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Composition of Volatile Compounds of Horseradish Roots (Armoracia rusticana L.) Depending on the Genotype

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Horseradish is a perennial plant with significant antioxidant properties, and it contains about 0.2% to 1.0% of essential oil, mainly sinigrin, sinigrin-derived allylisothiocyanate and diallylsulphide. The aim of the study was to determine composition of volatile compounds of horseradish (A. rusticana L.) roots depending on the genotype. Volatiles from fresh horseradish roots of nine genotypes were extracted using solid phase microextraction with DVB/Car/PDMS fibre and were further analysed using gas chromatography-mass spectrometry. The volatile compounds were identified by comparing their mass spectra with mass spectral libraries (Nist98) and by calculating linear retention indexes and comparing them with the literature data. The studied horseradish genotypes differed both in the quantitative and qualitative content of aroma compounds. Totally 15 volatile compounds were detected, and their highest amount was found in genotype G12B. The main aroma compound of all horseradish samples was allylisothiocyanate, which formed 64-82% of the total identified volatile compounds. The obtained results were compared with those found in the literature. All horseradish samples contained significant amounts of phenylethylisothiocyanate (4-18%) that is formed from glucosinolate - gluconasturtin. The study revealed that genotype has great influence on the content of volatiles in horseradish roots.
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© Latvia University of Agriculture (LLU) 2013
Proc. Latv. Univ. Agr., 2013, 29(324)
DOI: 10.2478/plua-2013-0001
___________________________
* Corresponding author’s email:
Lolita.Tomsone@llu.lv
Composition of Volatile Compounds of Horseradish Roots
(Armoracia rusticana L.) Depending on the Genotype
Lolita Tomsone*, Zanda Kruma, Ruta Galoburda
Department of Food Technology, LLU
Thierry Talou
National Polytechnic Institute of Toulouse, France
Abstract. Horseradish is a perennial plant with signicant antioxidant properties, and it contains about 0.2% to
1.0% of essential oil, mainly sinigrin, sinigrin-derived allylisothiocyanate and diallylsulphide. The aim of the
study was to determine composition of volatile compounds of horseradish (A. rusticana L.) roots depending
on the genotype. Volatiles from fresh horseradish roots of nine genotypes were extracted using solid phase
microextraction with DVB/Car/PDMS bre and were further analysed using gas chromatography–mass
spectrometry. The volatile compounds were identied by comparing their mass spectra with mass spectral
libraries (Nist98) and by calculating linear retention indexes and comparing them with the literature data. The
studied horseradish genotypes differed both in the quantitative and qualitative content of aroma compounds.
Totally 15 volatile compounds were detected, and their highest amount was found in genotype G12B. The
main aroma compound of all horseradish samples was allylisothiocyanate, which formed 64–82% of the total
identied volatile compounds. The obtained results were compared with those found in the literature. All
horseradish samples contained signicant amounts of phenylethylisothiocyanate (4–18%) that is formed from
glucosinolate – gluconasturtin. The study revealed that genotype has great inuence on the content of volatiles
in horseradish roots.
Key words: Genotype, horseradish, volatile compounds, allylisothiocyanate.
Abbreviations
AC – allylcyanate
AITC – allylisothiocyanate
ATC – allylthiocyanate
BITC – benzylisothiocyanate
BuITC – butylisothiocyanate
CETP – 1-cyano-2,3-epithiopropane
CPITC – cyclopentylisothiocyanate
DAS – diallylsulde
EN – epithionitrile
IBuITC – isobutylisothiocyanate
IPITC – isopropylisothiocyanate
ITC – isothiocyanate
MITC – methylisothiocyanate
ODN – oxazolidinethione
PEITC – phenylethylisothiocyanate
PETC – phenethylthiocyanate
PITC – phenylisothiocyanate
PPTC – phenylpropylthiocyanate
TC – thiocyanate
Introduction
Horseradish (Armoracia rusticana L.) is a
member of the family Brassicaceae. It is a perennial
plant possessing a particularly pungent avour and
signicant antioxidant properties. Horseradish is
indigenous to Eastern and Northern Europe and
the Mediterranean and is also cultivated in Central
Europe. Horseradish root has a brown outer skin
and a eshy white interior. The root by itself does
not give much aroma, but releases a pungent,
burning, mustard-like aroma upon grating, cutting
or shredding, and it disappears very quickly.
Horseradish has a sharp, acrid, burning, bitter taste
and it contains about 0.2% to 1.0% of essential oil,
mainly sinigrin, sinigrin-derived AITC, DAS, PPTC
and PETC (Raghavan Uhl, 2000).
ITCs are hydrolysed products of sulphur-
containing compounds called glucosinolates
which occur naturally in cruciferous vegetables
such as watercress, Brussels sprouts, broccoli,
cabbage, kai choi, kale, horseradish, radish and
turnip (Wu, Kassie, & Mersch-Sundermann, 2005).
Enzymes and substrates come in contact upon
damage to plant tissues, such as during injury or
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
chewing, resulting in hydrolysis of the glucosinolates
to liberate glucose and sulfate and form unstable
aglucones that spontaneously rearrange to form
ITCs, TCs, nitriles, ENs, or ODNs (Rask et al., 2000;
Matusheski & Jeffery, 2001; Wittstock & Halkier,
2002; Bones & Rossiter, 2006). Hydrolysis reaction
is catalysed by myrosinase bond to the cell wall
(Neoh, Yamamoto, Ikefuji, Furuta, & Yoshii, 2012).
The nature of the hydrolysis products depends on
the structure of the glucosinolate side chain, the plant
species, and the reaction conditions (Rask et al., 2000;
Matusheski & Jeffery, 2001; Wittstock & Halkier,
2002; Bones & Rossiter, 2006). The pH also affects
the production of glucosinolate compounds. AC
production proceeds at pH 4.0 (low pH environment
favours the formation of nitriles), whereas AITC is
produced at pH 7.0 (Gil & MacLeod, 1980; Bones &
Rossiter, 1996). At neutral pH and upon inactivation
of a protein factor, for example, the epithiospecier
protein, the products are principally ITCs (Gil &
MacLeod, 1980; Bones & Rossiter, 1996; Wittstock
& Halkier, 2002).
The complexity of the host plant glucosinolate
prole is further inuenced by the array of
ssion products that arise after tissue is damaged.
Glucosinolates accumulate in cell vacuoles isolated
from myrosinase, a thioglucoside glucohydrolase
responsible for initiating glucosinolate degradation
(Andreasson, Jorgensen, Hoglund, Rask, &
Meijer, 2001). Glucosinolates are β-thioglucoside
N-hydroxysulfates with more than 120 unique
side chains derived from common amino
acids: Phe or Tyr which give rise to aromatic
glucosinolates; Ala, Leu, Ile, Met, or Val that
form aliphatic glucosinolates; and Trp that takes
part in a reaction forming indole glucosinolates
(Fahey, Zalcmann, & Talalay, 2001; Halkier &
Gershenzon, 2006). The damage by insects or
any kind of injury alter glucosinolate metabolism
in cruciferous vegetables, and plants release a
plethora of volatile compounds including indoles,
monoterpenes and sesquiterpenes (Olsson &
Jonasson, 1994). While glucosinolates are major
players in determining the chemo-ecological
relationships between Brassicaceae hosts and their
insect pests, other allelochemicals are likely to be
involved (Bodnaryk, Luo, & Kudryk, 1997; Pfalz,
Vogel, Mitchell-Olds, & Kroymann, 2007).
Glucosinolate (sinigrin) is hydrolyzed by
thioglucosidase (myrosinase) producing CETP,
AC, AITC, and ATC (Shahidi & Gabon, 1990).
Myrosinase has been suggested to be a cell wall or
membrane-bound enzyme. Several researchers have
reported that sinigrin is localized to protein bodies in
aleurone-like cells, and is absent from myrosin cells.
Glucosinolates are composed of a sulfonated oxime,
a thioglucose group, and a variable carbon R-group,
which determines the name of the glucosinolate
compound (Whitmore & Naidu, 2000). Myrosinase
enzyme acts on sinigrin to give AITC as the major
product, which gives horseradish its burning taste
(Raghavan Uhl, 2000; Whitmore & Naidu, 2000).
Investigations about glucosinolates and AITC
have been carried out for several decades, and almost
40 years ago it was determined that more than 80%
of all glucosinolates identied are in the family of
Brassicaceae, considered as a chemotaxonomic
criterion for Brassica classication (Kjaer, 1976).
Several authors have reported on the content of
glucosinolates and AITC in plants, for example,
cabbage varieties contain from 4 to 146 ppm of
AITC, from 0 to 2.8 ppm of BITC, and from 1 to
6 ppm of PEITC. In papaya during growing, BITC
concentration in seeds has increased, whereas
in pulp – decreased (Whitmore & Naidu, 2000).
Mustard seeds have been observed to contain
about 93% of sinigrin (Shahidi & Gabon, 1990). In
broccoli, the ITC sulforaphane has not been found
in an intact plant, but has been actually derived from
its precursor – glucoraphanin (Dinkova-Kostova,
2008). The research data shows that in the mid-vein
and periphery of A.thaliana leaves, glucosinolates
have been detected at higher levels than in the inner
leaf lamina (Shroff, Vergara, Muck, Svatos, &
Gershenzon, 2008).
In Capperis grandis L. roots, also
4,5,6,7-tetrahydroxydecyl-ITC has been identied
(Gaind, Gandhi, Junega, Kjær, & Juhl, 1975). As
the main glucosinolate in seed oil and aerial parts of
caper, glucocapperin has been identied (Matthaus
& Özcan, 2002), whereas in oil from caper leaves –
2-hehenalbutyl-ITC and IPITC (Afsharypuor, Jeiran,
& Jazy, 1998). Research on commercial caper has
shown that the major glucosinolate in this plant is
MITC, followed by BITC (Romeo, Ziino, Giuffrida,
Condurso, & Verzera, 2007; Tlili et al., 2011).
PEITC exists in nature as gluconasturtin, and
in particularly high levels is found in watercress
(Fenwick, Heaney, & Mullin, 1983). Among
ITCs, PEITC has been extensively investigated
for its chemopreventive action. PEITC is able
to inhibit chemically induced lung, forestomach
and esophageal tumorigenesis effectively
(Wu, Kassie, & Mersch-Sundermann, 2005). Some
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
researchers have determined that different cultivars
of the same species show different levels of AITC
(Mayton, 1996).
ITC has a high biological activity. Korean
researchers have reported that AITC is the most
effective antimicrobial compound compared to garlic
oil and trans-cinnamaldehyde (Gamage, Park, &
Kim, 2009). Addition of AITC (less than 0.1%) to
kimchi, a traditional fermented Korean dish, is an
effective way of enhancing its shelf-life (Ko, Kim,
& Park, 2012). In China, ITCs (AITC, n-PITC and
IBuITC) isolated from Brassicaceae family plants
have been used to avoid Chongcai paste avour
and colour changes during the storage (Li, Xue, Xu,
Ren, & Pan, 2012). Italian researchers have reported
on the use of glucosinolate-derived ITC for preserving
fruits, and the results showed that the analysed ITC
(BITC, butenyl-ITC, AITC and others) had benecial
effect on stone fruit quality during storage (Mari,
Leoni, Bernardi, Neri, & Palmieri, 2008).
Many ITCs have proved to be effective
chemopreventive agents against carcinogen-induced
cancers in experimental animals (Wu, Kassie, &
Mersch-Sundermann, 2005). Also horseradish has
benecial effect on human health traditionally
it was used by Europeans to treat gout, kidney
stones, asthma, and bladder infections. Horseradish
was also used in Europe to prevent scurvy before
vitamin C was discovered. Grated horseradish mixed
into a paste is a home remedy for chest congestion
and stiff muscles because it brings blood to the
surface of the skin and warms the skin. Horseradish
has antioxidant and antimicrobial properties
(Raghavan Uhl, 2000).
Several genotypes of horseradish are included
in the collection of vegetable genetic resources of
Latvian origin in the Pūre Horticultural Research
Centre. Until now, biologically active substances
of horseradish have not been studied in Latvian
horseradish collection. No references concerning the
chemical composition of the volatiles of this plant
were found in the literature.
The aim of the present study was to determine the
composition of volatile compounds of A. rusticana L.
roots depending on the genotype.
Materials and Methods
Plant material
Nine genotypes of horseradish (Armoracia
rusticana L.) were collected at the Pūre Horticultural
Research Centre collection eld (latitude – 57° 03’ N;
longitude – 22° 91’ E). All genotypes were of Latvian
origin (from different regions) with the exception of
genotype No. 2 originating in Belarus. The genotypes
were marked as follows: G1 – genotype 1; G2 –
genotype 2; G3 – genotype 3; G12B – genotype
12B; G104 – genotype 104; G105 genotype 105;
G280 – genotype 280; and G281 – genotype 281. The
horseradish roots were harvested in September 2011
to determine composition of volatile compounds.
Analyses were performed within two weeks after
harvest. Freshly harvested roots were washed, peeled,
homogenized and immediately analysed.
Solid phase microextraction (SPME)
Volatiles from the horseradish roots were
extracted using SPME. A total of 5 g of a sample was
weighed into a 20-ml headspace vial and capped with
a septum. For SPME extraction, a divinylbenzene/
carboxen/polydimethylsiloxane (DVB/Car/PDMS)
bre (Supelco Inc., Bellefonte, PA, USA) was used.
The headspace SPME is based on the absorption of
the analytes on a bre coating placed in the sample’s
headspace volume and on the partition of the target
analytes between the sampling matrix and the bre.
SPME parameters were: incubation time – 10 min;
extraction temperature – 35±1 °C; and extraction
duration – 10 min.
After the extraction, the volatile compounds
were thermally desorbed and transferred onto
the chromatographic column where they were
separated. Desorption parameters: 15 min at
250 °C. That time was enough to ensure total
desorption. Finally, the volatile compounds were
transferred to the mass spectrometer for their
identication.
Gas chromatography–mass spectrometry
analysis (GC/MS)
For analysis of the SPME extracts, a Perkin Elmer
Clarus 500 GC/MS and an Elite-Wax ETR columns
(60 m × 0.25 mm i.d.; DF 0.25 μm) were used.
Working conditions: injector 250 °C; transfer line
to MSD – 260 °C; oven temperature start – 40 °C,
hold 10 min, programmed from 40 to 60 °C at
2 °C min-1, and from 60 to 250 °C at 20 °C min-1, hold
5 min; carrier gas (He) – 1 ml min-1; split ratio – 2:1;
ionization – EI+ mode; acquisition parameters in full
scan mode – scanned m/z 40–400.
The volatile compounds were identied by
comparing their mass spectra with mass spectral
libraries (Nist98) and by calculating linear retention
indexes and comparing them with the literature data.
All analyses were performed in triplicate. Compounds
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
in the Tables are shown in the order of the retention
time. As a quantitative measure, the share in the total
GC peak area for each compound is given.
Statistical analysis
The experimental results were analyzed by
Microsoft Excel 2010 and SPSS 17.00. Analysis
of variance (ANOVA) and Tukey’s test were
used to determine differences among the samples.
Differences were considered signicant at p<0.05.
Hierarchical cluster analysis was performed to
classify horseradish genotypes in clusters depending
on the composition of volatiles. The method used was
the between-group linkage. The distances between
samples were calculated using square Euclidean
distances. As pre-treatment of data, transformation
of the values of variables (average zero and standard
deviation 1) called Z scores was carried out. The
dendrogram similarity scales that were generated by
the SPSS program ranged from zero (greater similarity)
to 25 (lower similarity). Similarities between the
analyzed samples are presented in the dendrogram
(see Fig. 1). The linear correlation analysis was
performed in order to determine relationship between
* Mean values within the same row followed by different letters (a, b, c, and d)
signicantly differ according to the LSD test (p<0.05).
Fig. 2. RPAU (relative peak area units) of the volatile compounds of
horseradish roots depending on the genotype.
0 5 10 15 20 25
G 2
G 104
G 105
G 281
G 12B
G 280
G 1
G 3
G 106
Fig. 1. The dendrogram obtained by hierarchical cluster analysis using means of
the volatile compounds of horseradish roots.
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
Table 1
The volatile avour compounds (%) as measured by solid phase microextraction followed by gas chromatography–mass
spectrometry in horseradish roots depending on the genotype
Compounds RT G12B G2 G105 G1 G280 G104 G281 G3 G106
N.i. 4.11 0.02±0.00 0.03±0.01 0.04±0.01 0.06±0.01 0.04±0.00 0.04±0.03 0.09±0.08 0.02±0.00 0.24±0.03
2-butylisothiocyanate 20.07 1.82±0.06 0.81±0.13 1.92±0.03 2.00±0.09 2.81±0.01 1.01±0.34 1.32±0.03 1.18±0.02 2.15±0.41
Isobuthylisothiocyanate 21.50 n.d. n.d. 0.14±0.02 0.10±0.01 n.d. 0.08±0.00 n.d. 0.21±0.06 0.06±0.05
Allylisothiocyanate 22.71 75.61±0.07 68.99±0.17 74.46±0.09 81.82±0.73 79.10±0.01 69.65±0.81 73.85±0.98 71.34±0.56 63.60±0.25
3-methylbutylisothiocyanate 24.08 14.58±0.02 11.11±0.05 12.62±0.14 5.14±0.05 12.74±0.10 11.53±0.01 11.23±0.57 2.64±0.06 6.38±0.08
3-butenylisothiocyanate 24.74 0.48±0.01 0.34±0.01 0.42±0.07 0.53±0.01 0.28±0.01 0.33±0.05 0.43±0.08 0.41±0.03 0.20±0.07
Pentylisothiocyanate 25.35 0.10±0.01 0.21±0.02 0.02±0.04 0.11±0.01 0.04±0.00 0.16±0.00 0.07±0.01 0.30±0.01 n.d.
Cyclopentylisothiocyanate 26.56 2.10±0.01 2.82±0.09 0.37±0.11 3.20±0.06 0.26±0.01 2.20±0.10 0.39±0.15 4.36±0.34 0.69±0.07
N.i. 28.86 0.11±0.01 0.14±0.03 0.02±0.02 0.13±0.03 0.02±0.00 0.08±0.01 0.03±0.00 0.33±0.04 0.04±0.01
N.i. 32.23 0.01±0.01 n.d. 0.01±0.00 0.08±0.01 n.d. 0.01±0.00 n.d. 0.29±0.01 0.01±0.00
N.i. 32.81 n.d. 0.02±0.00 0.05±0.01 0.01±0.00 n.d. 0.04±0.00 0.05±0.01 n.d. 0.13±0.00
N.i. 34.04 0.05±0.00 0.45±0.03 0.03±0.00 0.13±0.09 0.09±0.00 0.54±0.02 0.03±0.00 0.14±0.02 n.d.
Benzylisothiocyanate 35.96 0.25±0.02 0.36±0.04 0.32±0.05 0.31±0.08 0.33±0.01 0.50±0.01 0.35±0.02 0.76±0.01 0.65±0.02
2-phenethylisothiocyanate 38.49 4.83±0.11 14.58±0.45 9.49±0.51 6.26±0.08 4.22±0.06 13.74±0.29 11.89±0.67 17.70±0.37 25.74±0.26
Others 0.05±0.00 0.12±0.01 0.06±0.01 0.10±0.00 0.06±0.01 0.11±0.03 0.29±0.03 0.31±0.04 0.11±0.01
RT – retention time; N.i. – not identied; n.d. – not detected
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
the volatile compounds. Differences were considered
signicant at p<0.05.
Results and Discussion
Volatile compounds released from foods are
closely related to their aroma and can be used for
quality assessment. The composition and content
of volatiles vary greatly depending on the genetic
background.
Our results of the total relative peak area (RPA)
of the volatile compounds detected basing on the
genotype origin showed that RPA of genotype G12B
was signicantly (p<0.05) the highest, whereas
genotypes G281, G3 and G106 had a signicantly
(p<0.05) lower RPA (Fig. 2).
Table 1 lists the major volatiles (more than 0.1%)
and some particular volatiles in each of the genotype.
A total of 15 volatile compounds were detected,
of which two were found only in some genotypes
(IBuITC was found in G105, G1, G104, G3, and
G106; pentyl-ITC in all genotypes except G106).
From the identied compounds, ITCs constituted
the major class of volatiles (totally nine ITCs were
identied); the main compound of all horseradish
samples was AITC forming 64–82% of total identied
volatile compounds.
The horseradish roots contained also signicant
(p<0.05) amounts of 2-phenethyl-ITC, CPITC, and
2-butyl-ITC, and the highest concentration of these
compounds was detected in genotypes G106, G3, and
G280, respectively. Among the nine genotypes, the
roots of G1, G104 and G105 contained the highest
number of volatile compounds.
Korean researchers have reported that horseradish
essential oil contains 94% of AITC, an ITC-class
compound (Park et al., 2006). Our results show
a similar tendency compared to other volatile
compounds detected in horseradish roots, AITC
was found in greatest amounts. According to
the literature data, the most important volatile
compounds detected in other plants also belong to the
ITC class.
Researchers in Italy (Romeo, Ziino, Giuffrida,
Condurso, & Verzera, 2007) have found that
sulphur compounds in the volatile fraction of
pickled ower (Capparis spinosa L.) buds are MITC
(441.22 ppm) and BITC (17.62 ppm). Another
group of researchers (Kulisic-Bilusic, Schmöller,
Schnäbele, Siracusa, & Ruberto, 2012) have
detected that MITC (92.06%) is the main
volatile compound in the essential oil from
caper (Capparis spinosa L.), whereas BuITC and
sec-BuITC constitute only 0.38% and 0.25%,
respectively.
The results of our research demonstrated that the
content of volatiles in horeseradish roots varied from
0% to 81.82% and depended on the genotype. Tukey’s
test revealed that differences between individual
compounds in different genotypes were signicant
(p<0.05). The highest content of IBuITC, CPITC
and BITC was identied in G3, whereas genotype
G106 had the greatest amount of 2-phenethyl-ITC.
Also researchers from New Zealand have reported
that volatile composition in Actinidia arguta is
inuenced by the genotype (Matich et al., 2003).
There are research ndings on aerial parts of six
genotypes of Hyptis pectinata collected in different
stages of maturation, demonstrating that the content
of volatiles in the genotypes was different (Arrigoni-
Blank et al., 2008).
Regression and correlation analyses were
performed to determine relationship between the
volatile compounds (Table 2). A very strong positive
correlation was found between the nonidentied
compounds (28.86) and CPITC, but correlation
between PEITC and AITC was very strong and
negative (p<0.01).
Hierarchical cluster analysis was applied to a
data set of 15 variables (volatile compounds) and
9 genotypes of horseradish roots. The dendrogram
(Fig. 1) shows that the samples of horseradish
roots were not quite homogeneous. Besides, some
genotypes markedly differed from the others.
According to the hierarchical cluster analysis, at
the distance of three, horseradish genotypes can be
grouped as follows:
cluster A: genotypes 2, 104, and 105;
cluster B: genotypes 281, 12B, and 280;
cluster C: genotype 1;
cluster D: genotype 3;
cluster E: genotype 106.
The cluster analysis based on the concentrations
of identied volatiles showed that genotypes
G1, G3 and G106 separated out among other
genotypes of horseradish samples by having lower
levels of total aroma concentration (Fig. 1). Clusters
obtained in our previous research basing on the
total phenolic content and scavenging activity
(Tomsone, Krūma, Lepse, & Alsina, 2012) did not
show any congruence with the grouping according
to volatile composition made in the present research.
This may be explained by the fact that volatile
compounds and phenolic compounds are formed
in the result of different biosynthetic processes
(Velišek & Cejpek, 2008).
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Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
Table 2
Pearson’s coefcients between volatile compounds
Compounds
Compounds
N.i.
(4.11)
2-butyl isothiocyanate
Isobuthyl isothiocyanate
Allyl isothiocyanate
3-methylbutylisothiocyanate
3-butenyl isothiocyanate
Pentyl isothiocyanate
Cyclopentylisothiocyanate
N.i.
(28.86)
N.i.
(32.23)
N.i.
(32.81)
N.i.
(34.04)
Benzyl isothiocyanate
N.i. (4.11) 1
2-butylisothiocyanate 0.138 1
isobuthylisothiocyanate -0.020 -0.170 1
allylisothiocyanate -0.341 0.293 0.002 1
3-methylbutylisothiocyanate -0.183 0.058 -0.561** 0.283 1
3-butenylisothiocyanate -0.301 -0.209 0.257 0.689** 0.091 1
pentylisothiocyanate -0.488** -0.679** 0.387*-0.095 -0.399*0.210 1
cyclopentylisothiocyanate -0.372 -0.485*0.451*0.001 -0.566** 0.345 0.873** 1
N.i. (28.86) -0.355 -0.423*0.559** -0.074 -0.614** 0.254 0.881** 0.912** 1
N.i. (32.23) -0.221 -0.219 0.727** 0.035 -0.706** 0.254 0.685** 0.718** 0.899** 1
N.i. (32.81) 0.501** 0.178 -.0130 -0.730** -0.280 -0.650** -0.440*-0.380 -0.362 -0.280 1
N.i. (34.04) -0.286 -0.622** -0.023 -0.245 0.072 -0.108 0.546** 0.403*0.207 -0.066 -0.188 1
Benzylisothiocyanate 0.173 -0.143 0.432*-0.712** -0.751** -0.499** 0.372 0.336 0.511** 0.568** 0.488** 0.084 1
2-phenethylisothiocyanate 0.428*-0.211 0.179 -0.927** -0.595** -0.633** 0.121 0.097 0.187 0.172 0.775** 0.102 0.848**
* – correlation is signicant at the 0.05 level (two-tailed); ** – correlation is signicant at the 0.01 level (two-tailed); N.i. – not identied
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L. Tomsone et al.
Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
Conclusion
1. The genotype has an important impact on the
content of volatile compounds of horseradish
roots.
2. Totally 15 volatile compounds were detected.
3. From all the identied compounds,
isothiocyanates constituted the major class of
volatile compounds; the main compound of all
horseradish samples was allylisothiocyanate
forming 64–82% of total identied volatile
compounds.
4. All horseradish samples contained large amounts
of 2-phenylethylisothiocyanate (4–26%) that is
formed from glucosinolate gluconasturtin.
5. Hierarchical cluster analysis can be performed to
group the horseradish genotypes according to the
composition of volatile compounds.
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Composition of Volatile Compounds of Horseradish Roots Depending on the Genotype
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Acknowledgement
The research has been performed within the framework of the “Osmose” project between Latvia University
of Agriculture and National Polytechnic Institute of Toulouse entitled “Comparison of composition
and properties of forgotten aromatic plants and fungi of Latvia and Midi-Pyrenees” (Comparaison des
compositions et proprietes phytochimiques de plantes-champignons aromatiques oublies lettons et Midi-
Pyreneens). The authors acknowledge nancial support of the ERAF project „Promotion of scientic activities
of LLU”, contract No. 2010/0198/2DP/2.1.1.2.0/10/APIA/VIAA/020. The authors also acknowledge the Pūre
Horticultural Research Centre for the supply of horseradish roots.
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... In recent years, numerous studies addressed the phytochemical composition and pharmacological activities of metabolites from horseradish roots [4][5][6][7][8][47][48][49][50][51][52][53][54]. There are relatively few studies related to the phytoconstituents from horseradish leaves [1,7,8,55]. ...
... The spectra revealed a complex combination of low-molecular-weight components, of which some were detected. The mass spectra of the identified metabolites were compared with those of the NIST/EPA/NIH Mass Spectral Library 3.0 database, in addition to a literature review [7,48,55,66]. The mass spectrum and the phytoconstituents identified by the ESI-QTOF-MS analysis are presented in Figure 2 and Table 2, respectively. ...
... The mass spectrum and the phytoconstituents identified by the ESI-QTOF-MS analysis are presented in Figure 2 and Table 2, respectively. The metabolite profile from the horseradish sample conducted through the GC-MS and mass spectroscopy corroborated the data reported in the literature [6][7][8][48][49][50][51][52][53][54][55][63][64][65]. ...
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The myrosinase-glucosinolate system is involved in a range of biological activities affecting herbivorous insects, plants and fungi. The system characteristic of the order Capparales includes sulphur-containing substrates, the degradative enzymes myrosinases, and cofactors. The enzyme-catalyzed hydrolysis of glucosinolates initially involves cleavage of the thioglucoside linkage, yielding D-glucose and an unstable thiohydroximate-Ο-sulphonate that spontaneously rearranges, resulting in the production of sulphate and one of a wide range of possible reaction products. The products are generally a thiocyanate, isothiocyanate or nitrile, depending on factors such as substrate, pH or availability of ferrous ions. Glucosinolates in crucifers exemplify components that are often present in food and feed plants and are a major problem in the utilization of products from the plants. Toxic degradation products restrict the use of cultivated plants, e.g. those belonging to the Brassicaceae. The myrosinase-glucosinolate system may, however, have several functions in the plant. The glucosinolate degradation products are involved in defence against insects and phytopathogens, and potentially in sulphur and nitrogen metabolism and growth regulation. The compartmentalization of the components of the myrosinase-glucosinolate system and the cell-specific expression of the myrosinase represents a unique plant defence system. In this review, we summarize earlier results and discuss the organisation and biochemistry of the myrosinase-glucosinolate system.
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In the course of evolution, all eukaryotes have developed sophisticated defense systems that allow their survival and coevolution with other competing organisms. These include the biosynthesis of a wide array of small molecules (secondary metabolites) with extraordinarily sophisticated chemistry in plants, as well as elaborate enzymatic systems capable of coping with the toxicities of electrophiles and oxidants (phase 2 enzymes) in both plants and animals. Phase 2 enzymes catalyze enormously versatile chemical reactions that collectively lead to detoxification of various electrophiles and oxidants. Together with housekeeping antioxidant enzymes (e.g., catalase, superoxide dismutase) and small molecular mass direct antioxidants (e.g, ascorbic acid, tocopherol, glutathione), phase 2 enzymes constitute an integral part of the cellular defense. Furthermore, the discoveries that (1) phase 2 enzymes can be induced selectively (without concomitant induction of phase 1 enzymes) by a wide variety of stimuli that we now simply call “inducers” and (2) this “induced state” that we now refer to as “the phase 2 response” could explain how so many diverse chemical agents could block carcinogenesis in various animal models led to the birth of the hypothesis that induction of phase 2 enzymes could be a powerful strategy for protection against cancer and other chronic diseases [1-3].
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The sterol profile of canola, Brassica napus, was altered by treatment with 5 ppm of the systemic fungicides fenpropimorph and tridemorph. The usual Δ5-phytosterols sistosterol, campesterol, and stigmasterol were depleted in leaves and roots and replaced by unusual 4-alpha-methyl and 4-desmethyl sterols that were never observed in untreated plants. Growth, development, and survival of the bertha armyworm, Mamestra configurata, fed leaves of treated canola in the laboratory were affected adversely at specific stages in the life cycle. Larval survival was high and not significantly different in treated and control groups. Most of the mortality in the treated group occurred at pupation and during pupal-adult development. At ecolosion a high proportion of adults were deformed (crumpled wings, failure to exit the pupal case). The adverse effects of feeding on fenpropimorph-treated canola were not attributable to the fungicide itself because larvae fed an artificial diet containing a 10-fold higher concentratio...
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Root material of Capparis grandis, of Indian origin, contains a free isothiocyanate, identified as 4,5,6,7-tetrahydroxydecyl isothiocyanate 1 by spectroscopical and chemical means, yet without specification as to its stereochemistry. The presence of the parent glucosinolate, and three other, unidentified glucosinolates in C. grandis has been noted. The distribution of glucosinolates within the genus Capparis is reviewed and the biosynthetic origin of the individual compounds discussed.
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An active thioglucoside glucohydrolase extract was prepared from commercial mustard powder and its effect on the degradation of two pure glucosinolates was investigated. During reaction in a distilled water medium the pH of the solution decreased markedly and the ratio of products (isothiocyanate and nitrile) varied considerably. After 20–30 min, when the pH had fallen to ca 5.6, isothiocyanate production ceased whilst nitrile continued to be produced and in amounts which increased linearly with time for at least 40 min. This behaviour can be correlated with the changing pH of the medium. In controlled pH experiments it was confirmed that nitrile formation is favoured at lower pH levels and that the ratio of nitrile to isothiocyanate is directly related to the hydrogen ion concentration of the medium. No reason could therefore be found for the observed formation of nitrile in some natural systems at pHs greater than 7.
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