Speciality Chemicals Magazine JAN / FEB 2025 | Page 37

Figure 2 - 13 C IRMS isotopic deviation results for vanillin depending on origin

Vanillln blend ex-Wheat / ex-corn via GMM 3:7 -19 . l "t. 1:1 - ??. 4X» on an assessment made by the FDA . In fact , ex-ferulic vanillin made by fermentation has been determined to be ‘ a natural process resulting in a natural product ’ by the FDA .

Therefore , as natural flavour labelling becomes an increasingly important value for many brands , it is important to ensure that the natural vanillin used by manufacturers is indeed fully compliant with today ’ s stringent regulations .

Origin authentication

Natural vanillin is a product with high added value , which can lead to fraud or adulteration with products of so-called natural origin . Therefore , authentication analysis is critical to distinguish natural from synthetic vanillin and guarantee its authenticity status .

There are two main methods of authentication that focus on raw material origin : 14 C analysis and

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C IRMS analysis . The former is commonly used to date organic materials and thus makes it possible to discriminate between a recent and an old source .

In the case of vanillin , it can help to discriminate 100 % modern carbon , indicating that the vanillin comes from a natural source . If the value is close to 0 % it means that it is coming from a very old source , such as guaiacol from petroleum .

The advantages of 14 C activity analysis are that it makes it possible to discriminate products of petroleum origin from those of biosourced origin and no database is required . However , it cannot distinguish a chemical process from a natural one , such as ex-lignin vanillin , which is biosourced but not based on a natural process . Consequently , for many years , the industry has implemented other methods to determine the origin of vanillin flavours . 13 C IRMS analysis is based on the absorption of different carbon isotopes by plants , based on their photosynthesis pathways . Different categories can be defined :

• Plants with C 3 absorption , such as rice

• Plants with C 4 absorption like sugarcane and corn

• CAM plants such as orchids

Figure 1 shows the different values found for 12 C and 13 C ratios based on the different photosynthesis pathways .

Advanced analytical methods have been developed to discriminate botanical origins and can be used to check compliance with regulations for naturalness . Botanical origins of natural vanillin can be categorised using isotopic differentiation methods such as 13 C IRMS .

For instance , this methodology can confirm that vanillin ex-ferulic acid comes from rice and ex-eugenol

from cloves . Figure 2 shows the results obtained by 13 C IRMS isotopic analyses for different origins .

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C IRMS analysis is widely used in the flavours and fragrances industry and allows the identification of the main botanical origins of vanillin . It also clearly discriminates biosourced synthetic vanillin ( guaiacol , lignin ) from biosourced natural vanillin ( Figure 3 ).

However , it requires a representative database and does not detect or authenticate blends ( for example , a blend of vanillin ex-glucose ex-wheat and vanillin ex-glucose ex-corn would fall into the vanilla bean isotopic deviation ). This is an important aspect for the industry as consumers are pushing for more transparency . Therefore , other methods have been developed to increase the accuracy of identifying the raw material sources of vanillin .

SNIF-NMR

Site-Specific Natural Isotope Fractionation by Nuclear Magnetic Resonance ( SNIF-NMR ) can provide information on the origin - botanical , synthetic , geographical - of the molecule or product . It is a way of obtaining a vanillin ‘ fingerprint ’ linked to its origin .

Two methodologies have been developed : SNIF-NMR carbon and SNIF-NMR hydrogen . They are much more accurate and determine

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