ANALYSIS OF CINNAMON continued
Table 3 – (continued)
Exact mass of ion
dectected
164.0712 C9 164.0837 C10 166.0868 C9 176.0837 C11 204.1878 C15 205.1956 C15 220.1827 C15
221.1905 C15 279.1021 C18 H6 H8 O2 H12
H12 H24 H24 H24
H24 H15 O2 O2 O2
[M+NH4 M+
[M+NH4 M+ M+
O M+
]+ Coumarin Eugenol
Formula Ion detected
Compound assignment
√
]+ Cinnamic acid nd Cinnamyl acetate nd β-Carophyllene nd
[M+H]+ β-Carophyllene √ √
Carophyllene oxide
O [M+H]+ Carophyllene oxide
O3 M+
a b
Cinnamalde- hyde-cinnamic acid dimer
√ nd
√—greater than 1% relative abundance in the mass spectrum. nd—not detected.
Table 4 – Possible isobars in cinnamon samples
Exact mass
Formula Compound 1 Compound 2 Ions 131.0497 C9 H6
O 1-Phenyl-2- propyn-1-one
163.0759 C10H10 O2 Safrole 148.0524 C9 O2 H8
3-Phenyl- 3-propynal
2-Methoxy cinnamal- dehyde
Cinnamic acid 2-Hydroxy cinnamal- dehyde
204.1878 C15H24 β-Carophyllene trans-α- Bergamotene
detected [M+H]+
[M+H]+ M+ , [M+H]+ M+, [M+H]+
Compound identification in cinnamon samples A list of masses routinely found among the samples was combined with a list of compounds identified in cinnamon analyses by other methods cited in the literature. Table 3 shows these mass peaks and their assignments along with their detection using DART-MS for ground and solid samples. The table highlights the extent to which DART-MS can produce mass data from a single sample, although, with the exception of the standards, these compound as- signments are tentative and should be confirmed by another method.
Several compounds have isobars that correspond to compounds found in both plants and cinnamon; Table 4 shows possible isobars. Experiments under identical conditions using standards of all possible compounds would be needed to verify which isobar (or both) is actually present.
AMERICAN LABORATORY 38
Major compounds detected in ground and solid cinnamon samples The four most intense peaks in each sample form are listed in Table 5. Cinnamaldehyde was the most intense peak in both ground and solid samples. The coumarin peak was next in intensity for all ground samples, except for the Ceylonese samples. Solid samples varied more from sample to sample and among multiple analyses of the same sample than the ground form. As noted earlier, some of the masses could only be identified by their elemental formula, and these are listed with the most likely compound.
The results show a fingerprint for the sourced samples, with the major differences between the ground and solid samples being additional plant- based compounds. Eugenol was not detected in high amounts in any of the samples, although it is usually listed as a major component in the literature. Using DART-MS, eugenol and cinnamic acid were detected at similar levels, around 10 mg/L. Several authors cite cinnamic acid as typi- cally being higher in concentration than eugenol in cinnamon samples.4,11 This discrepancy may be attributed to the sensitivity of these compounds using the DART-MS instrument.
Ground samples of the four sourced samples were clearly distinguishable by different coumarin levels, with the Ceylonese cinnamon having the lowest amount. The Indonesian and Vietnamese ground samples showed higher amounts of coumarin than their solid counterparts. Overall, the solid samples were more variable from analysis to analysis, most notably in their coumarin levels. The ground, nonsourced sample of brand A was comparable to a Chinese-sourced ground sample, while brand B was close to both a Chinese-sourced solid sample and Indonesian source solid sample. No coumarin was detected in the brand B solid sample.
APRIL 2016 Detected in ground samples
nd nd nd nd √ √ √
√ √ √ √
nd nd nd nd √
nd √ √
nd nd nd √ √
nd √ √
nd √
Detected in solid samples
Ceylonese Chinese Indonesian Vietnamese Ceylonese Chinese Indonesian Vietnamese nd
√
nd nd nd √
nd √ nd
nd nd nd √
nd √
√ √
nd nd nd nd √ √ √
√ nd √
nd nd nd √ √ √
√ √
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