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Continuous Gradient Temperature Raman Spectroscopy of Oleic and Linoleic Acids from −100 to 50 °C

Abstract

We analyzed the unsaturated fatty acids oleic (OA, 18:1n-9) and linoleic (LA, 18:2n-3), and a 3:1 LA:OA mixture from −100 to 50 °C with continuous gradient temperature Raman spectroscopy (GTRS). The 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allowed rapid, complete assignment of solid, liquid, and transition state vibrational modes. For OA, large spectral and line width changes occurred in the solid state γ to α transition near −4 °C, and the melt (13 °C) over a range of only 1 °C. For LA, major intensity reductions from 200 to 1750 cm−1 and some peak shifts marked one solid state phase transition at −50 °C. A second solid state transition (−33 °C) had minor spectral changes. Large spectral and line width changes occurred at the melt transition (−7 °C) over a narrow temperature range. For both molecules, melting initiates at the diene structure, then progresses towards the ends. In the 3:1 LA:OA mixture, some less intense and lower frequencies present in the individual lipids are weaker or absent. For example, modes assignable to C8 rocking, C9H–C10H wagging, C10H–C11H wagging, and CH3 rocking are present in OA but absent in LA:OA. Our data quantify the concept of lipid premelting and identify the flexible structures within OA and LA, which have characteristic vibrational modes beginning at cryogenic temperatures.

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Abbreviations

CCD:

Charge-coupled device

DSC:

Differential scanning calorimetry

FA:

Fatty acid

PUFA:

Polyunsaturated fatty acid

LCPUFA:

Long chain polyunsaturated fatty acid

GTRS:

Gradient temperature Raman spectroscopy

HT:

High temperature

IR:

Infrared

LA:

Linoleic acid

LN2 :

Liquid nitrogen

LT:

Low temperature

MT:

Mid temperature

OA:

Oleic acid

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Correspondence to C. Leigh Broadhurst.

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Broadhurst, C.L., Schmidt, W.F., Kim, M.S. et al. Continuous Gradient Temperature Raman Spectroscopy of Oleic and Linoleic Acids from −100 to 50 °C. Lipids 51, 1289–1302 (2016). https://doi.org/10.1007/s11745-016-4194-1

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  • DOI: https://doi.org/10.1007/s11745-016-4194-1

Keywords

  • Gradient temperature Raman spectroscopy
  • Oleic acid
  • Linoleic acid
  • Polyunsaturated fatty acids
  • Raman spectroscopy