Abstract
Aromaticity has been used as a criterion to explain the gas chromatographic (GC) retention of cata-condensed polycyclic aromatic sulfur heterocycles (PASHs) C12H8S, C16H10S, C20H12S; and peri-condensed PASHs C18H10S, in a GC column with 50% phenyl/50% dimethyl silphenylene polymer. To establish the aromaticity, nucleus-independent chemical shifts at the level of the molecular plane, NICS(0), and at 1 Å above the surface of the molecular plane, NICS(1), have been used. It has been found that the GC retention of cata-condensed PASHs C12H8S, C16H10S, and C20H12S is satisfactorily defined by the aromaticity of the entire molecule, and the GC retention of peri-condensed PASHs C18H10S is satisfactorily defined by the local aromaticity in the sulfur pentagonal ring. In addition, the positive slope between GC retention and NICS(0) of the entire molecule for cata-condensed PASHs, C12H8S and C16H10S, and by NICS(1) in the pentagonal ring for peri-condensed PASHs, C18H10S, is explained by the interaction between the electrons of the heterocycle molecule and the positive pole of the silicon atom in the GC column, as suggested with PAHs. In contrast, the negative slope between GC retention and aromaticity for cata-condensed C20H12S is explained by the presence of bay, cove, or fjord regions in the vicinity of the sulfur atom that generates either higher GC retention and lower aromaticity or lower GC retention and higher aromaticity.
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References
García-Valverde M, Torroba T (2005) Sulfur-nitrogen heterocycles. Molecules 10:318–320
Yuan ZX, Sikka HC, Munir S, Kumar A, Muruganandam AV, Kumar S (2003) Metabolism of the polynuclear sulfur heterocycle benzo[b]phenanthro[2,3-d]thiophene by rodent liver microsomes: evidence for multiple pathways in the bioactivation of benzo[b]phenanthro[2,3-d]thiophene. Chem Res Toxicol 16:1581–1588
Wise SA, Benner BA, Chesler SN, Hilpert LR, Vogt CR, May WE (1986) Characterization of the polycyclic aromatic hydrocarbons from two standard reference material air particulate samples. Anal Chem 58:3067–3077
Yang C, Zhang G, Wang Z, Yang Z, Hollebone B, Landriault M, Shah K, Brown CE (2014) Development of a methodology for accurate quantitation of alkylated polycyclic aromatic hydrocarbons in petroleum and oil contaminated environmental samples. Anal Methods 6:7760–7771
Mössner SG, Wise SA (1999) Determination of polycyclic aromatic sulfur heterocycles in fossil fuel-related samples. Anal Chem 71:58–69
Schade T, Andersson JT (2006) Speciation of alkylated dibenzothiophenes through correlation of structure and gas chromatographic retention indexes. J Chromatogr A 1117:206–213
Zeigler CD, Robbat A Jr (2012) Comprehensive profiling of coal tar and crude oil to obtain mass spectra and retention indices for alkylated PAH shows why current methods err. Environ Sci Technol 46:3935–3942
Radecki A, Lamparczyk H, Kaliszan R (1979) A relationship between the retention indices on nematic and isotropic phases and the shape of polycyclic aromatic hydrocarbons. Chromatographia 12:595–599
Wilson WB, Sander LC, Oña-Ruales JO, Mössner S, Sidisky LM, Lee ML, Wise SA (2017) Retention behavior of isomeric polycyclic aromatic sulfur heterocycles in gas chromatography on stationary phases of different selectivity. J Chromatogr A 1485:120–130
Oña-Ruales JO, Wilson WB, Nalin F, Sander LC, Schubert-Ullrich P, Wise SA (2016) The influence of the aromatic character in the gas chromatography elution order: the case of polycyclic aromatic hydrocarbons. Mol Phys 114:3533–3545
Schleyer PvR, Maerker C, Dransfeld A, Jiao H, Hommes NJRvE (1996) Nucleus-independent chemical shifts: a simple and efficient aromaticity probe. J Am Chem Soc 118:6317–6318
Ruiz-Morales Y (2004) The agreement between Clar structures and nucleus-independent chemical shift values in pericondensed benzenoid polycyclic aromatic hydrocarbons: an application of the Y-Rule. J Phys Chem A 108:10873–10896
Ruiz-Morales Y (2002) HOMO–LUMO gap as an index of molecular size and structure for polycyclic aromatic hydrocarbons (PAHs) and asphaltenes: a theoretical study. I. J Phys Chem A 106:11283–11308
Ditchfield R (1974) Self-consistent perturbation theory of diamagnetism. I. A gauge-invariant LCAO method for NMR chemical shifts. Mol Phys 27:789–807
Wolinski K, Hinton JF, Pulay P (1990) Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J Am Chem Soc 112:8251–8260
Frisch MJ et al (2009) Gaussian 09, revision A.2. Gaussian, Inc. Wallingford
Becke A (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789
Perdew JP, Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:13244–13549
Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys 92:508–517
Delley B (2000) From molecules to solids with the DMol3 approach. J Chem Phys 113:7756–7764
DMol3, release 4.0 (2001) Accelrys, Inc.: San Diego
Accelrys MS Modeling 5.5 (2010) Accelrys, Inc.: San Diego
Schleyer PvR, Manoharan M, Wang ZX, Kiran B, Jiao H, Puchta R, Hommes NJRvE (2001) Dissected nucleus-independent chemical shift analysis of π-aromaticity and antiaromaticity. Org Lett 3:2465–2468
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Oña-Ruales, J.O., Ruiz-Morales, Y., Alvarez-Ramírez, F. et al. The Influence of Aromaticity in Gas Chromatography Retention: The Case of Polycyclic Aromatic Sulfur Heterocycles. Chromatographia 81, 479–486 (2018). https://doi.org/10.1007/s10337-017-3465-1
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DOI: https://doi.org/10.1007/s10337-017-3465-1