The kinetics of the H/D exchange reaction in angiotensin II, hexaglycine (Gly), Co(II)tetra(3-carboxyphenyl)porphyrin, and tetra(4-carboxyphenyl)porphyrin were followed in real time by mass spectrometry employing desorption/ionization induced by neutral SO clusters. The change of the isotope patterns with increasing degree of deuteration was recorded as a function of DO exposure and the underlying H/D exchange kinetics, i.e., the dependence of the different degrees of deuteration on time, were deduced. The results were modeled by means of Monte Carlo simulations taking into account different reaction constants for the H/D exchange reaction at different functional groups. In the case of the investigated porphyrins, the rate constants were directly assigned to the functional groups involved; in the case of the peptides, reaction at the explicit functional groups and the backbone chain of the molecules could be discriminated.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jpcb.7b06897 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Catalytic H/D exchange of (hetero)arenes with early-late polyhydride heterobimetallic complexes: impact of transition metal pairs.
Dalton Trans
January 2025
Laboratory of Catalysis, Polymerization, Processes and Materials (CP2 M UMR 5128), CNRS, Universite Claude Bernard Lyon 1, CPE-Lyon, Institut de Chimie de Lyon, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
Metal-catalyzed hydrogen isotope exchange (HIE) has become a valuable method for incorporating deuterium and tritium into organic molecules, with applications in a wide range of scientific fields. This study explores the role of transition metal cooperativity in enhancing catalytic hydrogen/deuterium (H/D) exchange using early-late heterobimetallic polyhydride (ELHB) complexes. A series of four ELHB complexes, of general formula [M(CHBu)(H)M'Cp*], combining early transition metals (M = Hf, Ta) with late metals (M' = Ir, Os), were synthesized and evaluated for their catalytic activity in HIE of (hetero)arenes.
View Article and Find Full Text PDFRigorous Analysis of Multimodal HDX-MS Spectra.
J Am Soc Mass Spectrom
January 2025
Department of Medicinal Chemistry, University of Washington, Seattle, Washington 98195, United States.
An inherent strength of hydrogen/deuterium exchange coupled to mass spectrometry (HDX-MS) is its ability to detect the presence of multiple conformational states of a protein, which often manifest as multimodal isotopic envelopes. However, the statistical considerations for accurate analysis of multimodal spectra have yet to be established. Here we outline an unrestrained binomial distribution fitting approach with the corresponding statistical tests to accurately detect and, when possible, deconvolute isotopic distributions that contain multiple subpopulations.
View Article and Find Full Text PDFMesoporous Silica Nanoparticle Rigid Anchor Attached Pt Complex for Catalytic H/D Exchange of Aromatic Substrates.
Inorg Chem
January 2025
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States.
A Pt(II) aqua complex supported by mesoporous silica nanoparticle (MSN)-immobilized sulfonated CNN pincer ligand featuring a rigid SiO tether was prepared. This hybrid material was tested as a catalyst in H/D exchange reactions of C(sp)-H bonds of selected aromatic substrates and DO-2,2,2-trifluoroethanol- (TFE-) mixtures or CDCOD acting as a source of exchangeable deuterium. The catalyst immobilization served as a means to not only enable the catalyst's recyclability but also minimize the coordination of sulfonate groups and the metal centers originating from different catalyst's moieties that would preserve reactive Pt(OH) fragments needed for catalytic C-H bond activation.
View Article and Find Full Text PDFSingle GAF Domain Phytochrome Exhibits a pH-Dependent Shunt on the Millisecond Timescale.
Chemphyschem
January 2025
Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt am Main, Max-von-Laue-Straße 7, 60438, Frankfurt, Germany.
The light-sensing activity of phytochromes is based on the reversible light-induced switching between two isomerization states of the bilin chromophore. These photo-transformations may not necessarily be only unidirectional, but could potentially branch back to the initial ground state in a thermally driven process termed shunt. Such shunts have been rarely reported, and thus our understanding of this process and its governing factors are limited.
View Article and Find Full Text PDFProton diffusion and hydrogen/deuterium exchange in amorphous solid water at temperatures from 114 to 134 K.
J 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 PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!