesis of structurally diverse aminomethylnaphthols. The latter easily form 1,3-dihydronaphthoxazines through reaction with formaldehyde. The absolute configurations of the new aminomethylnaphthols synthesized have been determined through advanced nuclear magnetic resonance (NMR) experiments and confirmed by X-ray crystallography. The chiral steroidal aminomethylnaphthols obtained as pure diastereoisomers have been evaluated as pre-catalysts in the enantioselective addition of diethylzinc to aldehydes with enantioselectivities of up to 97% ee.

The Effect of Different Freeze-Thaw Cycles on Mortar Gas Permeability and Pore Structure

Two different freeze-thaw cycles (FTC) are considered in this study to assess the related impact on gas permeability and micro-pore structure of a mortar. These are the water-freezing/water-thawing (WF-WT) and the air-freezing/air-thawing (AF-AT) cycles. The problem is addressed experimentally through an advanced nuclear magnetic resonance (NMR) technique able to provide meaningful information on the relationships among gas permeability, pore structure, mechanical properties, and the number of cycles. It is shown that the mortar gas permeability increases with the number of FTCs, the increase factor being 20 and 12.83 after 40 cycles for the WF-WT and AF-AT, respectively. The results also confirm that gas permeability hysteresis phenomena occur during the confining pressure loading and unloading process.

V2O5-P2O5-TeO2 glass anodes for Li-ion batteries

Understanding the role of network formers in affecting the electrochemical performances of the glass anodes for Li-ion batteries (LIBs) is of great importance for developing novel glass anode materials. In this work, we substitute the network former P2O5 for partial amount of TeO2 in V2O5-TeO2 glass composition and probe the effect of this substitution on both the microstructure and performances of the LIB anodes. The network structure of the glass before and after discharging/charging cycles is revealed at atomistic level by advanced Solid-State Nuclear Magnetic Resonance spectroscopy and X-ray photoelectron spectroscopy. The results show that, upon the insertion/extraction of Li+ ions, the structural network of the glass anode is irreversibly disassociated into many polyhedral species that congregate to form different kinds of nanoclusters. The substitution of P2O5 for TeO2 promotes the formation of Li2Te and the reduction of V5+ to V4+, and thereby enhances the capacity of the glass anodes.

Role of the sedimentary organic matter structure and microporosity on the degradation of nonylphenol by potassium ferrate

In this study, the role of organic matter structure and microporosity in the adsorption and degradation of radioactive nonylphenol in sediments treated with potassium ferrate solutions was investigated. The demineralized fractions and acid non-hydrolyzable fractions were isolated and characterized via advanced solid-state 13C nuclear magnetic resonance and CO2 gas adsorption technology, respectively. Radioactive nonylphenol in the sediments was also fractionated into 14CO2, water-soluble residues, extractable residues, and strongly bound residues after treatment with potassium ferrate. A first-order, two-compartment kinetic model well described the mineralization and degradation kinetics of radioactive nonylphenol in the sediment (R2 > 0.99). The degradation percentages of spiked nonylphenol were highly negatively correlated with aromatic carbon, aliphatic carbon, and microporosity estimated from acid-non-hydrolyzable fractions in the bulk sediments (R2 > 0.82, p < 0.01). The percentages of adsorbed parent nonylphenol residues were highly positively correlated with aromatic carbon, aliphatic carbon, and microporosity estimated from acid-non-hydrolyzable fractions in the bulk sediments (R2 > 0.90, p < 0.01). The parent nonylphenol compound desorbed into the aqueous phase and was completely degraded. This study is the first to demonstrate the important role of aromatic carbon, aliphatic carbon, and microporosity in acid non-hydrolyzable fractions on the degradation of nonylphenol during the potassium ferrate oxidation treatment process.

A nuclear quadrupolar spin quantum heat engine

We give an implementable scheme which uses intrinsic quadrupolar nuclear spin interactions to harvest efficient energy from a quantum Otto cycle. We employ realistic parameter regimes for the 23Na nucleus in sodium nitrate. The processes of the cycle are accomplished by orienting the sample with respect to the static magnetic field. The effects of stroke duration on the work output and efficiency are revealed in detail. Finite-time adiabatic transformations leading to quantum friction are found to substantially reduce cycle outputs which are stimulated from the non-secular parts of the quadrupolar interaction. An estimation for the power output at maximum efficiency is also given. We show that with the precise control and manipulation of the intrinsic nuclear spin interactions, for example in an advanced nuclear magnetic resonance setup, makes our scheme implement as a powerful quantum Otto cycle.