Lipids

, Volume 39, Issue 9, pp 897–906 | Cite as

Multivariate prediction of clarified butter composition using raman spectroscopy

  • J. Renwick Beattie
  • Steven E. J. Bell
  • C. Borgaard
  • A. M. Fearon
  • Bruce W. Moss
Articles

Abstract

Raman spectroscopy has been used to predict the abundance of the FA in clarified butterfat that was obtained from dairy cows fed a range of levels of rapeseed oil in their diet. Partial least squares regression of the Raman spectra against FA compositions obtained by GC showed that good prediction of the five major (abundance >5%) FA gave R2=0.74–0.92 with a SE of prediction (RMSEP) that was 5–7% of the mean. In general, the prediction accuracy fell with decreasing abundance in the sample, but the RMSEP was <10% for all but one of the 10 FA present at levels >1.25%. The Raman method has the best prediction ability for unsaturated FA (R2=0.85–0.92), and in particular trans unsaturated FA (best-predicted FA was 18∶1tΔ9). This enhancement was attributed to the isolation of the unsaturated modes from the saturated modes and the significantly higher spectral response of unsaturated bonds compared with saturated bonds. Raman spectra of the melted butter samples could also be used to predict bulk parameters calculated from standard analyzes, such as iodine value (R2=0.80) and solid fat content at low temperature (R2=0.87). For solid fat contents determined at higher temperatures, the prediction ability was significantly reduced (R2=0.42), and this decrease in performance was attributed to the smaller range of values in solid fat content at the higher temperatures. Finally, although the prediction errors for the abundances of each of the FA in a given sample are much larger with Raman than with full GC analysis, the accuracy is acceptably high for quality control applications. This, combined with the fact that Raman spectra can be obtained with no sample preparation and with 60-s data collection times, means that high-throughput, on-line Raman analysis of butter samples should be possible.

Abbreviations

IV

iodine value

PLS

partial least squares

QC

quality control

RMSEP

standard error of prediction

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References

  1. 1.
    Fearon, A.M. (2001) Optimising Milkfat Composition and Processing Properties, Austral. J. Dairy Technol. 56, 104–108.Google Scholar
  2. 2.
    Johnson, G.L., Machado, R.M., Freidl, K.G., Achenbach, M.L., Clark, P.J., and Reidy, S.K. (2002) Evaluation of Raman Spectroscopy for Determining cis and trans-Isomers in Partially Hydrogenated Soybean Oil, Org. Process Res. Dev. 6, 637–644.CrossRefGoogle Scholar
  3. 3.
    Barthus, R.C., and Poppi, R.J. (2001). Determination of the Total Unsaturation in Vegetable Oils by Fourier Transform Raman Spectroscopy and Multivariate Calibration, Vib. Spectrosc. 26, 99–105.CrossRefGoogle Scholar
  4. 4.
    Chmielarz, B., Bajdor, K., Labudzinska, A., and Klukowskamajewska, Z. (1995) Studies on the Double-Bond Positional Isomerization Process in Linseed Oil by UV, IR and Raman Spectroscopy, J. Mol. Struct. 348, 313–316.CrossRefGoogle Scholar
  5. 5.
    Beattie, J.R., Bell, S.E.J., and Moss, B.W. (2000) Raman Studies of Lipid Structure and Composition, in XVII International Conference on Raman Spectroscopy (Beattie, J.R., Bell, S.E.J., and Moss, B.W., eds.), pp. 708–709, John Wiley & Sons, Beijing.Google Scholar
  6. 6.
    Muik, B., Lendl, B., Molina-Diaz, A., and Ayora-Canada, M.J. (2003) Direct, Reagent-free Determination of Free Fatty Acid Content in Olive Oil and Olives by Fourier Transform Raman Spectrometry, Anal. Chim. Acta 487, 211–220.CrossRefGoogle Scholar
  7. 7.
    Simpson, T.D., and Hagemann, J.W. (1982) Evidence of Two β′ Phases in Tristearin, J. Am. Oil. Chem. Soc. 59, 169–171.Google Scholar
  8. 8.
    Sato, T., Takahashi, M., and Matsunaga, R. (2002) Use of NIR Spectroscopy for Estimation of FA Composition of Soy Flour, JAOCS J. Am. Oil. Chem. Soc. 79, 535–537.Google Scholar
  9. 9.
    Velasco, L., Mollers, C., and Becker, H.C. (1999) Estimation of Seed Weight, Oil Content and Fatty Acid Composition in Intact Single Seeds of Rapeseed (Brassica napus L) by Near-Infrared Reflectance Spectroscopy, Euphytica 106, 79–85.CrossRefGoogle Scholar
  10. 10.
    Kohler, P., and Kallweit, E. (1999) Determination of Fatty Acid Composition of Intramuscular Fat in Sheep by Near-Infrared Transmission Spectroscopy (NIT) and Their Importance for the Meat Production, Agribiol. Res.—Zeitschrift fur Agrarbiologie Agrikulturchemie Okologie 52, 145–154.Google Scholar
  11. 11.
    Molette, C., Berzaghi, P., Zotte, A.D., Remignon, H., and Babile, R. (2001) The Use of Near-Infrared Reflectance Spectroscopy in the Prediction of the Chemical Composition of Goose Fatty Liver, Poult. Sci. 80, 1625–1629.PubMedGoogle Scholar
  12. 12.
    Beattie, J.R., Bell, S.J., and Moss, B.W. (2004) A Critical Evaluation of Raman Spectroscopy for the Analysis of Lipids: Fatty Acid Methyl Esters, Lipids 39, 407–419.PubMedCrossRefGoogle Scholar
  13. 13.
    Oakes, R.E., Beattie, J.R., Moss, B., and Bell, S.E.J. (2002) Conformations, Vibrational Frequencies and Raman Intensities of Short Chain Fatty Acid Methyl Esters Using DFT with 6–31 G(d) and Sadlej pVTZ Basis Sets, J. Mol. Struct. 586, 91–110.CrossRefGoogle Scholar
  14. 14.
    Oakes, R.E., Beattie, J.R., Moss, B.W., and Bell, S.E.J. (2003) DFT Studies of Long-Chain FAMES: Theoretical Justification for Determining Chain Length and Unsaturation from Experimental Raman Spectra, J. Mol. Struct.-Theochem. 626, 27–45.CrossRefGoogle Scholar
  15. 15.
    Beattie, J.R., Bell, S.E.J., and Moss, B.W. (1999). Preliminary Investigation on the Use of Raman Spectroscopy to Characterise Adipose Tissue, in 45th International Congress of Meat Science and Technology, (Beattie, J.R., Bell, S.E.J. and Moss, B.W., eds.) Vol. 2, pp. 668–669, Yokohama, Japan.Google Scholar
  16. 16.
    Fearon, A.M., Mayne, C.S., Beattie, J.A.M., and Bruce, D.W. (2004) Effect of Level of Oil Inclusion in the Diet of Dairy Cows at Pasture on Animal Performance and Milk Composition and Properties, J. Sci. Food Agric. 84, 497–504.CrossRefGoogle Scholar
  17. 17.
    Princeton (1993) CSMA, 2.3a ed., Princeton Instruments.Google Scholar
  18. 18.
    AOCS, Iodine Value of Fats and Oils Cyclohexane Method, in Official Methods and Recommended Practices of the American Oil Chemists' Society, 4th edn., American Oil Chemists' Society, Champaign, 1990, Method Cd 1b-87.Google Scholar
  19. 19.
    Pearson, D. (1970) Chemical Analysis of Food, J&A Churchill, London, p. 510.Google Scholar
  20. 20.
    Sadeghi-Jorabchi, H., Hendra, P.J., Wilson, R.H., and Belton, P.S. (1990) Determination of the Total Unsaturation in Oils and Fats by Fourier Transform Raman Spectroscopy, J. Am. Oil Chem. Soc. 67, 483–486.Google Scholar
  21. 21.
    Butler, M., Salem, N., Hoss, W., and Spoonhower, J. (1979) Raman Spectral Analysis of the 1300 cm−1 Region for Lipid and Membrane Studies, Chem. Phys. Lipids 29, 99–102.CrossRefGoogle Scholar
  22. 22.
    Snyder, R.G., Cameron, D.G., Casal, H.L., Compton, D.A.C., and Mantsch, H.H. (1982) Studies on Determining Conformational Order in N-Alkanes and Phospholipids from the 1130cm−1 Raman Band, Biochim. Biophys. Acta. 684, 111–116.CrossRefGoogle Scholar
  23. 23.
    Lawson, E.E., Anigbogu, A.N.C., Williams, A.C., Barry, B.W., and Edwards, H.G.M. (1998) Thermally Induced Molecular Disorder in Human Stratum Corneum Lipids Compared with a Model Phospholipid System: FT-Raman Spectroscopy, Spectrochim. Acta Part A: Mol. Biomol. Spectrosc. 54, 543–558.CrossRefGoogle Scholar
  24. 24.
    Susi, H., Sampugna, J., Hampson, J.W., and Ard, J.S. (1979) Laser-Raman Investigation of Phospholipid-Polypeptide Interactions in Model Membranes, Biochemistry 18, 297–301.PubMedCrossRefGoogle Scholar
  25. 25.
    Kint, S., Wermer, P.H., and Scherer, J.R. (1992) Raman Spectra of Hydrated Phospholipid Bilayers. 2. Water and Headgroup Interactions, J. Phys. Chem. 96, 446–452.CrossRefGoogle Scholar

Copyright information

© AOCS Press 2004

Authors and Affiliations

  • J. Renwick Beattie
    • 1
  • Steven E. J. Bell
    • 1
  • C. Borgaard
    • 2
  • A. M. Fearon
    • 1
  • Bruce W. Moss
    • 3
  1. 1.School of ChemistryQueen's UniversityBelfastNorthern Ireland
  2. 2.Danish Meat Research InstituteRoskildeDenmark
  3. 3.School of Agriculture and Food ScienceQueen's UniversityBelfastNorthern Ireland

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