We have experimentally demonstrated a pulse sequence for the acquisition of heterodyned two-dimensional infrared (2D IR) spectra that correlates the overtone and combination bands to the fundamental frequencies. The spectra are generated by Fourier transforming the time domain signal that is allowed to evolve during one- and two-quantum coherence times. In this manner, the overtone and combination bands appear along the two-quantum axis, resulting in a direct determination of the diagonal and off-diagonal anharmonicities. To demonstrate this pulse sequence, we have collected two-quantum 2D IR spectra of a ruthenium dicarbonyl complex, extracted the diagonal and off-diagonal anharmonicities, and simulated the spectra using an exciton model. Several polarization conditions are presented that suppress the diagonal or cross peaks and we have used them to improve the accuracy of the measurement.
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http://dx.doi.org/10.1063/1.1649725 | DOI Listing |
J Biomol NMR
January 2025
Research Unit Molecular Biophysics, Leibniz-Forschungsinstitut für Molekulare Pharmakologie, Robert- Rössle-Straße 10, 13125, Berlin, Germany.
Chemical shift assignments of large membrane proteins by solid-state NMR experiments are challenging. Recent advancements in sensitivity-enhanced pulse sequences, have made it feasible to acquire H-detected 4D spectra of these challenging protein samples within reasonable timeframes. However, obtaining unambiguous assignments remains difficult without access to side-chain chemical shifts.
View Article and Find Full Text PDFAnal Chem
January 2025
Experimental Physics III, TU Dortmund University, Dortmund 44227, Germany.
Spectral dispersion in low-field nuclear magnetic resonance (NMR) can significantly affect NMR spectral analysis, particularly when studying complex mixtures like metabolic profiling of biological samples. To address signal superposition in these spectra, we employed spectral editing with selective excitation pulses, proving it to be a suitable approach. Optimal control pulses were implemented in low-field NMR and demonstrated their capability to selectively excite and eliminate specific amino acids, such as phenylalanine and taurine, either individually or simultaneously.
View Article and Find Full Text PDFFront Neurosci
January 2025
School of Electronic Information and Communications, Huazhong University of Science and Technology, Wuhan City, China.
Introduction: Transcranial magnetic stimulation (TMS) is widely used for the noninvasive activation of neurons in the human brain. It utilizes a pulsed magnetic field to induce electric pulses that act on the central nervous system, altering the membrane potential of nerve cells in the cerebral cortex to treat certain mental diseases. However, the effectiveness of TMS can be compromised by significant heat generation and the clicking noise produced by the pulse in the TMS coil.
View Article and Find Full Text PDFAm J Clin Nutr
January 2025
Department of Nutrition, Center for Big Data and Population Health of IHM, The Second Affiliated Hospital of Anhui Medical University, School of Public Health, Anhui Medical University, Hefei, China. Electronic address:
Background: Hippuric acid (HA), a host-microbe co-metabolite, normally derives from gut microbial catabolism of dietary polyphenols.
Objectives: We investigated the potential interplay between dietary polyphenols and gut microbiota on circulating HA levels, and examined the associations between serum concentrations of HA and cardiometabolic risk markers.
Methods: In a 1-year cohort of 754 community-dwelling adults, serum HA and its precursor [benzoic acid (BA)] and fecal microbiota were assayed using liquid chromatography-tandem mass spectrometry and 16S ribosomal RNA sequencing, respectively.
Front Immunol
January 2025
Rudolf Virchow Center, Center for Integrative and Translational Bioimaging, Julius-Maximilians-Universität of Würzburg, Würzburg, Germany.
Background: The immunopeptidome is constantly monitored by T cells to detect foreign or aberrant HLA peptides. It is highly dynamic and reflects the current cellular state, enabling the immune system to recognize abnormal cellular conditions, such as those present in cancer cells. To precisely determine how changes in cellular processes, such as those induced by drug treatment, affect the immunopeptidome, quantitative immunopeptidomics approaches are essential.
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