The Renaissance of H/D Exchange
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The increasing demand for stable isotopically labeled compounds has led to an increased interest in H/D-exchange reactions at carbon centers. Today deuterium-labeled compounds are used as internal standards in mass spectrometry or to help elucidate mechanistic theories. Access to these deuterated compounds takes place significantly more efficiently and more cost effectively by exchange of hydrogen by deuterium in the target molecule than by classical synthesis. This Review will concentrate on the preparative application of the H/D-exchange reaction in the preparation of deuterium-labeled compounds. Advances over the last ten years are brought together and critically evaluated.Keywords:
Hydrogen–deuterium exchange
Hydrogen–deuterium exchange
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Pyrrole
Hydrogen–deuterium exchange
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Because of its apparent simplicity, diffusion of hydrogen in solids can be regarded as a general model system for diffusion. However, only rudimentary knowledge exists for the dynamics of hydrogen in complex hydrides. Insight into the specific diffusion process is given by hydrogen−deuterium exchange experiments. Thermogravimetry and Raman spectroscopy are used to measure the hydrogen−deuterium exchange during the decomposition of LiBH4. At a temperature of 523 K the self-diffusion constant of deuterium in LiBH4 is estimated to be D ≃ 7·10−14 m 2 s−1. A careful analysis of the Raman spectra shows that hydrogen is statistically exchanged by deuterium in LiBH4; i.e., the diffusing species is assumed to be the single hydrogen atom.
Hydrogen–deuterium exchange
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An apparatus for measuring exchange equilibria and rates of exchange of molecular deuterium with hydrogen containing compounds is described. The gas density balance is used to analyze the hydrogen-deuterium mixtures. Results on the equilibria H2+2DCl = D2+2HCl, H2+DCl = HD+HCl are reported which check the theoretical values to within the limits of the experimental errors.
Hydrogen–deuterium exchange
Hydrogen chloride
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Deuterium-labeled organic compounds, reagents, and drugs are widely used in many scientific research fields. Isotopic purity as the feature parameter of deuterated compounds is of great importance. In this article, we used electrospray ionization with high-resolution mass spectrometry (ESI-HRMS) to study isotopic purity of deuterium-labeled organic compounds based on assigning and distinguishing the corresponding H/D (hydrogen-deuterium) isotopolog ions of deuterated compounds.We systematically considered the specific requirements of accuracy and resolution of ESI-HRMS when measuring isotopic purity and demonstrated some actual cases using ESI-HRMS and ultraperformance liquid chromatography (UPLC)-HRMS. Meanwhile, ESI-HRMS/MS of deuterated compounds was performed to obtain more information on deuterium-labeled position characterization.Two isotopic purity calculation methods based on the relative abundance in ESI-HRMS and UPLC-HRMS of H/D isotopolog ions (D0 -Dn ) were compared, which gave consistent isotopic purity values and were in good agreement with the certified isotopic purity values. We further studied and monitored the H/D exchange reaction of ethyl 3-(4-bromophenyl)-3-oxopropanoate (EBPO) by evaluating the dynamic isotopic purity changes in EBPO-D2 in the H/D exchange reaction in situ.The isotopic purity characterization methods using ESI-HRMS discussed in this article have some outstanding advantages: rapid, highly sensitive, very low sample consumption (even below nanogram level), and deuterated solvent-free. Thus, this low-impact analytical method requires less time and is cost effective and might have good application potential for in-situ isotopic purity analysis and for monitoring the H/D exchange reactions.
Hydrogen–deuterium exchange
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Hydrogen–deuterium exchange
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Pd/C is found to catalyse efficient and chemoselective exchange of deuterium derived from D2O with hydrogens on a benzylic carbon in the presence of a catalytic amount of hydrogen at room temperature.
Hydrogen–deuterium exchange
Carbon fibers
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Deuterium/hydrogen exchange in combination with mass spectrometry (DH MS) is a sensitive technique for detection of changes in protein conformation and dynamics. Since temperature, pH and timing control are the key elements for reliable and efficient measurement of hydrogen/deuterium content in proteins and peptides, we have developed a small, semiautomatic interface for deuterium exchange that interfaces the HPLC pumps with a mass spectrometer. This interface is relatively inexpensive to build, and provides efficient temperature and timing control in all stages of enzyme digestion, HPLC separation and mass analysis of the resulting peptides. We have tested this system with a series of standard tryptic peptides reconstituted in a solvent containing increasing concentration of deuterium. Our results demonstrate the use of this interface results in minimal loss of deuterium due to back exchange during HPLC desalting and separation. For peptides reconstituted in a buffer containing 100% deuterium, and assuming that all amide linkages have exchanged hydrogen with deuterium, the maximum loss of deuterium content is only 17% of the label, indicating the loss of only one deuterium molecule per peptide.
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Amide
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Abstract Dimethylpyridines undergo deuterium‐hydrogen exchange when heated in deuterium oxide containing potassium carbonate at ring positions 2 and 6 when these positions are unsubstituted and at methyl groups located at ring positions 2,4, and 6 exclusively.
Hydrogen–deuterium exchange
Potassium carbonate
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We present the investigation of hydrogen/deuterium (H/D) exchange of carbohydrates ions occurring in the electrospray ion source. The shape of the deuterium distribution was observed to be considerably dependent on the temperature of the ion transfer tube and the solvent used. If deuterated alcohol (EtOD or MeOD) or D2O/deuterated alcohol is used as an electrospray solvent, then for high temperatures (>350 °C), intensive back exchange is observed, resulting in ∼30% depth of the deuterium exchange. At low temperatures (<150 °C), the back exchange is weaker and the depth of the deuterium exchange is ∼70%. In the intermediate temperature region (∼250 °C), the deuterium distribution is unusually wide for methanol and bimodal for ethanol. The addition of 1% formic acid results in low (∼30%) depth of the deuterium exchange for any temperature in the operating region. The bimodal distribution for the ethanol can be possibly explained by the presence of differently folded gas-phase ions of carbohydrates.
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