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Recent studies have demonstrated that the presence of water in deep eutectic solvents (DESs) significantly affects their dynamics, structure, and physical properties. Although the structural changes due to the addition of water are well understood, the microscopic dynamics of these changes have been rarely studied. Here, we performed molecular dynamics simulation of 30% (v/v) (∼0.57 molar fraction) water mixture of DES containing CH3CONH2 and NaSCN/KSCN at various salt fractions to understand the microscopic structure and dynamics of water. The simulated results reveal a heterogeneous environment for water molecules in aqueous DES (ADES), which is influenced by the nature of the cation. The diffusion coefficients of water in ADESs are significantly lower than that in neat water and concentrated aqueous NaSCN/KSCN solution. When Na+ ions are replaced by K+ ions in the ADES system, the diffusion coefficient increases, which is consistent with the measured nuclear magnetic resonance data. Self-dynamic structure factor for water and other simulated dynamic quantities, such as reorientation, hydrogen-bond, and residence time correlation functions, show markedly slower dynamics inside ADES than in the neat water and aqueous salt solution. Moreover, these dynamics become faster when Na+ ions in ADES are replaced by K+ ions. The results suggest that the structural environment of water in Na+-rich ADES is rigid due to the presence of cation-bound water and geometrically constrained water. The medium becomes less rigid as the KSCN fraction increases due to the relatively weaker interaction of K+ ions with water than Na+ ions, which accelerates the dynamical processes. [ABSTRACT FROM AUTHOR]

Thermodynamic hydrate promoters and kinetic hydrate promoters can be used to reduce the P–T conditions for clathrate hydrate synthesis to decrease the nucleation induction time while increasing growth rates. Two commonly used promoters for hydrate research are tetrahydrofuran (THF) and sodium dodecyl sulfate (SDS), which can increase the overall hydrate promotion when used in tandem as compared to individually. There are several molecular theories regarding how SDS promotes hydrate growth. This study explores the micellular theory, for which hydrate formation depends on surfactant aggregates (micelles) at a critical micelle concentration (CMC) to increase the interfacial surface area. The micellular theory is the most investigated and criticized surfactant hydrate promotion theory. To address questions related to micellar behavior, this study investigates the intermolecular behavior between SDS and THF for the identification of micelles at hydrate-forming conditions. The systems explored contained THF at 3 and 5 wt. % with varying concentrations of SDS below and above the CMC. Several methods including a qualitative visual method, conductivity, interfacial tensiometry, 13C Liquid-state Nuclear Magnetic Resonance (NMR) spectroscopy, and 1H diffusion NMR spectroscopy were evaluated at temperatures below the Krafft point of SDS and above 0 °C. The presence of THF at low concentrations decreased the critical temperature for the formation of SDS micelles, where SDS is solubilized in THF/water solution at hydrate-forming temperatures without precipitation. The CMC of SDS was decreased significantly even at hydrate-forming conditions. Mixed surfactant–cosolvent micellular behavior of SDS in the presence of low concentrations of THF was confirmed at hydrate-forming conditions above 0 °C. [ABSTRACT FROM AUTHOR]

The structure of calcium aluminosilicate glasses (CaO)x(Al2O3)y(SiO2)1−x−y with the near tectosilicate compositions x ≃ 0.19 and 1 − x − y ≃ 0.61 or x ≃ 0.26 and 1 − x − y ≃ 0.49 was investigated by in situ high-pressure neutron diffraction and 27Al nuclear magnetic resonance (NMR) spectroscopy. The results show three distinct pressure regimes for the transformation of the aluminum coordination environment from tetrahedral to octahedral, which map onto the deformations observed in the production of permanently densified materials. The oxygen packing fraction serves as a marker for signaling a change to the coordination number of the network forming motifs. For a wide variety of permanently densified aluminosilicates, the aluminum speciation shares a common dependence on the reduced density ρ′ = ρ/ρ0, where ρ is the density and ρ0 is its value for the uncompressed material. The observed increase in the Al–O coordination number with ρ′ originates primarily from the formation of six-coordinated aluminum Al(VI) species, the fraction of which increases rapidly beyond a threshold ρ thr ′ ∼ 1.1. The findings are combined to produce a self-consistent model for pressure-induced structural change. Provided the glass network is depolymerized, one-coordinated non-bridging oxygen atoms are consumed to produce two-coordinated bridging oxygen atoms, thus increasing the network connectivity in accordance with the results from 17O NMR experiments. Otherwise, three-coordinated oxygen atoms or triclusters appear, and their fraction is quantified by reference to the mean coordination number of the silicon plus aluminum species. The impact of treating Al(VI) as a network modifier is discussed. [ABSTRACT FROM AUTHOR]

The results of relativistic calculations of nuclear magnetic resonance shielding tensors (σ) for the thallium monocation (Tl+), thallium hydride (TlH), and thallium halides (TlF, TlCl, TlBr, TlI, and TlAt) are presented as obtained within a four-component polarization propagator formalism and a two-component linear response approach within the zeroth-order regular approximation. In addition to a detailed analysis of relativistic effects performed in this work, some quantum electrodynamical (QED) effects on those nuclear magnetic resonance shieldings and other small contributions are estimated. A strong dependence of σ(Tl) on the bonding partner is found, together with a very weak dependence of QED effects with them. In order to explain the trends observed, the excitation patterns associated with relativistic ee (or paramagnetic-like) and pp (or diamagnetic-like) contributions to σ are analyzed. For this purpose, the electronic spin-free and spin-dependent contributions are separated within the two-component zeroth-order regular approximation, and the influence of spin–orbit coupling on involved molecular orbitals is studied, which allows for a thorough understanding of the underlying mechanisms. [ABSTRACT FROM AUTHOR]

The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI−) or hexafluorophosphate (PF6−) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior. It was observed that the PC molecules are the faster species. For the monovalent cations (Li+, Na+, K+), the PC solvent diffusion was enhanced as the cation size increased, while for the divalent cations (Mg2+, Ca2+, Sr2+, Ba2+), the opposite trend was observed, i.e., the diffusion coefficients decreased as the cation size increased. The anion diffusion in LiTFSI and NaTFSI solutions was found to be similar, while in electrolytes with divalent cations, a decrease in anion diffusion with increasing cation size was observed. It was shown that non-polarizable charge-scaled force fields could correspond perfectly to the experimental values of the anion and PC solvent diffusion coefficients in salt solutions of both monovalent (Li+, Na+, K+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations at a range of operational temperatures. Finally, after calculating the radial distribution functions between cations, anions, and solvent molecules, the increase in the PC diffusion coefficient established with the increase in cation size for monovalent cations was clearly explained by the large hydration shell of small Li+ cations, due to their strong interaction with the PC solvent. In solutions with larger monovalent cations, such as Na+, and with a smaller solvation shell of PC, the PC diffusion is faster due to more liberated solvent molecules. In the salt solutions with divalent cations, both the anion and the PC diffusion coefficients decreased as the cation size increased due to an enhanced cation–anion coordination, which was accompanied by an increase in the amount of PC in the cation solvation shell due to the presence of anions. [ABSTRACT FROM AUTHOR]

This paper is dedicated to the quantum chemical package Jaguar, which is commercial software developed and distributed by Schrödinger, Inc. We discuss Jaguar's scientific features that are relevant to chemical research as well as describe those aspects of the program that are pertinent to the user interface, the organization of the computer code, and its maintenance and testing. Among the scientific topics that feature prominently in this paper are the quantum chemical methods grounded in the pseudospectral approach. A number of multistep workflows dependent on Jaguar are covered: prediction of protonation equilibria in aqueous solutions (particularly calculations of tautomeric stability and pKa), reactivity predictions based on automated transition state search, assembly of Boltzmann-averaged spectra such as vibrational and electronic circular dichroism, as well as nuclear magnetic resonance. Discussed also are quantum chemical calculations that are oriented toward materials science applications, in particular, prediction of properties of optoelectronic materials and organic semiconductors, and molecular catalyst design. The topic of treatment of conformations inevitably comes up in real world research projects and is considered as part of all the workflows mentioned above. In addition, we examine the role of machine learning methods in quantum chemical calculations performed by Jaguar, from auxiliary functions that return the approximate calculation runtime in a user interface, to prediction of actual molecular properties. The current work is second in a series of reviews of Jaguar, the first having been published more than ten years ago. Thus, this paper serves as a rare milestone on the path that is being traversed by Jaguar's development in more than thirty years of its existence. [ABSTRACT FROM AUTHOR]

We investigate water dynamics in mesoporous silica across partial crystallization by combining broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and molecular dynamics simulations (MDS). Exploiting the fact that not only BDS but also NMR field-cycling relaxometry and stimulated-echo experiments provide access to dynamical susceptibilities in broad frequency and temperature ranges, we study both the fully liquid state above the melting point Tm and the dynamics of coexisting water and ice phases below this temperature. It is found that partial crystallization leads to a change in the temperature dependence of rotational correlation times τ, which occurs in addition to previously reported dynamical crossovers of confined water and depends on the pore diameter. Furthermore, we observe that dynamical susceptibilities of water are strongly asymmetric in the fully liquid state, whereas they are much broader and nearly symmetric in the partially frozen state. Finally, water in the nonfreezable interfacial layer below Tm does not exhibit a much debated dynamical crossover at ∼220 K. We argue that its dynamics is governed by a static energy landscape, which results from the interaction with the bordering silica and ice surfaces and features a Gaussian-like barrier distribution. Consistently, our MDS analysis of the motional mechanism reveals a hopping motion of water in thin interfacial layers. The rotational correlation times of the confined ice phases follow Arrhenius laws. While the values of τ depend on the pore diameter, freezable water in various types of confinements and mixtures shows similar activation energies of Ea ≈ 0.43 eV. [ABSTRACT FROM AUTHOR]

This article presents the application of continuous Floquet theory in solid-state nuclear magnetic resonance (NMR). Continuous Floquet theory extends the traditional Floquet theory to non-continuous Hamiltonians, enabling the description of observable effects not fully captured by the traditional Floquet theory due to its requirement for a periodic Hamiltonian. We present closed-form expressions for computing first- and second-order effective Hamiltonians, streamlining integration with the traditional Floquet theory and facilitating application in NMR experiments featuring multiple modulation frequencies. Subsequently, we show examples of the practical application of continuous Floquet theory by investigating several solid-state NMR experiments. These examples illustrate the importance of the duration of the pulse scheme regarding the width of the resonance conditions and the near-resonance behavior. [ABSTRACT FROM AUTHOR]

An approach is presented for simulating multipulse nuclear magnetic resonance (NMR) spectra of polycrystalline solids directly in the frequency domain. The approach integrates the symmetry pathway concept for multipulse NMR with efficient algorithms for calculating spinning sideband amplitudes and performing interpolated finite-element numerical integration over all crystallite orientations in a polycrystalline sample. The numerical efficiency is achieved through a set of assumptions used to approximate the evolution of a sparse density matrix through a pulse sequence as a set of individual transition pathway signals. The utility of this approach for simulating the spectra of complex materials, such as glasses and other structurally disordered materials, is demonstrated. [ABSTRACT FROM AUTHOR]

1H spin-lattice Nuclear Magnetic Resonance relaxometry experiments have been performed for collagen and collagen-based artificial tissues in the frequency range of 10 kHz–20 MHz. The studies were performed for non-hydrated and hydrated materials. The relaxation data have been interpreted as including relaxation contributions originating from 1H–1H and 1H–14N dipole–dipole interactions, the latter leading to Quadrupole Relaxation Enhancement effects. The 1H–1H relaxation contributions have been decomposed into terms associated with dynamical processes on different time scales. A comparison of the parameters for the non-hydrated and hydrated systems has shown that hydration leads to a decrease in the dipolar relaxation constants without significantly affecting the dynamical processes. In the next step, the relaxation data for the hydrated systems were interpreted in terms of a model assuming two-dimensional translational diffusion of water molecules in the vicinity of the macromolecular surfaces and a sub-diffusive motion leading to a power law of the frequency dependencies of the relaxation rates. It was found that the water diffusion process is slowed down by at least two orders of magnitude compared to bulk water diffusion. The frequency dependencies of the relaxation rates in hydrated tissues and hydrated collagen are characterized by different power laws ( ω H − β , where ωH denotes the 1H resonance frequency): the first of about 0.4 and the second close to unity. [ABSTRACT FROM AUTHOR]

This study explores how magnetization manipulation occurs in a flowing medium over a pipe geometry using nuclear magnetic resonance methods. In particular, the experimental conditions on radio frequency pulsing and the signal detection are studied in an ultra-low frequency regime of a few kilohertz. An analytical model of the magnetization preparation is presented, which calculates the magnetization distribution of an excited flowing segment. The effective flip angle distribution is mapped to simulate the temporal development of the magnetization in the segment. The simulation results are compared to the experimental data from a flow metering setup. As a result, the quantitative impact of the flow profile on the magnetic signal is shown. [ABSTRACT FROM AUTHOR]

The study of electrolytic solutions is of relevance in many research fields, ranging from biophysics, materials, and colloid science to catalysis and electrochemistry. The dependence of solution dynamics on the nature of electrolytes and their concentrations has been the subject of many experimental and computational studies, yet it remains challenging to obtain a full understanding of the factors that govern solution behavior. Here, we provide additional insights into the behavior of aqueous solutions of alkali chlorides by combining 17O relaxation data with diffusion and viscosity data and contrast their behavior with 1H nuclear magnetic resonance relaxation data. The main findings are that 17O relaxation correlates well with viscosity data but not with diffusion data, while 1H relaxation correlates with neither. Certain ionic trends match known ion-specific series behavior, especially at high concentrations. Notably, we also examine the ranges of the interactions and conclude that the majority of the effects are tied to local water reorientation dynamics. [ABSTRACT FROM AUTHOR]

In nuclear magnetic resonance, long-lived coherences constitute a class of zero-quantum (ZQ) coherences that have lifetimes that can be longer than the relaxation lifetimes T2 of transverse magnetization. So far, such coherences have been observed in systems with two coupled spins with spin quantum numbers I = 1/2, where a term S 0 T 0 + T 0 S 0 in the density operator corresponds to a coherent superposition between the singlet S 0 and the central triplet T 0 state. Here, we report on the excitation and detection of collective long-lived coherences in AA′MM′XX′ spin systems in molecules containing a chain of at least three methylene (–CH2–) groups. Several variants of excitation by polychromatic spin-lock induced crossing (poly-SLIC) are introduced that can excite a non-uniform distribution of the amplitudes of terms such as S 0 S 0 T 0 S 0 S 0 T 0 , S 0 T 0 S 0 S 0 T 0 S 0 , and T 0 S 0 S 0 T 0 S 0 S 0 . Once the radio frequency fields are switched off, these are not eigenstates, leading to ZQ precession involving all six protons, a process that can be understood as a propagation of spin order along the chain of CH2 groups before the reconversion into observable magnetization by a second poly-SLIC pulse that can be applied to any one or several of the CH2 groups. In the resulting 2D spectra, the ω2 domain shows SQ spectra with the chemical shifts of the CH2 groups irradiated during the reconversion, while the ω1 dimension shows ZQ signals in absorption mode with linewidths on the order of 0.1 Hz that are not affected by the inhomogeneity of the static magnetic field but can be broadened by chemical exchange as occurs in drug screening. The ZQ frequencies are primarily determined by differences ΔJ between vicinal J-couplings. [ABSTRACT FROM AUTHOR]

A new algorithm has been developed to simulate two-dimensional (2D) spectra with correlated anisotropic frequencies faster and more accurately than previous methods. The technique uses finite-element numerical integration on the sphere and an interpolation scheme based on the Alderman–Solum–Grant algorithm. This method is particularly useful for numerical calculations of joint probability distribution functions involving quantities with a parametric orientation dependence. The technique's efficiency also allows for practical least-squares fitting of experimental 2D solid-state nuclear magnetic resonance (NMR) datasets. The simulation method is illustrated for select 2D NMR methods, and a least-squares analysis is demonstrated in the extraction of paramagnetic shift and quadrupolar coupling tensors and their relative orientation from the experimental shifting-d echo 2H NMR spectrum of a NiCl2 · 2D2O salt. [ABSTRACT FROM AUTHOR]

This work presents the influence of host defect centers on the photoluminescence characteristics of Mg 1 − x Er x Al 2 O 4 (x = 0.005, 0.01, and 0.03) nanocrystals under UV and near-infrared (NIR) excitations. The spinel-structured nanocrystals are synthesized through the combustion method. The Rietveld refinement and nuclear magnetic resonance analyses estimated the Er 3 + ion occupancy at octahedral and other random sites of the MgAl 2 O 4 lattice, and the existence of various lattice defects. Diffuse reflectance spectra showed broad bands attributed to oxygen vacancies as well as antisite defects and sharp peaks attributed to f–f transitions of Er 3 + ions. The upconversion luminescence spectra consisted of sharp emission lines, ascribed to Er 3 + ions, in the green and red wavelength regions, which overlapped over the broad curve attributed to intrinsic defects. Further, the UV excited downconversion luminescence spectra showed two broad emission bands in blue–violet and red-NIR regions with a very weak Er 3 + ion emission feature. This up- and downconversion emission revealed energy transfer between host and Er 3 + ions via intrinsic defects. As a result, the emission color changes from bluish purple to white by varying the excitation wavelength from UV to NIR. This rare earth activated luminescence from MgAl 2 O 4 nanocrystals would exhibit potential applications in display devices and solid-state lighting. [ABSTRACT FROM AUTHOR]

Nuclear magnetic resonance (NMR) relaxation experiments shine light onto the dynamics of molecular systems in the picosecond to millisecond timescales. As these methods cannot provide an atomically resolved view of the motion of atoms, functional groups, or domains giving rise to such signals, relaxation techniques have been combined with molecular dynamics (MD) simulations to obtain mechanistic descriptions and gain insights into the functional role of side chain or domain motion. In this work, we present a comparison of five computational methods that permit the joint analysis of MD simulations and NMR relaxation experiments. We discuss their relative strengths and areas of applicability and demonstrate how they may be utilized to interpret the dynamics in MD simulations with the small protein ubiquitin as a test system. We focus on the aliphatic side chains given the rigidity of the backbone of this protein. We find encouraging agreement between experiment, Markov state models built in the χ1/χ2 rotamer space of isoleucine residues, explicit rotamer jump models, and a decomposition of the motion using ROMANCE. These methods allow us to ascribe the dynamics to specific rotamer jumps. Simulations with eight different combinations of force field and water model highlight how the different metrics may be employed to pinpoint force field deficiencies. Furthermore, the presented comparison offers a perspective on the utility of NMR relaxation to serve as validation data for the prediction of kinetics by state-of-the-art biomolecular force fields. [ABSTRACT FROM AUTHOR]

Kavaratamide A (1), a new linear lipodepsipeptide possessing an unusual isopropyl-O-methylpyrrolinone moiety, was discovered from the tropical marine filamentous cyanobacterium Moorena bouillonii collected from Kavaratti, India. A comparative chemogeographic analysis of M. bouillonii collected from six different geographical regions led to the prioritized isolation of this metabolite from India as distinctive among our data sets. AI-based structure annotation tools, including SMART 2.1 and DeepSAT, accelerated the structure elucidation by providing useful structural clues, and the full planar structure was elucidated based on comprehensive HRMS, MS/MS fragmentation, and NMR data interpretation. Subsequently, the absolute configuration of 1 was determined using advanced Marfey's analysis, modified Mosher's ester derivatization, and chiral-phase HPLC. The structures of kavaratamides B (2) and C (3) are proposed based on a detailed analysis of their MS/MS fragmentations. The biological activity of kavaratamide A was also investigated and found to show moderate cytotoxicity to the D283-medullablastoma cell line.

31P nuclear magnetic resonance (NMR) chemical shifts were shown to be very sensitive to the basis set used at the geometry optimization stage. Commonly used energy-optimized basis sets for a phosphorus atom containing only one polarization d-function were shown to be unable to provide correct equilibrium geometries for the calculations of phosphorus chemical shifts. The use of basis sets with at least two polarization d-functions on a phosphorus atom is strongly recommended. In this paper, an idea of creating the basis sets purposed for the geometry optimization that provide the least possible error coming from the geometry factor of accuracy in the resultant NMR shielding constants is proposed. The property-energy consisted algorithm with the target function in the form of the molecular energy gradient relative to P–P bond lengths was applied to create new geometry-oriented pecG-n (n = 1, 2) basis sets for a phosphorus atom. New basis sets have demonstrated by far superior performance as compared to the other commonly used energy-optimized basis sets in massive calculations of 31P NMR chemical shifts carried out at the gauge-including atomic orbital-coupled cluster singles and doubles/pecS-2 level of the theory by taking into account solvent, vibrational, and relativistic corrections. [ABSTRACT FROM AUTHOR]

The relaxation spectra of glass formers solely displaying an α-peak and excess wing contribution collected by various methods are reanalyzed to pin down their different spectral evolution. We show that master curve construction encompassing both α-peak and emerging excess wing works for depolarized light scattering (DLS) and nuclear magnetic resonance (NMR) relaxometry. It reveals the self-part of the slow dynamics' spectrum. Master curves are to be understood as a result of a more extensive scaling covering all temperatures instead of strict frequency–temperature superposition. DLS and NMR display identical relaxation spectra; yet, comparing different systems, we do not find a generic structural relaxation at variance with recent claims. Dielectric spectroscopy (DS) spectra show particularities, which render master curve construction obsolete. The DS α-peak is enhanced or suppressed with respect to that of DLS or NMR, yet, not correlated to the polarity of the liquid. Attempting to single out the excess wing from the overall spectrum discloses a stronger exponential temperature dependence of its amplitude compared to that below Tg and a link between its exponent and that of the fast dynamics' spectrum. Yet, such a decomposition of α-peak and excess wing appears to be unphysical. Among many different glasses, the amplitude of the excess wing power-law spectrum is found to be identical at Tg, interpreted as a relaxation analog to the Lindemann criterion. [ABSTRACT FROM AUTHOR]

We present a computational framework for reliably determining the frequency-dependent intermolecular and intramolecular nuclear magnetic resonance (NMR) dipole–dipole relaxation rates of spin 1/2 nuclei from Molecular Dynamics (MD) simulations. This approach avoids the alterations caused by the well-known finite-size effects of translational diffusion. Moreover, a procedure is derived to control and correct for effects caused by fixed distance-sampling cutoffs and periodic boundary conditions. By construction, this approach is capable of accurately predicting the correct low-frequency scaling behavior of the intermolecular NMR dipole–dipole relaxation rate and thus allows for the reliable calculation of the frequency-dependent relaxation rate over many orders of magnitude. Our approach is based on the utilization of the theory of Hwang and Freed for the intermolecular dipole–dipole correlation function and its corresponding spectral density [L.-P. Hwang and J. H. Freed, J. Chem. Phys. 63, 4017–4025 (1975)] and its combination with data from MD simulations. The deviations from the Hwang and Freed theory caused by periodic boundary conditions and sampling distance cutoffs are quantified by means of random walker Monte Carlo simulations. An expression based on the Hwang and Freed theory is also suggested for correcting those effects. As a proof of principle, our approach is demonstrated by computing the frequency-dependent intermolecular and intramolecular dipolar NMR relaxation rates of 1H nuclei in liquid water at 273 and 298 K based on the simulations of the TIP4P/2005 model. Our calculations are suggesting that the intermolecular contribution to the 1H NMR relaxation rate of the TIP4P/2005 model in the extreme narrowing limit has previously been substantially underestimated. [ABSTRACT FROM AUTHOR]

In this study, the performance of the doubles-corrected higher random-phase approximation [HRPA(D)] has been investigated in calculations of nuclear magnetic resonance spin–spin coupling constants (SSCCs) for 58 molecules with the experimental values used as the reference values. HRPA(D) is an approximation to the second-order polarization propagator approximation (SOPPA) and is, therefore, computationally less expensive than SOPPA. HRPA(D) performs comparable and sometimes even better than SOPPA, and therefore, when calculating SSCCs, it should be considered as an alternative to SOPPA. Furthermore, it was investigated whether a coupled-cluster singles, doubles and perturbative triples [CCSD(T)] or Møller-Plesset second order (MP2) geometry optimization was optimal for a SOPPA and a HRPA(D) SSCC calculation for eight smaller molecules. CCSD(T) is the optimal geometry optimization for the SOPPA calculation, and MP2 was optimal for HRPA(D) SSCC calculations. [ABSTRACT FROM AUTHOR]

The dynamics of viscoelastic fluids are governed by a memory function, essential yet challenging to compute, especially when diffusion faces boundary restrictions. We propose a computational method that captures memory effects by analyzing the time-correlation function of the pressure tensor, a viscosity indicator, through the Stokes–Einstein equation's analytic continuation into the Laplace domain. We integrate this equation with molecular dynamics simulations to derive necessary parameters. Our approach computes nuclear magnetic resonance (NMR) line shapes using a generalized diffusion coefficient, accounting for temperature and confinement geometry. This method directly links the memory function with thermal transport parameters, facilitating accurate NMR signal computation for non-Markovian fluids in confined geometries. [ABSTRACT FROM AUTHOR]

Despite the importance of rhodium complexes in catalysis, and the favorable 100% natural abundance of the spin-1/2 103Rh nucleus, there are few reports of 103Rh nuclear magnetic resonance (NMR) parameters in the literature. In part, this is the consequence of the very low gyromagnetic ratio of 103Rh and its dismal NMR sensitivity. In a previous paper [Harbor-Collins et al., J. Chem. Phys. 159, 104 307 (2023)], we demonstrated an NMR methodology for 1H-enhanced 103Rh NMR and demonstrated an application to the 103Rh NMR of the dirhodium formate paddlewheel complex. In this paper, we employ selective 18O labeling to break the magnetic equivalence of the 103Rh spin pair of dirhodium formate. This allows the estimation of the 103Rh–103Rh spin–spin coupling and provides access to the 103Rh singlet state. We present the first measurement of a 18O-induced 103Rh secondary isotope shift as well as the first instance of singlet order generated in a 103Rh spin pair. The field-dependence of 103Rh singlet relaxation is measured by field-cycling NMR experiments. [ABSTRACT FROM AUTHOR]

We present structural models for three different amyloid fibril polymorphs prepared from amylin20–29 (sequence SNNFGAILSS) and amyloid-β25–35 (Aβ25–35) (sequence GSNKGAIIGLM) peptides. These models are based on the amide C=O bond and Ramachandran ψ-dihedral angle data from Raman spectroscopy, which were used as structural constraints to guide molecular dynamics (MD) simulations. The resulting structural models indicate that the basic structural motif of amylin20–29 and Aβ25–35 fibrils is extended β-strands. Our data indicate that amylin20–29 forms both antiparallel and parallel β-sheet fibril polymorphs, while Aβ25–35 forms a parallel β-sheet fibril structure. Overall, our work lays the foundation for using Raman spectroscopy in conjunction with MD simulations to determine detailed molecular-level structural models of amyloid fibrils in a manner that complements gold-standard techniques, such as solid-state nuclear magnetic resonance and cryogenic electron microscopy. [ABSTRACT FROM AUTHOR]

Techniques for enhancing the signals arising from low-γ, insensitive (I) nuclei are central to solid-state nuclear magnetic resonance. One of the leading and best-established methods to sensitize these unreceptive species is Hartmann–Hahn cross polarization (HH-CP), a polarization transfer mechanism often executed under MAS. Herein, we explore the possibility of utilizing the 1H dipolar order created via adiabatic demagnetization in the rotating frame (ADRF), to enhance the unreceptive spins under MAS. It is found that an efficient polarization transfer via ADRF-CPMAS is not only possible but can exceed, at least in some instances involving plastic crystals, the efficiency of an optimized HH-CPMAS transfer. The experiment requires low radiofrequency nutation fields on both the 1H- and the I-spin channels, and displays unusual matching conditions that are reminiscent of the zero- and double-quantum matching conditions arising under CPMAS, albeit centered at zero frequency and demanding the simultaneous involvement of several spins. The origin of these multi-spin transfer processes is analytically derived and numerically simulated in predictions that compare well with experimental 13C and 15N results collected on model compounds at different spinning speeds. These derivations start from descriptions that depart from traditional thermodynamic arguments, and treat instead the ADRF processes in static and spinning solids on the basis of coherent evolutions. The predictions of these analytical derivations are corroborated by numerical simulations. The effects of additional factors, including chemical shift anisotropies, J-couplings, and radiofrequency inhomogeneities, are also theoretically and experimentally explored. [ABSTRACT FROM AUTHOR]

Nuclear spin hyperpolarization derived from parahydrogen is a technique for enhancing nuclear magnetic resonance (NMR) sensitivity. The key to hyperpolarization experiments is to achieve rapid transfer and detection to minimize relaxation losses, while also avoiding bubbles or turbulence to guarantee high spectral resolution. In this article, we describe an experimental approach for the interleaved joint modulation of parahydrogen-induced polarization and NMR. We provide schematic diagrams of parahydrogen-based polarizer with in situ high-pressure detection capability and low-field polarization transfer. This approach can help to control the experimental process and acquire experimental information, one example of which is the attainment of the highest hyperpolarization signal intensity at 3.6 s after closing the valve. The polarizer demonstrates in situ detection capability, allowing sample to be restabilized within 0.3 ± 0.1 s and high-resolution NMR sampling under a pressure of 3 bars. Moreover, it can transfer polarized samples from the polarization transfer field to the detection region of NMR within 1 ± 0.3 s for completing signal amplification by reversible exchange experiments. [ABSTRACT FROM AUTHOR]

We present a gauge-origin invariant exact two-component (X2C) approach within a modern density functional framework, supporting meta-generalized gradient approximations such as TPSS and range-separated hybrid functionals such as CAM-B3LYP. The complete exchange-correlation kernel is applied, including the direct contribution of the field-dependent basis functions and the reorthonormalization contribution from the perturbed overlap matrix. Additionally, the finite nucleus model is available for the electron-nucleus potential and the vector potential throughout. Efficiency is ensured by the diagonal local approximation to the unitary decoupling transformation in X2C as well as the (multipole-accelerated) resolution of the identity approximation for the Coulomb term (MARI-J, RI-J) and the seminumerical exchange approximation. Errors introduced by these approximations are assessed and found to be clearly negligible. The applicability of our implementation to large-scale calculations is demonstrated for a tin pincer-type system as well as low-valent tin and lead complexes. Here, the calculation of the Sn nuclear magnetic resonance shifts for the pincer-type ligand with about 2400 basis functions requires less than 1 h for hybrid density functionals. Further, the impact of spin–orbit coupling on the nucleus-independent chemical shifts and the corresponding ring currents of all-metal aromatic systems is studied. [ABSTRACT FROM AUTHOR]

We report measurements of the Meissner screening profile in a Nb (300 nm)/ Al 2 O 3 thin film using 8 Li β -detected nuclear magnetic resonance (β -NMR). The NMR probe 8 Li was ion-implanted into the Nb film at energies ≤ 20 keV, corresponding to mean stopping depths comparable to Nb 's magnetic penetration depth λ. 8 Li 's strong dipole–dipole coupling with the host 93 Nb nuclei provided a "cross-relaxation" channel that dominated in low magnetic fields, which conferred indirect sensitivity to the local magnetic field via the spin-lattice relaxation (SLR) rate 1 / T 1. From a fit of the 1 / T 1 data to a model accounting for its dependence on temperature, magnetic field, and 8 Li + implantation energy, we obtained a magnetic penetration depth λ 0 = 51.5(22) nm, consistent with a relatively short carrier mean-free-path ℓ = 18.7(29) nm typical of similarly prepared Nb films. The results presented here constitute an important step toward using 8 Li β -NMR to characterize bulk Nb samples with engineered surfaces, which are often used in the fabrication of particle accelerators. [ABSTRACT FROM AUTHOR]

In hyperpolarization experiments using parahydrogen, a partially negative line (PNL) of o-H2 is occasionally spotted in the nuclear magnetic resonance (NMR) spectra. This is a manifestation of the two-spin order (TSO) of the proton spins, appearing transiently in o-H2 molecules freshly derived from p-H2. For the TSO to be observable, the o-H2 NMR signal must be split into a doublet. In the literature, the splitting is believed to originate from a slow exchange of the dissolved dihydrogen with the dihydride moiety bound to a catalyst present in the reaction mixture. Because this hypothesis may be debatable, in this work a different splitting mechanism is proposed. It employs a residual dipolar coupling (RDC) between the hydrogen protons, originating from a partial orientation of the H2 molecules by the external magnetic field. The orientation effect is due to the anisotropic magnetic polarizability of H2. In a magnetic field of 11.74 T at room temperature, the currently predicted value of the RDC is −0.0024 Hz. Even such small RDC values are sufficient for the PNL effect to be clearly visible in NMR spectra for physically reasonable levels of the TSO in the o-H2 molecules. For RDC values much smaller than the natural linewidth of o-H2, the theoretical frequency distance between the minimum and maximum of PNL proves to be practically independent of the RDC and is of the order of the linewidth. The calculated amplitudes of the PNLs are proportional to the RDC values used in the calculations. [ABSTRACT FROM AUTHOR]

In hyperpolarization experiments using parahydrogen, a partially negative line (PNL) of o-H2 is occasionally spotted in the nuclear magnetic resonance (NMR) spectra. This is a manifestation of the two-spin order (TSO) of the proton spins, appearing transiently in o-H2 molecules freshly derived from p-H2. For the TSO to be observable, the o-H2 NMR signal must be split into a doublet. In the literature, the splitting is believed to originate from a slow exchange of the dissolved dihydrogen with the dihydride moiety bound to a catalyst present in the reaction mixture. Because this hypothesis may be debatable, in this work a different splitting mechanism is proposed. It employs a residual dipolar coupling (RDC) between the hydrogen protons, originating from a partial orientation of the H2 molecules by the external magnetic field. The orientation effect is due to the anisotropic magnetic polarizability of H2. In a magnetic field of 11.74 T at room temperature, the currently predicted value of the RDC is −0.0024 Hz. Even such small RDC values are sufficient for the PNL effect to be clearly visible in NMR spectra for physically reasonable levels of the TSO in the o-H2 molecules. For RDC values much smaller than the natural linewidth of o-H2, the theoretical frequency distance between the minimum and maximum of PNL proves to be practically independent of the RDC and is of the order of the linewidth. The calculated amplitudes of the PNLs are proportional to the RDC values used in the calculations. [ABSTRACT FROM AUTHOR]

The nuclear magnetic resonance (NMR) spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging due to the low NMR signal strength. Methodology for the rapid acquisition of 103Rh NMR parameters is demonstrated for the case of the rhodium formate "paddlewheel" complex R h 2 (H C O 2 ) 4 . A scheme is described for enhancing the 103Rh signal strength by polarization transfer from 1H nuclei, which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-γ nuclei. The 103Rh relaxation time constants T1 and T2 are measured within 20 min by using 1H-detected experiments. The field dependence of the 103Rh T1 is measured. The high-field relaxation is dominated by the chemical shift anisotropy mechanism. The 103Rh shielding anisotropy is found to be very large: |Δσ| = 9900 ± 540 ppm. This estimate is compared with density functional theory calculations. [ABSTRACT FROM AUTHOR]

The Protein Ensemble Database (PED) (URL: https://proteinensemble.org) is the primary resource for depositing structural ensembles of intrinsically disordered proteins. This updated version of PED reflects advancements in the field, denoting a continual expansion with a total of 461 entries and 538 ensembles, including those generated without explicit experimental data through novel machine learning (ML) techniques. With this significant increment in the number of ensembles, a few yet-unprecedented new entries entered the database, including those also determined or refined by electron paramagnetic resonance or circular dichroism data. In addition, PED was enriched with several new features, including a novel deposition service, improved user interface, new database cross-referencing options and integration with the 3D-Beacons network-all representing efforts to improve the FAIRness of the database. Foreseeably, PED will keep growing in size and expanding with new types of ensembles generated by accurate and fast ML-based generative models and coarse-grained simulations. Therefore, among future efforts, priority will be given to further develop the database to be compatible with ensembles modeled at a coarse-grained level.

The growth mechanism of thiolate-protected gold nanoclusters (AuNCs) has been advanced, but precise crystal structure information is lacking. Recent mass spectrometry and nuclear magnetic resonance analysis experiments traced the Au24(SR)18 cluster as a non-negligible byproduct intermediate during the reaction between [Au25(SR)18]−, the flagship cluster of the remarkable nanocluster ship, and Au25(SR)19, a cluster with 25 Au atoms but featuring a completely different structure than the [Au25(SR)18]− cluster. However, the precise structure of the Au24(SR)18 cluster is unknown. In this study, a total of seven Au24(SR)18 isomers were constructed using the grand unified model. Density functional theory calculations demonstrated that two of them could be considered quasi-degenerate suggesting that both might coexist in experiments. Geometrical features, electronic structures, and absorption spectra were calculated for potential future comparisons. This work contributes to fully interpreting the growth mechanism of AuNCs. [ABSTRACT FROM AUTHOR]

The NIST gas chromatographic retention index database is widely used in gas chromatography–mass spectrometry analysis. For many compounds, the NIST database contains many entries that are presumably obtained independently of each other. We showed with specific examples that there are cases in the NIST database where several entries exist for the same compound, and all of them are equally erroneous (an error of more than 100 units). In particular, we demonstrated that all retention index values for such an important compound as imidazole for non-polar stationary phases in the NIST database are erroneous. In addition to imidazole, a similar situation is observed for four more nitrogen-containing heterocyclic compounds. For certainty, measurements were performed under several conditions, using various temperature programs, and using two specimens of columns. The structures were confirmed using nuclear magnetic resonance and mass spectrometry. It was shown with specific examples that many values are not reliable: either data were obtained using standard samples of undescribed origin without confirmation (without even using mass spectrometry) or, in some cases, standard samples were not used at all, and the retention index was obtained for a mixture component identified using a mass spectral library search. Some "independent" values are not such but are repeated publications of the same data (secondary sources), or simply several values taken from the same source. In the work, an analysis was carried out and assumptions were made about how several equally incorrect retention index values could appear in the NIST database. [ABSTRACT FROM AUTHOR]

It is of significant importance to public health that reliable monitoring of nitroimidazoles be conducted, while certified reference materials (CRMs) are essential for accurate and reliable detection. A project has been initiated with the objective of developing nitroimidazole purity CRMs to ensure that results from nationwide monitoring laboratories for nitroimidazoles in antibiotic residues can be compared and traced. The candidates were successively characterized in terms of their structure by means of infrared (IR) spectroscopy and mass spectrometry (MS). The mass balance (MB) method and the quantitative nuclear magnetic resonance (qNMR) method were utilized to determine the purity of nitroimidazoles with remarkable accuracy. Furthermore, a methodical investigation was conducted on homogeneity, stability, and uncertainty. Six nitroimidazole purity CRMs, including tinidazole (GBW09252), secnidazole (GBW09286), ronidazole (GBW09288), metronidazole (GBW(E)090755), dimetridazole (GBW(E)090819), and ornidazole (GBW(E)090820), were finally manufactured following authorization from China's State Administration for Market Regulation (SAMR). By using these CRMs, it is possible to improve the traceability, accuracy, and comparability of nitroimidazole measurements in a range of agricultural products, protecting public health. [ABSTRACT FROM AUTHOR]

Currently, there has been a growing interest in fermented foods and plant-based beverages (PBBs) by the consumers because of the benefits they provide to human health or due to restrictions in the diet associated to some pathologies or personal choices. Nuclear magnetic resonance (NMR) is a versatile technique that presents many advantages for the identification and quantification of metabolites in food with a variety of one- and two-dimensional experiments. This review delves into the current applications of NMR in the fields of fermented foods and PBBs. The interest from researchers in the analysis of fermented foods by NMR in the recent literature mainly focused on three main sub-areas: characterization of exopolysaccharides (EPS) and their functional, and rheological properties; metabolomics to find discriminant markers during and after the process of fermentation for the optimization of the productive process or development of products; and characterization of traditional and novel foods. However, the area of plant-based beverages studies by NMR presented a remarkable literature gap. The opportunities for future investigations concerning food authentication, traceability, and functional food development, among others, are presented. [ABSTRACT FROM AUTHOR]

Metabolomics aims to study the downstream effects of variables like diet, environment, or disease on a given biological system. However, inconsistencies in sample preparation, data acquisition/processing protocols lead to reproducibility and accuracy concerns. A systematic study was conducted to assess how sample preparation methods and data analysis platforms affect metabolite susceptibility. A targeted panel of 25 metabolites was evaluated in 69 clinical metabolomics samples prepared following three different protocols: intact, ultrafiltration, and protein precipitation. The resulting metabolic profiles were characterized by 1D 1H nuclear magnetic resonance (NMR) spectroscopy and analyzed with Chenomx v8.3 and SMolESY software packages. Greater than 90% of the metabolites were extracted more efficiently using protein precipitation than filtration, which aligns with previously reported results. Additionally, analysis of data processing software suggests that metabolite concentrations were overestimated by Chenomx batch-fitting, which only appears reliable for determining relative fold changes rather than absolute quantification. However, an assisted-fit method provided sufficient guidance to achieve accurate results while avoiding a time-consuming fully manual-fitting approach. By combining our results with previous studies, we can now provide a list of 5 common metabolites [2-hydroxybutyrate (2-HB), choline, dimethylamine (DMA), glutamate, lactate] with a high degree of variability in reported fold changes and standard deviations that need careful consideration before being annotated as potential biomarkers. Our results show that sample preparation and data processing package critically impact clinical metabolomics study success. There is a clear need for an increased degree of standardization and harmonization of methods across the metabolomics community to ensure reliable outcomes. [ABSTRACT FROM AUTHOR]

Glasses of enlarged chemical composition in the xCsBr-(100- x)B 2 O 3 system, with x = 30–80 mol% have been prepared and studied for the first time. The hydrothermal preparation method is used to prepare fine powdered samples. The X-ray Diffraction (XRD), Fourier Transform Infrared spectra (FTIR) and 11B Nuclear Magnetic Resonance (11B NMR) are the tools used to study the structure of glasses. Even at the high CsBr concentration (30–60 mol%), XRD results revealed an amorphous structure characterized most of the examined compositions. But glasses enriched with CsBr (70 and 80 mol%) possess some ordered sub-structures impeded in the main amorphous network. 11B NMR and FTIR spectroscopy confirmed the presence of BO 3 triangle as the major and dominant structural units. The four coordinated boron (BO 4), on the other hand, can't be detected in the all analyzed compositions. An extremely low concentration from BBr 4 tetrahedral groups (boron coupled with Br) is formed. The B-O bonds of planar BO 3 triangles, which are the fundamental units, were involved in the production of amorphous clusters of the type Cs 4 B 5 O 9 ]Br. Density (D) measurement and calculating molar volume (V m), packing density and free volume(V f) have been studied. The added CsBr can't play a role of modifier but it might be inserted interstitially between the borate structural units causing increasing of molar volume and free space in the glass network structure. The results based on transmission electron microscopy (TEM-EDP) and X-ray diffraction pattern (XRD) are in good agreement, indicating that the amorphous-clustered species are developed in the studied glasses. [ABSTRACT FROM AUTHOR]

Essential oils are a vast class of compounds that have many interesting therapeutical properties. In this sense, tea tree oil (TTO) stands out for its antioxidant, antifungal, antibacterial, anti-inflammatory, and antihyperproliferative potential. However, the low stability and solubility of these compounds can limit their therapeutical capacity, making it necessary to adopt a strategy to overcome this mishap. In that regard, nanoencapsulation can be highlighted as a promising maneuver capable of protecting the active and increasing its solubility in water, promoting greater compatibility and bioavailability. Based on the above, the main objective of this study was to evaluate polycaprolactone/Pluronic F-127 PCL/F-127 polymeric nanoparticles loaded with 10–30% w/w TTO obtained via nanoprecipitation. The obtained particles were evaluated by atomic force microscopy and UV–Vis spectroscopy to determine retention efficiency and obtain the release profile (with the evaluation of release models), time-domain nuclear magnetic resonance, antimicrobial activity, and cytotoxicity in fibroblasts and epithelial cells. The obtained results show the formation of particles of spherical-type morphology particles with smooth surfaces and particle sizes around 400 nm, with retention efficiencies between 60 and 70% and sustained release profile for up to about 6 or 7 h and compatible with the Higuchi model. Regarding the antimicrobial activity of the systems, it was observed that TTO presents antimicrobial activity against the evaluated strains (S. aureus, C.albicans, and E.coli) and that the encapsulation process can increase the activity against the strain of E. coli. Finally, the cytocompatibility analyses showed that the NNPs obtained are not cytotoxic to the cell lines evaluated. [ABSTRACT FROM AUTHOR]

The radioelement Technetium (element 43) pertains to various domains including the nuclear enterprise (i.e., spent nuclear fuel (SNF) reprocessing and nuclear waste remediation) and nuclear medicine (i.e., development of new imaging agents) as well as to the fundamental science of transition metals (i.e., chemical trends in catalytic properties). One method that can provide critical information to improve knowledge in these domains is 99Tc nuclear magnetic resonance (NMR) spectroscopy. The review, presented here, summarizes the pivotal role of 99Tc NMR spectroscopy over the past two decades and presents prospects of the method to tackle challenges in Tc chemistry. The radioelement technetium is central in spent nuclear fuel reprocessing and waste remediation, the development of new imaging agents, as well as in fundamental science of transition metals. Here, the authors review the pivotal role of 99Tc NMR spectroscopy over the past two decades and present prospects of the method to tackle challenges in Tc chemistry. [ABSTRACT FROM AUTHOR]

A novel sanitizer tablet containing clove essential oil (CO) microemulsion was developed. A preformulation study using nuclear magnetic resonance and thermal analyses showed component compatibility. The main components of the samples remained intact despite a color change, probably due to a strong acid-base interaction between eugenol and diethanolamine. The CO microemulsion showed acaricidal and larvicidal activities superior to the commercial product, with product efficacy of 99.9% and larvae mortality of 94%. Optimal spray-drying conditions were achieved with inlet and outlet temperatures of 50°C and 40°C, respectively, an aspiration rate of 1 m3 min⁻1, and a 0.25 L h⁻1 injection flow. The feed suspension comprised 50% (v/v) liquid soap, 37.5% (v/v) water, 12.5% (v/v) ethanol, and 5.0% (w/v) silica. This formulation and processing parameters allowed for successful free-flow powder formation, providing a suitable matrix for incorporating the CO microemulsion via wet granulation without heating. Finally, sanitizer tablets produced from such granules resulted in a uniform product with low weight variation (coefficient of variation of 0.15%), eugenol content of 95.5% ± 3.3, and friability of 0.58%. Furthermore, the tablets showed rapid aqueous dispersion, forming a colloidal system with particle sizes of 221 nm and a zeta potential of -17.2 mV. Antimicrobial activity tests demonstrated the effectiveness of the sanitizer tablet against bacteria and fungi, exhibiting comparable antimicrobial potency to isolated CO. Hence, the sanitizer tablet developed represents a promising candidate as a practical and efficient solution for pest control, offering strong antimicrobial and acaricidal activity. [ABSTRACT FROM AUTHOR]

Self‐hygroscopic hydrogels, characterized by high evaporation enthalpy, cooling efficiency, and self‐regulating properties, have garnered significant attention. However, most current research focuses on enhancing the hygroscopic and desorption performance, often overlooking the importance of monitoring the self‐regulation process, which limits its further application. Advanced visualization technologies, such as in situ electrical impedance tomography, low‐field nuclear magnetic resonance, and hyperspectral imaging, offer potential insights into this behavior, yet they often require additional devices, incur high costs, and involve complex sample preparation processes. Therefore, drawing inspiration from nature, humidity‐color‐sensitive hydrogels (HCSHs) strategy is proposed for visualized cooling. Benefiting from the strong polar responsiveness of the aggregation‐induced emission (AIE) molecules, the hydrogel's fluorescence significantly changes with varying interior water content, thereby its self‐regulation process is monitored easily. Further, the obtained hydrogel could be applied in the electronic device cooling owing to the polymer skeletons’ high swelling ratio, strong adhesion, and excellent self‐hygroscopic properties. This strategy overcomes current limitations in the visual technology of self‐hygroscopic materials and provides new insights into intelligent thermal management for electronic devices. [ABSTRACT FROM AUTHOR]

Commercial SSZ‐13 zeolite with different n(Si)/n(Al) ratios and from different suppliers were subjected to a post‐synthetic treatment in order to create mesopores of up to 15 nm. Furthermore, the materials were modified with copper ions and thoroughly physico‐chemically characterized. The modified textural properties varied the nature of copper species, and thus, activity in the selective catalytic reduction of NOx with ammonia (NH3‐SCR‐DeNOx). Pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) studies with hexane as probe liquid revealed improved intracrystalline diffusion for some Cu‐containing SSZ‐13 materials. The NH3‐SCR‐DeNOx pathways are verified via in situ DR UV‐Vis, in situ FT‐IR and EPR, temperature‐programmed studies as well as SSITKA studies that provide a mechanistic understanding of the reaction. Kinetic modelling results demonstrate the highest NH3‐SCR‐DeNOx reaction rates and up to 20 % lower energy barriers with n(Si)/n(Al) ratio of 6.5 for all modified forms (i. e., (NH4)Cu‐SSZ‐13_6.5 and Cu‐SSZ‐13_6.5_NaOH/0.1) and cause only negligible parasitic ammonia oxidation. The modelling of the stop‐flow experiments further demonstrates that the SCR pathway via the HONO surface intermediate is present but barely contributes to the overall NO conversion compared to the dominant path between adsorbed NH3 and NO from the gas phase. [ABSTRACT FROM AUTHOR]

The significance of incorporating anion species into electrolyte solvation structures, particularly with doubly charged Mg2 + ions, is investigated using the grand canonical density functional theory (GC‐DFT) approach. In an extension of previously established methodology, the work explores the thermodynamic stability in acetonitrile (AN) at the interface with Mg3Bi2 and Mg2Sn. Two different anions, TFSI− and ClO4−$\text{ClO}_4^-$, are strategically incorporated based on energy comparisons. Despite the known chemical compatibility of alloy anodes with the electrolyte solution, the research reveals a novel form of solvent degradation, which is also reported in the case of pure Mg anode with conventional electrolytes. Notably, the AN molecule adjacent to anion species exhibits reduced susceptibility to reduction (−0.8 – −0.4 V vs Mg2 +/Mg) in the lower potential range in comparison with the solvation structure of full dissociation. Charge density difference and density of states analyses detail solvent molecules becoming electrophilic, with the LUMO overlapping with the Fermi level at lower potentials when the electrostatic interaction with anion species are considered. Experimental studies using nuclear magnetic resonance (NMR) spectroscopy and linear sweep voltammetry (LSV) validate the theoretical results, providing a comprehensive understanding. This methodology, augmenting prior approaches, provides valuable guidance for electrolyte composition based on predominant solvation structures in multivalent solutions. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis of seleno‐substituted chromenes from selenoalkynes and phenols. In this cascade reaction, the applied gold catalyst not only functions as a π‐acid, but also as a Lewis acid, enabling the propargylic substitution in the first step to connect the oxygen carbon bond. Under the optimal reaction condition a total of 26 chromenes were accessible by this modular access. During scale up experiments, the hydrolysis of the vinylselenium substructure to the corresponding chromenones was observed. By revisiting the electron‐rich starting materials, four chromenones were produced following a one‐pot reaction using a single gold catalyst. To better understand the interaction of gold and selenium, a series of nuclear magnetic resonance studies and high‐resolution mass spectrometry studies were performed, which led to the proposal of a mechanism for this transformation. [ABSTRACT FROM AUTHOR]

The aim of this study was to explore the intricate relationship between serum metabolomics and lifestyle factors, shedding light on their impact on health in the context of breast cancer risk. Detailed metabolic profiles of 2283 female participants in the Trøndelag Health Study (HUNT study) were obtained through nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). We show that lifestyle-related variables can explain up to 30% of the variance in individual metabolites. Age and obesity were the primary factors affecting the serum metabolic profile, both associated with increased levels of triglyceride-rich very low-density lipoproteins (VLDL) and intermediate-density lipoproteins (IDL), amino acids and glycolysis-related metabolites, and decreased levels of high-density lipoproteins (HDL). Moreover, factors like hormonal changes associated with menstruation and contraceptive use or education level influence the metabolite levels. Participants were clustered into three distinct clusters based on lifestyle-related factors, revealing metabolic similarities between obese and older individuals, despite diverse lifestyle factors, suggesting accelerated metabolic aging with obesity. Our results show that metabolic associations to cancer risk may partly be explained by modifiable lifestyle factors. Lifestyle-related factors account for up to 30% of serum metabolic variance, with age and obesity as key factors. Metabolic similarities in obese and older women suggest that modifiable lifestyle factors may affect breast cancer risk. [ABSTRACT FROM AUTHOR]

Quaternary mudstone biogas reservoirs in the Qaidam Basin have shown great potential. However, complex pore structures with high clay contents and high heterogeneity limit the understanding of the storage and migration principles of these reservoirs. In this paper, HPMI and nitrogen adsorption experiments, in combination with NMR experiments under water saturation, centrifugation, various drying temperatures and other conditions, were adopted to determine the pore structure characteristics. Specifically, the reservoir space types and pore radius distribution characteristics were clarified. The cutoff values for different types of pores were identified based on the water-saturated mudstone NMR T2 spectra for full aperture distribution scales jointly characterized by mercury injection and nitrogen adsorption experiments. Furthermore, the three pore components and the saturation of different fluids were obtained. The research results indicate that the mudstone biogas reservoir has developed various reservoir spaces, and the pore size is primarily in the micronanometer range. The average total porosity reaches 27.28%, but the proportion of movable water pores is only 9.23% with poor fluid mobility, and the fluids in the pores are mostly capillary-bound water and clay-bound water. Among the different lithologies, argillaceous sand is more likely to become a good production layer. [ABSTRACT FROM AUTHOR]

Open‐shell organic radical semiconductor materials have received increasing attention in recent years due to their distinctive properties compared to the traditional materials with closed‐shell singlet ground state. However, their poor chemical and photothermal stability in ambient conditions remains a significant challenge, primarily owing to their high reactivity with oxygen. Herein, a novel open‐shell poly(3,4‐dioxythiophene) radical PTTO2 is designed and readily synthesized for the first time using low‐cost raw material via a straightforward BBr3‐demethylation of the copolymer PTTOMe2 precursor. The open‐shell character of PTTO2 is carefully studied and confirmed via the signal‐silent 1H nuclear magnetic resonance spectrum, highly enhanced electron spin resonance signal compared with PTTOMe2, as well as the ultra‐wide ultraviolet‐visible‐near nfraredUV–vis–NIR absorption and other technologies. Interestingly, the powder of PTTO2 exhibits an extraordinary absorption range spanning from 300 to 2500 nm and can reach 274 °C under the irradiation of 1.2 W cm−2, substantially higher than the 108 °C achieved by PTTOMe2. The low‐cost PTTO2 stands as one of the best photothermal conversion materials among the pure organic photothermal materials and provides a new scaffold for the design of stable non‐doped open‐shell polymers. [ABSTRACT FROM AUTHOR]