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Predicting equilibrium intramolecular isotope distribution within a large organic molecule by the cutoff calculation
He YY(何雨旸)1,2; Bao HM2,3; Liu Y3,4

A predicted equilibrium intramolecular isotope distribution (Intra-ID) serves as a reference for measured position-specific (PS) isotope composition variation in an organic molecule. Equilibrium Intra-ID can be estimated from calculated reduced partition function ratios (RPFR or beta factor), which are largely absent to date. For relatively small molecules, the PS beta factor can be calculated directly. However, estimating the PS beta factor considering an entire, large organic molecule is computationally prohibitive. The isotope effect is local in that the vibrational frequencies of an atom are only affected by its proximal bonding environment. Therefore, the cutoff calculation, which simplifies the calculation of an entire molecule to a local area, was previously proposed for large organic molecules. However, the cutoff size was not validated, which has hindered the application of the cutoff calculation. Here, we calculated a series of small organic molecules with 2-18 carbon atoms to test the influence of cutoff size on the (13)beta value estimation of a target carbon position in a carbon chain or a carbon ring. We calculated nineteen small molecules that have a methyl carbon and a functional group that is at least three bonds away from the target methyl position. The result showed that the equilibrium C-13 enrichment of the methyl group relative to CO2 at 25 degrees C (ln(13)alpha((eq))) for the nineteen molecules varied in a small range, with a standard deviation of 0.2 parts per thousand. Fourteen aromatic hydrocarbons with a benzene and one adjacent functional group were calculated to test the influence of different adjacent functional groups on similar carbon positions in benzene. The results showed that different adjacent functional groups had significant influence only on the predicted ln(13)alpha((eq)) value of the carbon position directly connected to them (standard deviation = 1.0 parts per thousand, n = 14), with a negligible influence on the predicted ln(13)alpha((eq)) value of the remaining carbons in benzene (standard deviation = 0.2 parts per thousand, n = 14). The PS (13)beta value of a specific carbon position in CoA calculated by the cutoff calculation differed from that of the entire-molecule calculation by 0.0-0.3 parts per thousand. We concluded that the cutoff calculation simplified the calculation of a target position from an entire molecule to a cluster of three proximal bonds in a chain and/or an adjacent ring, providing PS (13)beta values of sufficient accuracy for large organic molecules. (C) 2019 Elsevier Ltd. All rights reserved.

KeywordReduced partition function ratio Position-specific isotope composition KIE Solvent effect CoA
Indexed BySCI
WOS IDWOS:000502332400016
WOS Research AreaGeochemistry & Geophysics
WOS SubjectGeochemistry & Geophysics
Funding ProjectNational Natural Science Foundation of China[41490635] ; National Natural Science Foundation of China[41530210] ; Chinese Academy of Sciences[XDB18010100]
Funding OrganizationNational Natural Science Foundation of China ; Chinese Academy of Sciences
ContributorHe, Yuyang
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Cited Times:2[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Affiliation1.Chinese Acad Sci, Inst Mech, 15 Beisihuanxi Rd, Beijing 100190, Peoples R China;
2.Louisiana State Univ, Dept Geol & Geophys, E235 Howe Russell Kniffen, Baton Rouge, LA 70803 USA;
3.Chinese Acad Sci, Inst Geochem, Guiyang 550081, Guizhou, Peoples R China;
4.CAS Ctr Excellence Comparat Planetol, Hefei 230026, Anhui, Peoples R China
Recommended Citation
GB/T 7714
He YY,Bao HM,Liu Y. Predicting equilibrium intramolecular isotope distribution within a large organic molecule by the cutoff calculation[J]. GEOCHIMICA ET COSMOCHIMICA ACTA,2020,269:292-302.
APA He YY,Bao HM,&Liu Y.(2020).Predicting equilibrium intramolecular isotope distribution within a large organic molecule by the cutoff calculation.GEOCHIMICA ET COSMOCHIMICA ACTA,269,292-302.
MLA He YY,et al."Predicting equilibrium intramolecular isotope distribution within a large organic molecule by the cutoff calculation".GEOCHIMICA ET COSMOCHIMICA ACTA 269(2020):292-302.
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