Magnetic Resonance in Chemistry最新文献

HRMAS (high-resolution magic angle spinning) nuclear magnetic resonance (NMR) spectroscopy of low-density polyethylene (LDPE) affords ¹H and ¹³C NMR spectra with superior resolution. For acquiring HRMAS NMR spectra, the polymer is first swollen with representative organic solvents. Then, the samples are measured with a conventional solid-state NMR spectrometer in the wideline mode or at the low spinning speed of 2 kHz. Anisotropic interactions like CSA (chemical shift anisotropy) and dipolar interactions are reduced due to the additional mobility of the polymer chains in the presence of the solvent within the polymer network. The combined effect of this mobility and MAS leads to signals with substantially reduced halfwidths as compared to classic MAS of the dry polymer. With HRMAS, all signals of the polymer become visible, and the spectra can be used for a quick and easy assessment of the polymer swelling behavior in diverse solvents. Being able to characterize polymers on the molecular level, and identifying the solvents that penetrate the polymer network best, enables the study of post-synthesis modifications of the polymers. It is demonstrated by paramagnetic HRMAS that the metallocene nickelocene (Cp₂Ni) penetrates the LDPE network along with the solvent and is homogeneously dispersed in the polymer. SEM images prove that the structure of the polymer is not altered by the presence of a solvent and Cp₂Ni. The impact of the paramagnetic Cp₂Ni on the ¹H signal halfwidth and T₁ time of LDPE is studied. HRMAS allows a quick assessment of metal complexes regarding their ability to penetrate the LDPE network and therefore supports future studies of catalytic polymer degradation.

One new monacolin analog, monacolin V (1), together with two new monacolin-like natural products, 6-hydroxyl monacolin P (2) and 3-keto monacolin S (3), were isolated from the ethyl acetate portion of red yeast rice ethanol extract. Their structures were identified by HRESIMS and NMR experiments, and the complete assignments of ¹H and ¹³C NMR data for three compounds were obtained by the aid of HSQC, HMBC, ¹H-¹H COSY, and NOESY data. This is the first time that the NMR data of compounds 2 and 3 have been fully assigned.

A chemically cross-linked version of polystyrene is presented here that allows the preparation of reversibly mechanically compressible gels as NMR weakly aligning media. The gels can be successfully swollen in aromatic solvents such as toluene-d₈ and pyridine-d₅, as well as in CDCl₃, and provided accurate measurements of ¹D_CH RDCs and ¹³C-RCSAs.

In this work, we introduce a novel NMR apodization function designed to enhance spectral resolution while maintaining compatibility with qNMR standards. This function is based on a modified Savitzky-Golay filter, adapted for time-domain application. It effectively suppresses the negative components typically associated with derivative spectra, while also ensuring the preservation of quantitative integrity in NMR analyses.

The removal of heavy metal ions from wastewater often necessitates the use of ion exchange resins. Current methods for assessing ion exchange efficiency are indirect and destructive. Some heavy metal ions, such as Cu²⁺ and Ni²⁺, are paramagnetic and influence the NMR relaxation times of water protons. NMR relaxometry can therefore be utilized to track the removal of these ions by ion exchange resins. In this study, we use relaxometry to monitor in situ the loading with Ni²⁺ and Cu²⁺ of Amberlite IR120 and Dowex Marathon MSC resins, with the resin column inserted into a low-field NMR device. The multiexponential transverse relaxation curves were fitted using a biexponential model. Before and during the loading of the resin, the water with the slowest relaxation corresponds to treated water (free of Ni²⁺ or Cu²⁺) flowing between the resin beads. After saturation, the slowest fraction corresponds to the untreated solution (containing Ni²⁺ or Cu²⁺) flowing between the resin beads saturated with paramagnetic ions. The evolution with time of the transverse relaxation rate and the amplitude of the slowly relaxing water fraction shows a clear transition, occurring later at the bottom of the resin bed compared with the middle and top. This is interpreted as an indication of the saturation of the studied zone with paramagnetic ions, confirmed by the quantification of Ni²⁺ or Cu²⁺ in the effluent using AES spectroscopy. This proof-of-concept study demonstrates that NMR relaxometry can be used in situ to monitor the loading of a resin bed with paramagnetic ions.

The application of quantum-based NMR methods for the structural elucidation of natural and unnatural products has grown significantly. However, accurately calculating the conformational landscape of flexible molecules with intricate intramolecular hydrogen bonding (IHB) networks continues to be a major challenge. In this work, we thoroughly studied the effect of entropic contributions (trough Gibbs free energies calculations) in the DP4+ performance. Our results show that to solve biased systems with strong IHB interactions requires computing the Boltzmann contributions using Gibbs free energies computed with at least triple-ξ basis set and SMD solvation model. In response to this finding, we have updated our DP4+App, a user-friendly Python applet that automates the entire process of calculating DP4+ probabilities. In the new version, the program allows for calculating of conformational contributions at any selected theory level, using either SCF or Gibbs free energies.

Glutathione (GSH) and its oxidized dimer (GSSG) play an important role in living systems as an antioxidant, balancing the presence of reactive oxygen species (ROS). The central thiol (-S-S-) bond in GSSG can undergo free rotation, providing multiple conformations with respect to the S-S bridge. The six titratable sites of GSSG, which are influenced by pH variations, affect these conformations in solution, whereas in solids, additionally crystal packing effects come into play. In view of differing reports about the structure of GSSG in literature, we have here conducted an extensive reexamination of its conformations using NMR, and contrasting results have been obtained for solution and solid state. In solution, the existence of more than one antiparallel orientation of the monomer unit with different hydrogen bonding schemes has been indicated by NOE and amide temperature coefficient results. On the other hand, in the solid-state, a ¹H-¹H double-quantum (DQ) to ¹³C single-quantum (SQ) correlation study has confirmed a parallel orientation, consistent with the reported X-ray crystal structure. Experimentally assigned solid-state NMR resonances have been validated using GIPAW calculations incorporated in the Quantum ESPRESSO package.

The interaction between humic acid (HA) and engineered nanoparticles (NPs) is critical in environmental sciences, especially for understanding the behavior of NPs in natural waters. This study employs ¹H 2D Multi-Exponential Transverse Relaxation (METR) NMR spectroscopy to examine the molecular-level interactions between Pahokee Peat humic acid (HA) and carboxyl-functionalized iron oxide nanoparticles (NPCOs). First, ¹H 2D METR NMR spectroscopy allowed not only the identification of HA in terms of its chemical composition but also the separation of molecules with the same chemical shift values but different rates of molecular tumbling. Then, using solutions with varying NPCO concentrations (0, 10, 40, and 100 μM), we observed significant changes in the T₂ relaxation times of HA components, indicating interactions between HA and NPCO. Analysis showed the biggest effect on two chemical shift regions, corresponding to lipids and carbohydrates, revealing that smaller molecules within these regions exhibit the most significant changes in T₂ values upon the addition of NPCO. This suggests that these molecules are the initial sites of interaction, with the entire HA system being affected at higher NPCO concentrations. These findings highlight the utility of METR NMR spectroscopy in studying complex environmental mixtures and provide insights into the behavior of HA and NPs, essential for understanding the fate of NPs in the environment.

Brønsted acids, such as phosphoric acids derived from chiral 1,1'-bi-2-naphthol (BINOL), are important catalysts in the formation of carbon-carbon and carbon-heteroatom bonds, for example. The catalytic activity of these Brønsted acids is strongly linked to their acidity, and as such, the evaluation of compounds to determine pK_a values provides insight into their catalytic activity. Herein, a ¹⁹F{¹H} NMR methodology is detailed to determine the pK_a of a fluorinated binaphthyl-derived phosphinic acid, rac-1, in acetonitrile and in the presence of a fluorinated sulfonamide reference compound (2-4). The approach was tested initially using 2 and 3, with the ΔpK_a (0.08) in strong agreement with previously reported values (6.6 for 2 and 6.68/6.73 for 3). Sigmoidal curves of normalised chemical shift change (Δδ) against equivalents of the base phosphazene P₁-^tBu added overlapped for 2 and 3, but in the case of rac-1 and either 2, 3 or 4, there was significant separation. A variety of different approaches for determining the ΔpK_a were compared. Values of pK_a determined when the normalised Δδ was 90% were optimal for 2 and 3, whereas a normalised Δδ of 75% was optimal for 4, resulting in the pK_a of rac-1 being determined to be 8.47-8.71.

The quantitative solution conformations of 2-(hydroxymethyl)-tetrahydropyran, α-methyl-d-mannopyranoside, and 6-[α-d-mannopyranosyl]-d-mannopyranose (mannobiose) are described. Parametrized Karplus equations for redundant spin pairs across the terminal ω-torsion and the glycosidic ω-torsion for mannobiose are developed, including ω/θ-hypersurfaces for the terminal hydroxymethylene group. Experimental NMR data, algorithmic spectral simulation (clustered Hamiltonian method), molecular dynamics (MD) simulations (GLYCAM06), energy minimizations by DFT, and adjusted torsion angle populations weighted over the Karplus-type equations are used. We demonstrate that spectral simulation is a powerful tool in the refinement of initial J values obtained from static GAIO DFT calculations. We also show that only as few as one of multiple redundant torsions can be diagnostic for conformational analysis of the disaccharide.