Abstract
A mathematical model is proposed for revealing the absence of a compound to be identified in an electron impact mass spectral library. The mathematical model (developed based on PLS Discriminant Analysis) can be represented as a “black box” which provides an answer whether a compound to be sought is absent or present in a database. The match factors of top ten candidates among the possible ones were used as input data. More than 5000 objects (mass spectra) were used at the steps of training, validation, and testing. The developed classification model provides correct prediction (of whether a compound is absent from the library) in 28.4% cases, while only 1.2% of compounds present in the database were incorrectly classified as the absent ones.
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Stein, S., Anal. Chem., 2012, vol. 84, no. 17, p. 7274.
Milman, B.L. and Zhurkovich, I.K., TrAC, Trends Anal. Chem., 2016, vol. 80, p. 636.
Stein, S.E. and Scott, D.R., J. Am. Soc. Mass Spectrom., 1994, vol. 5, no. 9, p. 859.
McLafferty, F.W., Hertel, R.H., and Villwock, R.H., Org. Mass Spectrom., 1974, vol. 9, no. 7, p. 690.
Neudert, R., Bremser, W., and Wagner, H., Org. Mass Spectrom., 1978, vol. 22, no. 6, p. 321.
Domokos, L. and Henneberg, D., Anal. Chim. Acta, 1984, vol. 165, p. 75.
Varmuza, K., Int. J. Mass Spectrom. Ion Processes, 1992, vol. 118–119, p. 811.
Domokos, L., Henneberg, D., and Wiemann, B., Anal. Chim. Acta, 1984, vol. 5, p. 316.
Samokhin, A., Sotnezova, K., Lashin, V., and Revelsky, I., J. Mass Spectrom, 2015, vol. 50, no. 6, p. 820.
Koo, I., Zhang, X., and Kim, S., Anal. Chem., 2011, vol. 83, no. 14, p. 5631.
Stein, S.E., J. Am. Soc. Mass Spectrom., 1999, vol. 10, no. 8, p. 770.
Meyer, M.R., Peters, F.T., and Maurer, H.H., Clin. Chem., 2010, vol. 56, no. 4, p. 575.
Samokhin, A.S., Revel’skii, A.I., Chepelyanskii, D.A., Revel’skii, I.A., Mass-Spektrom., 2011, vol. 8, no. 1, p. 65.
Chemometrics course. Classification. http://rcs.chemometrics. ru/Tutorials/classification.htm. Cited August 24, 2016.
Dahn, V. and Nguyen David, M., Bioinformatics, 2002, vol. 18, no. 1, p. 39.
Zhu, W., Wang, X., Ma, Y., Rao, M., Glimm, J., and Kovach, J.S., Proc. Natl. Acad. Sci. U. S. A., 2003, vol. 100, no. 25, p. 14666.
Gupta, S., Variyar, P.S., and Sharma, A., Radiat. Phys. Chem., 2015, vol. 106, p. 348.
Ruiz-Samblas, C., Tres, A., Koot, A., Ruth, S.M., Gonzalez-Casado, A., and Cuadross-Rodriguez, L., Food Chem., 2012, vol. 134, no. 1, p. 589.
Baroni, M.V., Nores, M.L., Del Pilar Diaz, M., Chiabrando, G.A., Fassano, J.P., Costa, C., and Wunderlin, D.A., J. Agric. Food Chem., 2006, vol. 54, no. 19, p. 7235.
Villagra, E., Santos, L.S., Gontijovaz, B., Eberlin, M.N., and Laurie, F.V., Food Chem., 2012, vol. 131, no. 2, p. 692.
Cynkar, W., Dambergs, R., Smith, P., and Cozzolino, D., Anal. Chim. Acta, 2010, vol. 660, nos. 1–2, p. 227.
Curry, Bo. and Rumelhart, D.E., Tetrahedron Comput. Methodol., 1990, vol. 3, nos. 3–4, p. 213.
Lohninger, H. and Varmuza, K., Anal. Chem., 1987, vol. 59, no. 2, p. 236.
Varmuza, K. and Werther, W., Mass spectral classifiers for supporting systematic structure elucidation, J. Chem. Inf. Comput. Sci., 1996, vol. 36, no. 2, p. 323.
Werther, W., Lohninger, H., Stancl, F., and Varmuza, K., Chemom. Intell. Lab. Syst., 1994, vol. 22, no. 1, p. 63.
Vogt, L., Groger, T., and Zimmermann, R., J. Chromatogr., A, 2007, vol. 1150, nos. 1–2, p. 2.
Stein, S.E., J. Am. Soc. Mass Spectrom., 1994, vol. 5, no. 4, p. 316.
NIST MS Search User Guide, Gaithersburg: Natl. Inst. Standards Technol., 2008.
Ausloos, P., Clifton, C.L., Mikaya, A.I., Stein, S.E., Tchekhovskoi, D.V., Sparkman, O.D., Zaikin, V., and Zhu, D., J. Am. Soc. Mass Spectrom., 1999, vol. 10, no. 4, p. 287.
http://www.chemometrics.ru/materials/textbooks/projection. htm. Cited August 29, 2016.
Pomerantsev, A.L., Chemometrics in Excel, Wiley, 2014.
Sekulic, S., Seasholtz, M.-B., Wang, Z., Kowalski, B., Lee, S., and Holt, B., Anal. Chem., 1993, vol. 65, no. 19, p. 835.
Berglund, A. and Wold, S., J. Chemom., 1997, vol. 11, no. 2, p. 141.
Geladi, P., Hadjiiski, L., and Hopke, P., Chemom. Intell. Lab. Syst., 1999, vol. 47, no. 2, p. 165.
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Original Russian Text © K.M. Sotnezova, A.S. Samokhin, I.A. Revelsky, 2017, published in Mass-spektrometriya, 2017, Vol. 14, No. 2, pp. 95–102.
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Sotnezova, K.M., Samokhin, A.S. & Revelsky, I.A. Use of PLS Discriminant Analysis for Revealing the Absence of a Compound in an Electron Ionization Mass Spectral Database. J Anal Chem 72, 1419–1425 (2017). https://doi.org/10.1134/S1061934817140143
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DOI: https://doi.org/10.1134/S1061934817140143