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doi: 10.1111/1541-4337.12006
Stability of essential oils . . .
Terpenoids (Isoprenoids) Short-chained Aliphatics
Eugenol
3-Octanone
-Caryophyllene Camphor Thymol
Citral l o e n i C - 8 , 1 e n e n o m i L
Phenylpropanoids
3-Octanone
-
Figure 1Representative structures typical for essential oils.
hitherto scattered data on factors inuencing essential oil stability.
It sheds light on the chemistry of decomposition reactions and on
analytical approaches to reveal essential oil degradation.
Chemical Composition of Essential Oils
The broad range of possible applications described above results
from the large variety in the composition of essential oils. A multi-
tude of different, but often structurally closely related, components
have been identied in essential oils. Each oil in turn can be com-
posed of only a few up to a complex mixture of far more than 100
single substances, respectively (Blitzke 2009). Flavor contribution
of single compounds though does not strictly depend on their
respective concentration but relies on the specic odor threshold
that is determined by structure and volatility. Consequently, even
minor components deriving from oxidation or degradation reac-
tions may have a strong impact on the avor if their aroma value
is high enough (Grosch 2007).
For the most part, essential oil components can be as-
signed as lipophilic terpenoids, phenylpropanoids, or short-chain
aliphatic hydrocarbon derivatives (Kubeczka 1979) of low molec-
ular weight, with the rst being the most frequent and character-
istic constituents (Treibs and Merkel 1960). Among these, allylic,
mono-, bi-, or tricyclic mono- and sesquiterpenoids of different
chemical classes make up the major part in essential oils, such
as hydrocarbons, ketones, alcohols, oxides, aldehydes, phenols, or
esters. Representative structures are depicted in Figure 1. Due
to their low volatility, diterpenes are barely encountered in gen-
uine essential oils obtained by distillation, while tri- and higher
terpenoids such as sterols or carotenoids are only present in the
nonvolatile fractions such as plant resins or gums and will remain
in the residue (Treibs and Merkel 1960; Martinetz and Hartwig
1998; Humphrey and Beale 2006). Comprehensive reviews pro-
viding structures, occurrences, and uses of terpenoids or further
avorings have been compiled by Grayson (1990) as well as Sur-
burg and Panten (2006).
Constituents in essential oils generally originate from several
major biosynthetic pathways (Franz and Novak 2010). While
the aromatic phenylpropanoids are formed via the shikimic acid
pathway leading to phenylalanine (Pichersky and others 2006;
Colquhoun and others 2010), terpenoids derive from the C
5
-
building blocks isopentenyl diphosphate (IPP) and its isomer
dimethylallyl diphosphate (DMAPP). For structural elucidation
in this vast eld of compounds, the so-called isoprene rule, estab-
lished by Otto Wallach in 1887 and subsequently rened by Sir
Robert Robinson and Leopold Ru zi cka provided a fundamental
milestone, stating that each terpenoid can be basically composed
Figure 2Possible conversion reactions in essential oils.
from isoprene units (C
5
H
8
), mainly in a head-to-tail fashion, ei-
ther directly or by ways of cyclization, rearrangements, or further
conversions from aliphatic isoprenoid precursors (Ru zi cka 1953;
Banthorpe and others 1972; Hanson 2003). The knowledge of
these biochemical principles may be helpful for tracking structural
changes of genuine essential oil constituents.
Alterations of Essential Oils and Possible
Consequences
Due to their structural relationship within the same chemical
group, essential oil components are known to easily convert into
each other by oxidation, isomerization, cyclization, or dehydro-
genation reactions, triggered either enzymatically or chemically.
Upon stability evaluation of essential oils, it needs to be kept
in mind that the chemical composition may already vary in the
starting material, being inuenced by plant health, growth stage,
habitat including climate, edaphic factors, as well as harvest time
(Figueiredo and others 2008; Schmidt 2010). An example for
the structural pattern as a function of harvest time was given by
Masotti and others (2003) who found a decreasing concentration
of a hydrocarbon monoterpene in the essential oil throughout
the year while the amount of an oxidized immediate metabolic
successor rose coevally. Consequently, plant volatiles are subject
to natural uctuations in their composition (Kubeczka 1993) that
need to be considered upon quality evaluation.
As terpenoids tend to be both volatile and thermolabile and may
be easily oxidized or hydrolyzed depending on their respective
structure (Scott 2005), it is well accepted that the chemical com-
position of essential oils is moreover dependent on the conditions
during processing and storage of the plant material, upon distil-
lation as well as in the course of subsequent handling of the oil
itself (Schmaus and Kubeczka 1985; Carle and Fleischhauer 1987;
Fischer and others 1988; Baritaux and others 1992; Venskutonis
and others 1996; Mockut e and others 2005; Schweiggert and
others 2007).
Once deprived of the protective compartmentation in the plant
matrix (Treibs 1956), essential oil constituents are especially prone
to oxidative damage, chemical transformations, or polymerization
reactions (Figure 2). These aging processes generally come along
with a more or less pronounced quality loss (Fincke and Maurer
1974; Kubeczka 1993). In addition to the frequent development
of unpleasant and often pungent avors, shifting colors such as
the formation of a yellow staining in caraway oil (Preuss 1964)
or changes in consistency up to resinication have been reported
both upon degradation of essential oils as well as of single ter-
penoids (Bernhard and Marr 1960; T oth 1967; Dieckmann and
Palamand 1974; Pokorn y and others 1998; Grassmann and Elstner
2003; Sk old and others 2004; Blitzke 2009). For instance, the aro-
matic monoterpene p-cymene, often identied in aged essential
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2012 Institute of Food Technologists
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