Molecular Structure of Isocyanic Acid, HNCO, the Imide of Carbon Dioxide

Evers, Jürgen; Krumm, Burkhard; Axthammer, Quirin J.; Martens, Jörn; Blaha, Peter; Steemann, F. Xaver; Reith, Thomas; Mayer, Péter; Klapötke, Thomas M.

doi:10.1021/acs.jpca.8b00557

Cited by 8 publications

(3 citation statements)

References 33 publications

(78 reference statements)

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“…K33, however, demonstrated a higher carbamylation rate than K6 and K48 despite having an appreciably higher p K a , which suggests the presence of additional factors promoting carbamylation at this site. As K33 was not especially reactive to nonenzymatic acetylation, this points to a favorable environment for interacting with isocyanic acid and CO 2 . , Contrary to our previously reported CO 2 carbamylation assay, K63 was only modestly sensitive to irreversible carbamylation by isocyanic acid at physiological pH and temperature. These last two observations are being actively investigated.…”

Section: Discussioncontrasting

confidence: 63%

“…As K33 was not especially reactive to nonenzymatic acetylation, this points to a favorable environment for interacting with isocyanic acid and CO 2 . 29,71 Contrary to our previously reported CO 2 carbamylation assay, K63 was only modestly sensitive to irreversible carbamylation by isocyanic acid at physiological pH and temperature. These last two observations are being actively investigated.…”

Section: ■ Discussioncontrasting

confidence: 56%

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Site-Specific Detection and Characterization of Ubiquitin Carbamylation

et al. 2022

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The physiological consequences of varying in vivo CO2 levels point to a general mechanism for CO2 to influence cellular homeostasis beyond regulating pH. Aside from a few instances where CO2 has been observed to cause post-translational protein modification, by forming long-lived carbamates, little is known about how transitory and ubiquitous carbamylation events could induce a physiological response. Ubiquitin is a versatile protein involved in a multitude of cellular signaling pathways as polymeric chains of various lengths formed through one of the seven lysines or N-terminal amine. Unique polyubiquitin (polyUb) compositions present recognition signals for specific ubiquitin-receptors which enables this one protein to be involved in many different cellular processes. Advances in proteomic methods have allowed the capture and identification of protein carbamates in vivo, and Ub was found carbamylated at lysines K48 and K33. This was shown to negatively regulate ubiquitin-mediated signaling by inhibiting polyUb chain formation. Here, we expand upon these observations by characterizing the carbamylation susceptibility for all Ub amines simultaneously. Using NMR methods which directly probe 15N resonances, we determined carbamylation rates under various environmental conditions and related them to the intrinsic pK as. Our results show that the relatively low pK as for half of the Ub amines are correlated with enhanced susceptibility to carbamylation under physiological conditions. Two of these carbamylated amines, not observed by chemical capture, appear to be physiologically relevant post-translational modifications. These findings point to a mechanism for varying the levels of CO2 due to intracellular localization, cellular stresses, and metabolism to affect certain polyUb-mediated signaling pathways.

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Section: Discussioncontrasting

confidence: 63%

Section: ■ Discussioncontrasting

confidence: 56%

Site-Specific Detection and Characterization of Ubiquitin Carbamylation

et al. 2022

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“…Isocyanic acid, whose crystal structure resembles the one of carbon monoxide [77], is also supposed to play a role in the chemistry of interstellar ices and comets [78], therefore computational ab initio studies tried to understand its behavior in the extreme space conditions. In this sense, DFT has been used to calculate the vibrational spectrum of methyl isocyanates, in order to relate it with the astrophysical observations by Maté and collaborators [61].…”

Section: Ab Initio Studiesmentioning

confidence: 99%

Current State and Perspectives of Simulation and Modeling of Aliphatic Isocyanates and Polyisocyanates

et al. 2022

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Aliphatic isocyanates and polyisocyanates are central molecules in the fabrication of polyurethanes, coatings, and adhesives and, due to their excellent mechanical and stability properties, are continuously investigated in advanced applications; however, despite the growing interest in isocyanate-based systems, atomistic simulations on them have been limited by the lack of accurate parametrizations for these molecular species. In this review, we will first provide an overview of current research on isocyanate systems to highlight their most promising applications, especially in fields far from their typical usage, and to justify the need for further modeling works. Next, we will discuss the state of their modeling, from first-principle studies to atomistic molecular dynamics simulations and coarse-grained approaches, highlighting the recent advances in atomistic modeling. Finally, the most promising lines of research in the modeling of isocyanates are discussed in light of the possibilities opened by novel approaches, such as machine learning.

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The Simplest, Isolable, Alkynyl Isocyanate HC≡CNCO: Synthesis and Characterization

Qin¹,

Lü²,

Rauhut³

et al. 2019

Angewandte Chemie

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Alkynyl isocyanates have been postulated as highly reactive intermediates in synthetic chemistry. Herein, the parent molecule HC≡CNCO is isolated for the first time. In sharp contrast to the previously reported short lifetime (ca. 15 s) at room temperature, we found that HC≡CNCO has a lifetime of 55 h in the gas phase (2 mbar, 300 K) with a melting point of −79.5 °C and vaporization enthalpy (ΔHvap) of 23.1(1) kJ mol−1. Apart from the IR (gas, solid, and matrix), 1H and 13C NMR, and UV/Vis spectroscopic characterization, its photoisomerization with a acylnitrene HC≡CC(O)N and cyanoketene NCC(H)CO has been observed.

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Molecular Structure of Isocyanic Acid, HNCO, the Imide of Carbon Dioxide

Cited by 8 publications

References 33 publications

Site-Specific Detection and Characterization of Ubiquitin Carbamylation

Site-Specific Detection and Characterization of Ubiquitin Carbamylation

Current State and Perspectives of Simulation and Modeling of Aliphatic Isocyanates and Polyisocyanates

The Simplest, Isolable, Alkynyl Isocyanate HC≡CNCO: Synthesis and Characterization

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