A novel method, Spin-State-Selective (S) HMBC hetero, for accurate measurement of heteronuclear coupling constants is introduced. The method extends the S HMBC technique for measurement of homonuclear coupling constants by appending a pulse sequence element that interchanges the polarization in C-H methine pairs. This amounts to converting the spin-state selectivity from H spin states to C spin states in the spectra of long-range coupled H spins, allowing convenient measurement of heteronuclear coupling constants similar to other S or E.COSY-type methods. As usual in this type of techniques, the accuracy of coupling constant measurement is independent of the size of the coupling constant of interest. The merits of the new method are demonstrated by application to vinyl acetate, the alkaloid strychnine, and the carbohydrate methyl β-maltoside.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1016/j.jmr.2016.11.019 | DOI Listing |
Biochem Biophys Rep
March 2025
Department of Chemistry, University of Nebraska at Kearney, USA.
Human citrate synthase (hCS) was kinetically characterized through full progress curve kinetic modelling using kinetic simulation, global fitting of the direct AcCoA to CoA transition, and a coupled thiol probe reaction to better determine the kinetics with low substrate concentration. Our analysis provides one of the most rigorous kinetic analyses of any citrate synthase ruling out the need to invoke complex cooperative mechanisms to explain progress curve data. Furthermore, we collected and modeled stopped-flow pH-dependent kinetic data with CoA and popular thiol probes such as Ellman's reagent (DTNB) and 4,4'-Dithiodipyridine (DPS), providing the opportunity for detailed kinetic simulations using these thiol probes with CoA producing enzymes.
View Article and Find Full Text PDFNanoscale
January 2025
Department of Physics, University of Tehran, North Kargar Ave, Tehran 14395547, Iran.
In recent years, MAX phases and their two-dimensional counterparts, MXenes, have emerged as significant subjects of interest in the fields of science and engineering, owing to their varied geometries, compositions, and extensive range of applications. This research employs first-principles calculations to explore the geometrical structures, electronic characteristics, phonon dispersions, dynamic stability, electron-phonon coupling (EPC), and superconducting properties of 27 out-of-plane ordered double transition metal carbides, referred to as o-MAX phases, characterized by the general formula MM'AlC (where M = Nb, Mo, W and M' = Sc, Ti, Zr, Hf, V, Nb, Ta, Mo, W). We have identified 16 superconducting o-MAX phases, with four specific compounds WVAlC, WNbAlC, WTaAlC, and MoNbAlC exhibiting a critical temperature () that surpasses 10 K, representing the highest reported experimentally for MAX phases thus far.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Department of Chemistry, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, China.
Operando electron paramagnetic resonance is used to monitor the light-initiated generation of the diethylnitroxyl radical from diethylhydroxylamine (DEHA) and its decay kinetics, thereby unveiling solvent effects on both the electronic structure and stability of the nitroxyl radical. The observed trends in hyperfine coupling constants ( and ) across different solvents align with previously reported values of the 4-amino-2,2,6,6-tetramethylpiperidoxyl radical (ATEMPO). Regarding the stability of the DEHA radical in various solvents, the obtained decay-kinetic constants () correlated more strongly with than with the permittivity of the solvents.
View Article and Find Full Text PDFBiochemistry
January 2025
School of Biology, Biomedical Sciences Research Complex, University of St Andrews, St Andrews KY16 9ST, United Kingdom.
The enzyme 4-oxo-l-proline reductase (BDH2) has recently been identified in humans. BDH2, previously thought to be a cytosolic ()-3-hydroxybutyrate dehydrogenase, actually catalyzes the NADH-dependent reduction of 4-oxo-l-proline to -4-hydroxy-l-proline, a compound with known anticancer activity. Here we provide an initial mechanistic characterization of the BDH2-catalyzed reaction.
View Article and Find Full Text PDFFront Microbiol
January 2025
Laboratory of Molecular Biotechnology, National Center for Biotechnology, Astana, Kazakhstan.
fungal species are considered major plant pathogens, infecting various crops and resulting in significant agricultural losses. Additionally, these species can contaminate grain with multiple mycotoxins that are harmful to humans and animals. Efficient pest management relies on timely detection and identification of phytopathogens in plant and grain samples, facilitating prompt selection of a crop protection strategy.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!