We highlight a convenient synthesis to selectively deuterate an aryl C-H hydrogen bond donor in an arylethynyl bisurea supramolecular anion receptor and use the Perrin method of competitive titrations to study the deuterium equilibrium isotope effects (DEIE) of anion binding for HS, Cl, and Br. This work highlights the utility and also challenges in using this method to determine EIE with highly reactive and/or weakly binding anions.
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http://dx.doi.org/10.1039/d1ra05711a | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Universitat Bern, Department of Chemistry and Biochemistry, Freiestrasse 3, 3012, Bern, SWITZERLAND.
Isotope Exchange processes are becoming the preferred way to prepare isotopically labelled molecules, avoiding the redesign of multistep synthetic protocols. In the case of deuterium incorporation, the most used strategy has employed transition metals, that offer high reactivity under mild reaction conditions. Despite their success, the trade-off is that these metals are precious, and often exhibit high toxicity.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, USA.
The reaction coefficient for hydrogen/deuterium (H/D) exchange and the diffusion of hydrated excess protons within amorphous solid water (ASW) are characterized as a function of temperature. For these experiments, water films are deposited on a Pt(111) substrate at 108 K, and reactions with pre-adsorbed hydrogen atoms produce hydrated protons. Upon heating, protons diffuse within the water, and H/D exchange occurs when they encounter D2O probe molecules deposited in the films.
View Article and Find Full Text PDFSci Bull (Beijing)
December 2024
Key Laboratory for Laser Plasmas and Department of Physics and Astronomy, Collaborative Innovation Center of IFSA (CICIFSA), Shanghai Jiao Tong University, Shanghai 200240, China; Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China. Electronic address:
Although ignition had been achieved at the National Ignition Facility (NIF), recent observations of the experiments indicate novel physics that beyond theoretical predictions emerge, e.g., the neutron analysis of experiments has revealed deviations from the Maxwellian distributions in ion relative kinetic energies of burning plasmas, with the surprising emergence of supra-thermal deuterium and tritium (DT) ions that fall outside the predictions of macroscopic statistical hydrodynamic models.
View Article and Find Full Text PDFRSC Chem Biol
January 2025
Novartis Biomedical Research Basel Switzerland
The design of potent RAS inhibitors benefits from a molecular understanding of the dynamics in KRAS and NRAS and their oncogenic mutants. Here we characterize switch-1 dynamics in GTP-state KRAS and NRAS by P NMR, by N relaxation dispersion NMR, hydrogen-deuterium exchange mass spectrometry (HDX-MS), and molecular dynamics simulations. In GMPPNP-bound KRAS and NRAS, we see the co-existence of two conformational states, corresponding to an "inactive" state-1 and an "active" state-2, as previously reported.
View Article and Find Full Text PDFbioRxiv
November 2024
Structural Biology Initiative, CUNY Advanced Science Research Center, New York, NY 10031.
The general stress response (GSR) protects bacteria from a wide range of stressors. In , GSR activation is coordinated by HWE/HisKA2 family histidine kinases (HKs), which can exhibit non-canonical structure and function. For example, while most light-oxygen-voltage sensor-containing HKs are light activated dimers, the RT-HK has inverted "dark on, light off" signaling logic with a tunable monomer/dimer equilibrium.
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