NIR Spectroscopy with Chemometric
Analysis Allows One to Distinguish Cinnamon from Spent Cinnamon and Cassia
Reviewed: Shawky E, Selim DA. Rapid authentication and quality evaluation of
Cinnamomum verum powder using near-infrared
spectroscopy and multivariate analysis. Planta Med.
2018;84(18):1380-1387.
Keywords: Adulteration, cassia,
Cinnamomum
aromaticum, Cinnamomum verum, cinnamon, near-infrared
spectroscopy
Cinnamon
(Cinnamomum verum, syn. C. zeylanicum) has been used as a spice for thousands of
years. In addition to C. verum, the
American Spice Trade Association allows other Cinnamomum
species to be traded as cinnamon, such as cassia (C.
aromaticum, syn. C. cassia),
Saigon cinnamon (C. loureiroi), and Indonesian
cinnamon (C. burmannii). In traditional herbal
medicine, cinnamon is used for gastrointestinal complaints, such as mild cases
of spasms, flatulence, or diarrhea,1 among other indications. Modern
research suggests that cinnamon may also be beneficial as adjuvant treatment
for glycemic control. Much of the clinical research has been carried out with
cassia rather than cinnamon,2,3 although there are a number of
clinical investigations where the exact composition was poorly defined, and the
name of species used for the treatment was not provided.4 The
labeling regulations for dietary supplements in the United States require that
common names are consistent with those listed in the American
Herbal Products Associations Herbs of Commerce (HOC), which includes
cassia, camphor (C. camphora), Saigon cinnamon,
Indian cassia (C. tamala), and cinnamon as the Cinnamomum species in the herb trade.5 According
to HOC, the common name “cinnamon” can only be applied to C. verum, while
the common name “cassia” can only be applied to C.
aromaticum. Dietary
supplement manufacturers have to ensure that they have a means of
distinguishing among these species. The bark of the various cinnamon species reportedly
can be distinguished morphologically when in stick form based on the way the
bark curls,4,6 but species determination of powdered cinnamon is more
challenging, and is usually done by chemical analysis.
The
interchangeable use of different Cinnamomum spp.
as a spice is well-known. Similarly, it is reasonable to believe that several
species are used in food supplements labeled as “cinnamon”. However, the number
of Cinnamomum species that can be used as
herbal medicines is limited, with national pharmacopoeias describing which
species is acceptable. And while some manufacturers may regard the therapeutic
benefits of the species in trade as equal, and thus use them interchangeably,
Shawky and Selim suggest that cinnamon are also substituted/mixed with cassia
for financial gain. Such practices have been reported, e.g., in India, when a
study in 2014 found that seven out of 10 cinnamon market samples were actually
made from cassia.7 Another problem with the quality of cinnamon in
trade is the sale of spent cinnamon bark (cinnamon bark of which the essential
oil has been removed). The goal of this research project was to develop a quick
and economical analytical method to distinguish among cinnamon bark, spent
cinnamon bark, and cassia bark, and to detect admixture of spent cinnamon or
cassia to authentic cinnamon. For this purpose, 27 botanically authenticated
samples of each cinnamon and cassia bark were ground into a fine powder and
analyzed by near infrared (NIR) spectroscopy. Spent cinnamon bark was obtained
by exhaustive distillation and subsequent drying of nine cinnamon bark samples.
In
order to evaluate whether mixtures could be differentiated from cinnamon bark
material and if the NIR spectroscopy allowed quantitative measurements, binary
cinnamon-cassia, and cinnamon-spent cinnamon mixtures were made in 5%
increments, starting with 5% up to 95% adulterant. The spectral data were
subjected to multivariate statistics, using principal component analysis (PCA),
soft independent modeling by class analogy (SIMCA), and partial least square
(PLS) regression modeling. PCA and SIMCA both clustered the spent cinnamon,
cassia, and the cinnamon-adulterant mixtures separately from cinnamon. The PLS
regression model was used for quantitative prediction of the adulterant
concentration in binary mixtures with cinnamon, and yielded good correlations
between the predicted data and the actual data.
Comment: Species determination of cinnamon has been a challenge
for many in the dietary supplement industry. Methods to differentiate
among the species include the comparison of the essential oil fingerprints.4,8
In addition, the concentrations of coumarin and phenylpropanes (e.g.,
cinnamaldehyde, cinnamic acid, and eugenol) may be useful to discriminate among
the species. Cinnamon has been shown to contain lower amounts of coumarin than
the other species, but higher concentrations of eugenol.9,10 Finally,
Chen et al. presented a flow-injection mass spectrometric (FIMS) approach to
distinguish among the four species. Based on the PCA loadings plot, the
proanthocyanidins (A type in C. verum and C. burmannii; B type in C. aromaticum
and C. loureiroi), cinnamaldehyde and
coumarin were among the main compounds responsible for separating the species
into distinct clusters.11 The NIR method provides an economic
alternative to the mass spectrometric techniques, and is sensitive enough to
detect adulteration with cassia or spent cinnamon bark at low concentrations
(< 2%). Further work is needed to determine if Saigon and Indonesian
cinnamon are as easily differentiated from cinnamon as cassia by NIR
spectroscopy.
References
- Stahl-Biskup
E, Hiller K, Loew D. Cinnamomi cortex.
In: Blaschek W, ed. Wichtl - Teedrogen und
Phytopharmaka. Stuttgart, Germany: Wissenschaftliche
Verlagsgesellschaft mbH; 2016:180-182.
- Allen RW, Schwartzman E, Baker WL, Coleman
CI, Phung OJ. Cinnamon use in type 2 diabetes: an updated systematic review and
meta-analysis. Ann Fam Med. 2013;11(5):452-459.
- Costello RB, Dwyer JT, Saldhana L.
Bailey RL, Merkel J, Wambogo E. Do cinnamon supplements have a role in glycemic
control in type 2 diabetes? – A narrative review. J Acad Nutr
Diet. 2016;116(11):1794-1802.
- Oketch-Rabah HA, Marles RJ, Brinckmann
JA. Cinnamon and cassia nomenclature confusion: A challenge to the
applicability of clinical data. Clin Pharmacol Ther.
2018;104(33):435-445.
- McGuffin M, Kartesz JT, Leung AY, Tucker
AO. Herbs of Commerce. 2nd ed. Silver
Spring, MD: American Herbal Products Association; 2000.
- Information: Cassia and cinnamon. New
Delhi, India: Food Safety and Standards Authority in India. Available at:
http://old.fssai.gov.in/Portals/0/Pdf/CASSIA%2820-05-2013%29.pdf. Accessed
January 29, 2019.
- Swetha VP, Parvathy VA, Sheeja TE,
Sasikumar B. DNA Barcoding for discriminating the economically important Cinnamomum verum from its adulterants. Food
Biotechnol. 2014;28(3):183-194.
- Senanayake UM, Wijesekera ROB.
Chemsitry of cinnamon and cassia. In: Ravindran PN, Nirmal Babu K, Shylaja M,
eds. Cinnamon and Cassia: the Genus Cinnamomum.
Boca Raton, FL: CRC Press; 2004:80-120.
- Wang YH, Avula B, Nanayakkara NPD,
Zhao J, Khan IA. Cassia cinnamon as a source of coumarin in cinnamon-flavored
food and food supplements in the United States. J Agric
Food Chem. 2013;61(18):4470-4476.
- Avula B, Smillie TJ, Wang YH,
Zweigenbaum J, Khan IA. Authentication of true cinnamon (Cinnamon
verum [sic.]) utilising direct analysis in real time (DART)-QToF-MS.
Food Addit Cont Part A. 2015;32(1):1-8.
- Chen P, Sun J, Ford P. Differentiation
of the four major species of cinnamons (C. burmannii, C. verum,
C.
cassia, and C. loureiroi)
using a flow injection mass spectrometric (FIMS) fingerprinting method. J Agric Food Chem. 2014;62(12):2516-2521.