Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-024-05675-2

ORIGINAL ARTICLE

Essential oils from fennel plants as valuable chemical products: gas

chromatography–mass spectrometry, FTIR, quantum mechanical
investigation, and antifungal activity
Mamoun S. M. Abd El‑Kareem1 · Mohamed A. Rabbih1 · A. M. Rashad2 · Mervat EL‑Hefny3

Received: 22 February 2024 / Revised: 10 April 2024 / Accepted: 23 April 2024

© The Author(s) 2024

Abstract
In the present study, the biomass produced by fennel plants (Foeniculum vulgare Mill.) was converted to yield bioactive
chemicals, and the hydrodistillation method was used to extract the essential oils (EOs) from both the leaves and the umbels.
The antifungal activity of the EOs was tested using bioassay against the development of Fusarium oxysporum MW854649 and
Alternaria solani MT279570. Molecular spectroscopic detection techniques were used to evaluate the EO products using gas
chromatography–mass spectrometer (GC–MS) and Fourier transform infrared spectroscopy (FTIR). GC–MS equipped with
single quadruple analyzers have been used to measure the electron ionization (EI) mass spectra of the primary constituents
of fennel EOs at 70 eV. The main chemical compounds in the EO from leaves were anethole, estragole, D-limonene, trans-
β-ocimene, and fenchone, with percentages of 37.94, 35.56, 17.46, 1.53, and 1.49%, respectively. The abundant compounds
in the EO from umbels were estragole, anethole, D-limonene, fenchone, and γ-terpinene, with percentages of 51.18, 25.08,
12.22, 6.57, and 2.86%, respectively. EI mass spectral fragmentation of the major compounds D-limonene, estragole, anethole,
and fenchone has been investigated. Umbels and leaf EOs at 5000 mg/L displayed the strongest suppression of fungal growth
against A. solani, with values of 87.78% and 79.63%, respectively, compared to the positive control (94.44%). The EOs from
umbels and leaves at 5000 mg/L showed the highest inhibition of fungal growth against F. oxysprium as compared to the
positive control (94.44%), with values of 77.77% and 72.96%, respectively. All of the important ions—including a few dis-
tinctive fragment ions—have comprehensive fragmentation pathways defined. Based on EI, the main routes of fragmentation
for the primary compounds have been identified. The existence of alkenes, aliphatic alcohols, ethers, carboxylic acids, ester
compounds, alkanes, hydrogen-bonded alcohols, and phenols was demonstrated by the FTIR analysis of fennel EOs. On the
other hand, the reactive behavior of the studied molecules has been investigated using two quantum mechanics method: the
modified neglect of diatomic overlap (MNDO), a semi-empirical method, and the density functional theory (DFT)/B3LYP
hybrid density functional method with the 6-311G (d, p) basis set in the ground state for gas phase. The optimum geometries
have been obtained through the execution of computations and electrostatic potential. The obtained analytical and calculated
results were then used to understand the activity of the studied EOs in further medical applications.

Keywords Biomass conversion · GC–MS electron · Mass spectra · FTIR · DFT · Fennel oil · Antifungal activity

1 Introduction gastrointestinal, and hepatoprotective conditions [6–9].

Research has demonstrated the diuretic, anti-inflammatory,
The Apiaceae family includes the ancient spice plant fen- analgesic, and antioxidant properties of herbal medicine
nel (Foeniculum vulgare Mill), which is regarded as one of preparations [10, 11], ACE inhibition [12], anticancer activi-
the most significant medicinal herbs in the world [1]. The ties [13–16], and antimicrobial activities [6, 17, 18].
well-known perennial plant F. vulgare is indigenous to the Essential oils (EOs) are the main constituents of fen-
Mediterranean region [2, 3]. It is utilized to prepare herbal nel seeds and are being used as flavoring agents in vari-
drugs [4, 5] and is being utilized for a range of respiratory, ous foods, cosmetic, and pharmaceutical products [6, 19,
20]. Estragole (methyl chavicol) was the primary chemical
component of fennel seed EOs [21]. It has been observed
Extended author information available on the last page of the article that trans-anethole, fenchone, estragol, and α-phellandrene

Vol.:(0123456789)

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 Biomass Conversion and Biorefinery

are the main constituents of F. vulgare seed EOs [6]. The carried out, which included calculating thermodynamic
content of trans-anethole, the main component of the EO, parameters and optimizing geometrical forms. With the aid
varied between 81.63 and 87.85% according to the maturity of the collected data and the experimental data that has been
stage of fruits [22]. Trans-anethole, estragole, fenchone, and provided, it would be easier to comprehend the bioactivity
D-limonene were highly abundant in the EOs from fennel, of the essential oils, which would advance their usage for
with highly antimicrobial against Aspergillus flavus, Can- medicinal and bioactive purposes.
dida albicans, Bacillus cereus, and Staphylococcus aureus
and antioxidant activities [23].
Mass spectrometry (MS) techniques have played a major 2 Materials and methods
role in the development of the natural goods industry over
the last 5 years. It provided the basis for calculating out the 2.1 Plant materials
molecular weight and recognizing the identities or structures
of most natural compounds [24, 25]. Based on the electron Two botanical parts (leaves and umbels) from the biomass of
ionization mass spectra of the molecules, the MS methods fennel plants (Foeniculum vulgare Mill) were gathered and
can yield a great deal of structural information with minimal identified from plants growing in the nursery of the Depart-
investment in the molecules under study [26]. ment of Floriculture, Ornamental Horticulture, and Garden
The kinetic energy of an ionized molecule is the main fac- Design, Faculty of Agriculture (El-Shatby), Alexandria Uni-
tor affecting its capacity to fragment [27]. Moreover, semi- versity, Alexandria, Egypt, in May, 2023 (Fig. 1). The plant
empirical modified neglect of diatomic overlap (MNDO) was identified and vouchered with the number MERV. 0023.
and density functional theory (DFT) computations are the
most efficient means of computing the structure of the sub-
stance and supporting the experimental study [28, 29]. These 2.2 Extraction of essential oils
are quantum mechanical techniques that are widely used in
chemistry and physics to determine the electronic structure Fresh leaves and umbels of fennel plants each of 250 g were
of molecules and their thermochemical properties [30–37]. hydro-distilled for 3 h in a Clevenger-style apparatus [38,
In this study, the primary constituents of fennel EOs were 52]. Following its separation, anhydrous sodium sulfate
investigated using the DFT approach. The molecular char- ­(Na2SO4) was used to dry the essential oil (EO). EOs were
acteristics, charge distribution, chemical activity, and other stored at 4 °C in a refrigerator in a sealed Eppendorf tube
significant features of the monomeric components in an EO, until further analysis.
i.e., from Aethionema sancakense and Phlomis bruguieri,
can be inferred through DFT calculations [38–43]. 2.3 Gas chromatography–mass spectrometry
Fourier-transform infrared (FTIR) spectroscopy has been analysis, computational details and FTIR
used in conjunction with the GC–MS approach because spectral analysis
of its capacity to test the quality of EOs in a timely, cost-
effective, non-destructive manner [44]. The main advantage The EOs from fresh leaves and umbels of fennel plants were
of IR is that it requires little to no-sample preparation and analyzed for their chemical compounds using a Facous GC-
may be performed quickly and easily [45, 46]. Previously, DSQ mass spectrometer (Thermo Scientific, Waltham, MA,
mid-infrared spectroscopy was mainly used as a qualitative USA) [53]. The geometry of the investigated compounds was
technique for the verification of quality indicators in dis- optimized based on semi-empirical calculations using the
tillates or extracts from plants, or for the identification of MNDO and Polak–Ribiere conjugated gradient algorithms
unknown pure substances by providing structural charac- using the molecular modeling software Hyperchem7.5
terization based on a fingerprint spectrum and functional (W.Thiel 2003, HyperChemTM, Release 7.5 Pro 200) [54].
group vibration [47]. Due to the fact that plant extracts are Density functional theory (DFT/B3LYP) with 6-311G
multicomponent mixtures, IR spectra obtained from them (d, p) basis set in the ground state for gas phase was used to
are typically quite complicated [48, 49]. Band assignments compute the ground state electrostatic potential (ESP) of the
may be challenging due to peak overlapping and vibrational molecule under study [55–57]. Gauss View 05, a molecu-
mixing; every functional group within a single molecule lar visualization application, and the Gaussian 09 program
adds to the overall complexity of the spectrum [50, 51]. package were used for all of the computations [58]. The
Therefore, the main objectives of this study are to use spectra investigation of the fennel EOs was recorded using
GC–MS to determine the chemical composition of fen- attenuated-total-reflection Fourier transform infrared spec-
nel essential oils and to use their electron ionization mass troscopy (ATR-FTIR, Shimadzu IRTracer-100 spectrom-
spectra to elucidate the molecular structure of these con- eter). The IR beam enrolls in the 4000–400 ­cm−1 band and
stituents. Furthermore, DFT and MNDO calculations were has an incidence angle of 30° [59].

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Biomass Conversion and Biorefinery

Fig. 1  Biomass of fennel plants

and their parts used for the
extraction of essential oils

2.4 Antifungal activity of the essential oils 3 Results and discussion

Pure cultures of Alternaria solani MT279570 [60] and 3.1 The chemical constituents of the essential oils
Fusarium oxysporum MW854649 [61] were obtained from by GC–MS analysis
a culture that was grown on potato dextrose agar (PDA) for
1 week. A few drops of Tween-80 (0.01%) were added to The chemical components presented in the EO from the
0.01% dimethyl sulfoxide (DMSO) to dilute the EOs. To leaves of fennel plants are listed in Table 1. The abundant
perform the agar dilution procedure, the EOs were added constituents were anethole (37.94%), estragole (35.56%),
to the agar medium in the various amounts required. From D-limonene (17.46%), trans-β-ocimene (1.53%), and
the cultures that were still actively growing, one 5-mm fenchone (1.49%). Table 2 displays the chemical com-
culture disk of each A. solani and F. oxysporum was taken ponents identified in the EO from the umbels of fennel
and put in the center of the Petri dishes. Next, applying the plants. Estragole (51.18%), anethole (25.08%), D-limonene
method of poisoned food technique [62], a series of two- (12.22%), fenchone (6.57%), and γ-terpinene (2.86%) were
fold dilutions of the EOs ranging from 7.5 to 5000 mg/L the primary components reported for the EO extracted from
were made and compared with the reference fungicide, the umbels of fennel plants. Figure 2 shows the total ion
chlorothalonil (0.2 mg/L). The minimum inhibitory con- chromatogram recorded by GC–MS of the EO composition
centrations (MICs) of the fungal growth were determined of leaves (Fig. 2a) and umbels (Fig. 2b) from fennel plants.
after incubating the Petri dishes at 30 °C for 7 days [63]. Figure 3 displays the chemical structures of the major EO
Only PDA medium and fungus discs were present in the components found in the leaves and umbels of the fennel
controls. The growth reduction (%) of the tested two fungi plants.
was determined using the following formula: The growth
reduction (%) = [(Growth in control − Growth in treat-
ment)/Growth in control] × 100. 3.2 Mass fragmentations of the main compounds

As seen in Fig. 4, the 70-eV mass spectra of the main

2.5 Statistical analysis constituents of the EOs from the leaves and umbels of
fennel plants are recorded and analyzed. The peak of the
A two-way ANOVA analysis of variance (ANOVA) was mass spectrum (MS) in the EOs (Fig. 4a) at retention times
employed to investigate the effects of the two EOs and (RTs) of 10.95 and 10.94 min indicates the anethole com-
their concentrations on the fungal inhibition growth per- ponent, which is explained by its molecular formula of
centages using the STATISTICA program version 8. The ­C 10H 12O. The peak of the molecular ions was noted at
data were presented graphically as mean ± SD values and m/z 148, with relative intensity (RI) = 100% representing
were considered statistically significant when p < 0.05. the base peak, and the peak at 147 (RIn = 70%). Other

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 Biomass Conversion and Biorefinery

Table 1  The chemical Peak R.T.* Compound name Area % Molecu- Molecular formula R.I.**
composition of fennel leaf lar weight
essential oil by GC–MS analysis
1 4.54 β-Pinene 0.24 136 C10H16 979
2 5.29 D-Limonene 17.46 136 C10H16 1030
3 5.41 trans-β-Ocimene 1.53 136 C10H16 1049
4 5.84 γ-Terpinene 0.88 136 C10H16 1060
5 6.21 Fenchone 1.49 152 C10H16O 1096
6 8.83 Estragole 35.56 148 C10H12O 1196
7 9.82 Fenchyl acetate 0.62 196 C12H20O2 1223
8 10.96 Anethole 37.94 148 C10H12O 1286
9 14.59 β-Caryophyllene 0.24 204 C15H24 1419
10 16.01 α-Copaene 0.84 204 C15H24 1432
11 26.44 Estra-1,3,5(10)-trien-17β-ol 0.57 256 C18H24O 2259
12 29.16 Phytol 0.59 296 C20H40O 2114
13 31.53 2,6-Dimethyl-4-[(2,4,6-trimethylphen 0.80 270 C18H22O2 2329
oxy)methyl]-phenol
14 33.68 5-[5'-Ethoxy-bicyclo[4.4.1]u 0.90 305 C17H15N5O 3609
Ndeca-1',3',5',7',9'-pentaenylazo)-
1h-imidazole-4-carbo
Nitrile

*R.T., retention time (min); **R.I., retention index

Table 2  The chemical Peak R.T.* Compound name Area % Molecu- Molecular formula R.I.**
composition of fennel umbels lar
essential oil by GC–MS analysis weight

1 4.54 β-Pinene 0.51 136 C10H16 979

2 5.28 D-Limonene 12.22 136 C10H16 1030
3 5.40 trans-β-Ocimene 0.70 136 C10H16 1049
4 5.84 γ-Terpinene 2.86 136 C10H16 1060
5 6.22 Fenchone 6.57 152 C10H16O 1096
6 8.88 Estragole 51.18 148 C10H12O 1196
7 10.94 Anethole 25.08 148 C10H12O 1286
8 13.62 β-Caryophyllene 0.24 204 C15H24 1419
9 16.01 α-Copaene 0.84 204 C15H24 1432
10 28.83 Phytol 0.32 296 C20H40O 2114
11 31.53 2,4,6-Tris(dimethylaminomethyl)phenol 0.55 270 C18H22O2 2329
12 33.68 5-[5'-Ethoxy-bicyclo[4.4.1]undeca- 0.90 305 C17H15N5O 3609
1',3',5',7',9'-pentaenylazo)-
1h-imidazole-4-carbonitrile

*R.T., retention time (min); **R.I., retention index

significant fragment ions observed were 133 (25%), 121 The MS of the peak at RTs of 5.28 and 5.29 min (Fig. 4c)
(42%), 117 (30%), 105 (25%), 91 (21%), and 77 (19%). represents the D-limonene component ­(C10H16). At m/z 136,
The MS of the peak at RTs of 8.88 and 8.83 min the molecular ion signal was detected with RI = 21%. The
(Fig. 4b) represent the estragol component bringing out base peak was represented by further notable fragment ions,
its chemical formula C­ 10H12O. There was a peak for the which were 121 (32%), 107 (30%), 93 (92%), 79 (48%), and
molecular ions at m/z 148, with RI = 100% showing the 67 (100%).
base peak and a peak at 147 (RI = 68%). Other noteworthy The chemical formula C ­ 10H16O is suggested by the MS
fragment ions observed were 133 (20%), 121 (35%), 117 of the peak at RTs of 6.22 and 6.21 min (Fig. 4d), which
(38%), 105 (22%), 91 (26%), and 77 (25%). represents the fenchone component. The molecular ion peak

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Biomass Conversion and Biorefinery

Fig. 2  Total ion chromatogram of the fennel essential oils from leaves (a) and umbels (b) using GC–MS analysis

was observed at m/z 152 with RI = 15%. Other notable frag- represents the base peak in the MS. This suggests that this
ment ions found were 69 with RI (42%), and 81 (100%) particular molecule is the most stable. The first stage in the
represented the base peak. fragmentation process of the molecular ion of anethole is
the production of the fragment ion at m/z 147 (Fig. 5). The
3.3 Fragmentation pattern of anethole compound loss of ­H• from the molecular ion during the formation of
the [M-H]+• ion could be the cause of this occurrence. The
The molecular ion ­C10H12O+• is obtained from the EI-MS molecular ion fragments via three different pathways, each
of the anethole compound. This ion exhibited a base peak, involving the loss of C
­ H3 to form a different fragment ion:
and a molecular ion peak at m/z 148 with a high RI (100%) [M-CH3]+ at m/z 133, [M-C2H3]+ at m/z 121 due to the

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 Biomass Conversion and Biorefinery

Fig. 3  The chemical structures of the main components with their molecular formula (M.F.) and molecular weight (M.W.) of leaves and umbels
fennel essential oils

loss of ­C2H3•, and [M-CH3O]+ at m/z 117 due to the loss Most of the formatted heats are negative, which reflects
of ­CH3O•, are illustrated in Fig. 5. It is important to note the strong covalent bonds and lower enthalpy that charac-
that the estragole compound is an isomer of the molecule terize stable compounds relative to their elements. How-
anethole and that the MS and primary fragmentation mecha- ever, some stable compounds are found to have positive
nisms of the two compounds are almost the same. heats of formation, e.g., benzene and the condensed ring of
aromatic compounds, making it unwise to generalize from
3.4 Fragmentation pattern of D‑limonene this data alone. The heats of formation therefore permit a
compound precise comparison of the stability of the compounds. The
more negative the heat of formation, the greater the stabil-
The molecular ion of ­C10H16+• is obtained from the EI-MS ity. Therefore, in the present study, fenchone and anethole
of D-limonene. The molecular stability of this compound is compounds have the most negative heat of formation (− 39
demonstrated by the MS, which showed a base peak and a and − 15 kcal/mol) and so they have the highest stability in
molecular ion peak at m/z 136 with RI (31%). The fragmen- comparison with the other studied molecules [65].
tation process of the D-limonene compound was investigated The thermodynamic data calculated by the MNDO semi-
previously in basil EO with another fragmentation shape empirical method show that the major components have low
[64], as shown in Fig. 6. heat of formation (∆F(M) =  − 39 and − 15 kcal/mol for the
fenchone and anethole compounds, respectively), and 9.6
and 1.1 kcal/mol for estragole and limonene, respectively.
3.5 Fragmentation pattern of fenchone compound This indicates that fenchone and anethole have higher sta-
bility than the other two major components reported in the
The EI-MS of the fenchone gives the molecular ion fennel EOs (Table 3).
­C10H16O+•, which exhibits a base peak and a molecular ion
peak at m/z 152 with RI (22%). This indicates that the mol- 3.7 Molecular electrostatic potential (MEP)
ecule has normal stability. The formation of the fragment
ion at m/z 81 is the initial step in the fragmentation route of Figure 9 displays the molecular electrostatic potential (MEP)
the fenchone molecular ion (Fig. 7), where the production of plots of the four compounds studied. Because of the high
the ­[C6H9]+ ion could account for this. Furthermore, it was electron density, the areas of this molecule closest to the
observed that the molecular ion fragments at m/z 69 formed two oxygen atoms that are linked to the phenolic ring are the
the fragment ion ­[C4H5O]+. most electrophilic sites (red regions). The nucleophilic site
of the molecule is shown by the blue patches that are close
3.6 Computational details to the carbon atom.
The molecular charge distribution is not affected by the
The optimized molecular geometry of the main components external test charge. Although MEP is an effective technique for
of the EOs is shown in Fig. 8. locating reactive sites toward positively or negatively charged

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Biomass Conversion and Biorefinery

Fig. 4  The 70 eV mass spectra

of the leaves and umbels fennel
essential oil main components
a anethole, b estragole, c
D-limonene, and d fenchone

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 Biomass Conversion and Biorefinery

Fig. 5  Electron ionization frag-

mentation pattern of anethole
compound

Fig. 6  EI fragmentation pattern

of the D-limonene compound

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Biomass Conversion and Biorefinery

Fig. 7  EI fragmentation pattern

of the fenchone compound

Fig. 8  The numbering and optimized geometry structure of the main components of the fennel essential oils

Table 3  Thermochemical data for the studied four major components reactants, it also enables the establishment of hydrogen bond-
of the fennel essential oils ing and structure–activity relationships in the molecule [66].
Compound ∆F(M) ∆F(M)+ Dipole. M The dipole moment, electronegativity, and partial charges are
kcal/mol kcal/mol D strongly correlated with the electrostatic potential, according to
quantum chemistry calculations [67]. With the help of a visual
Fenchone − 39 177 2.448
representation of the size, shape, charge density, and reactive
Anethole − 15 164 1.111
sites of the molecules on the electrostatic potential energy
Estragole 9.6 179 1.249
surface, MEP offers a means of comprehending the relative
D-Limonene 1.1 208 0.132

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 Biomass Conversion and Biorefinery

Fig. 9  Electrostatic potential (ESP) and three-dimensional MEP surface maps of the studied molecules

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Biomass Conversion and Biorefinery

polarity of a molecule [68, 69]. Therefore, it can be proposed fennel oil, the peaks at 1734, 1609, 1509, and 1454 ­cm−1 corre-
a reaction mechanism wherein the oxygen atoms linked to the spond to the C = O (ketone), C = C, and aromatic ring, respec-
phenolic ring are targeted intramolecularly by a lone pair of tively. The presence of C–O, phenol, alcohol, epoxide, and
electrons, resulting in a ring closure. The process also involves ester as functional groups is indicated by the peaks at 1295,
the transfer of a proton to the negatively charged oxygen atom. 1242, 1176, 1111, and 1034 ­cm−1, respectively. The existence
The red- and yellow-colored regions (negative electro- of C–H and aromatic rings is indicated by the peaks at 996,
static potential) on the MEP surface are associated with 911, 814, 760, 708, 626, and 520 ­cm−1 [67]. All the wavenum-
electrophilic reactivity, while the blue-colored regions bers and transmittances are shown in Tables S1 and S2.
(positive electrostatic potential) of MEP are associated with
nucleophilic reactivity. Looking at Fig. 9, the oxygen atoms 3.9 Antifungal activity of the essential oils
attached to the carboxylic group in anethole, fenchone, and
estragole have a negative electron density and are shown in The antifungal activity of the EOs from the leaves and
red, while the C5, C6, C7, and C9 in D-limonene have a less umbels of fennel plants against the growth of Alternaria
negative electron density and are shown in yellow. solani is shown in Figs. 11 and 12. Fungal growth inhibi-
Actually, the molecular electrostatic potential (MESP) and tions increased with increasing EO concentrations, whereas
the molecular electrostatic potential (MEP) are the same. The entire growth was detected in the control treatment, and full
charge distributions of molecules are shown in three dimen- inhibitions were discovered in the positive control (Fig. 11).
sions by electrostatic potential maps, sometimes referred to as Umbels and leaf EOs at 5000 mg/L showed the highest fungal
molecular electrical potential surfaces or electrostatic potential growth inhibition against A. solani, with values of 87.78 ± 1.92%
energy maps [70, 71]. These maps give us the ability to see and 79.63 ± 0.64%, respectively, compared to the positive con-
a molecule’s variable charge areas. Understanding the dis- trol (94.44%). Additionally, they showed fungal growth inhibi-
tribution of charges allows one to determine the interactions tion values of 68.15 ± 1.69% and 66.67 ± 0.00% at 2500 mg/L,
between molecules. Three-dimensional diagrams of molecules 57.78 ± 1.11% and 56.67 ± 0.00% at 1250 mg/L, 50.74 ± 1.28%
are highly helpful when it comes to electrostatic potential map- and 45.55 ± 1.115% at 600 mg/L, and 50.74 ± 1.28% and
ping. They make it possible for us to see the charge distribu- 45.55 ± 1.115% at 300 mg/L, respectively (Fig. 12).
tions and charge-related characteristics of molecules. They Figures 13 and 14 demonstrate the antifungal activity of the
also enable us to see the dimensions and forms of molecules. EOs from the leaves and umbels of fennel plants against the
Electrostatic potential maps are very useful in organic chem- growth of Fusarium oxysporum. The inhibition of fungal growth
istry for estimating the behavior of complex compounds [72]. increased as the EO concentrations increased, while complete
MEP is the net electrostatic effect generated by the total inhibitions were found in the positive control and complete
charge distribution (electron + nuclei) of a molecule at a growth was observed in the control treatment (Fig. 13).
location in space around it. It connects dipole moments, Umbels and leaf EOs at 5000 mg/L demonstrated the
partial charges, electronegativity, and the molecule’s site of strongest fungal growth inhibition against F. oxysprium, with
chemical action to the overall charge distribution. The colors values of 77.77 ± 3.33% and 72.96 ± 1.28%, respectively, when
red, blue, and green indicate the varied electrostatic potential compared to the positive control (94.44%). Furthermore, they
values on the surface: red denotes the highest negative elec- displayed fungal growth inhibition values of 50.74 ± 1.28% and
trostatic potential, blue is the highest positive electrostatic 44.81 ± 1.28% at 2500 mg/L, 46.67 ± 1.11% and 37.40 ± 2.56%
potential, and green is the lowest potential [39]. at 1250 mg/L, and 37.41 ± 0.64% and 24.44 ± 2.94% at
600 mg/L, respectively (Fig. 14).
3.8 FTIR measurement The minimum inhibitory concentrations (MIC) for the
leaf EOs against A. solani and F. oxysporum growth were
FTIR analysis of the prepared fennel EOs helps to ascertain 15 and 30 mg/L, respectively, and for the umbel EO, they
the possible chemical structure and identify the functional were 7.5 and 7.5 mg/L.
groups of the presented bioactive components [66]. The From the above results, fennel EOs showed the presence
FTIR spectrum between 500 and 4000 ­cm−1 of diverse fen- of some bioactive compounds such as anethole, estragole,
nel EO was recorded, and definite wavenumbers and intensi- D-limonene, and fenchone.
ties were recorded and shown in Fig. 10. Several scientific and biological investigations have
The vibrations of the OH groups, carboxyl/carbonyl C = O, focused on the chemical components of fennel EOs.
C = C, and C–H bending, respectively, can be attributed to the Accordingly, the major components of fennel EO are
peaks at 3400, 2905, and 2836 ­cm−1 in the FTIR spectra of the trans-anethole, estragole, fenchone, and D-limonene
EOs from umbels (Fig. 10a) and leaves (Fig. 10b) of fennel depending on the chemotype [73–75]. According to Telci
plants. This shows that the phenolic, alcoholic, aromatic, and et al. [22], trans-anethole, a phenylpropanoid, made up
aliphatic components are present. In the FTIR spectrum of the majority of the EO at rates of 84.12% and 87.85% in

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 Biomass Conversion and Biorefinery

Fig. 10  The experimental FTIR spectra from umbels (a) and leaves (b) of the fennel essential oil

fruits from main umbels and 81.63% and 86.76% in fruits [76]. Trans-anethole and methyl chavicol are frequently
from subsidiary umbels. In another study, trans-anethole the main ingredients, according to other studies on the
was shown to be the primary EO component in fennel EO compositions of various locations [77, 78], though

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Biomass Conversion and Biorefinery

Fig. 11  The visual observation

of the antifungal activity of the
essential oils against Alternaria
solani

Fig. 12  Antifungal activity of umbels and leaf EOs against Alternaria solani at several concentrations compared to positive control (P. control)

Fig. 13  The visual observation

of the antifungal activity of the
essential oils against Fusarium
oxysporum

there are different chemotypes of fennel EO that also con- 8.7%, respectively) were abundant in the stem and inflo-
tain l-fenchone, α-phellandrene, limonene, and α-pinene rescences. The most common molecule, trans-anethole,
[76, 79]. Additionally, estragole, fenchone, limonene, and was present in all samples in trace amounts (traces,
-pinene were present in the EO from the seeds of plants 5.3%), whereas fenchone, which occurs often, was only
growing in Egypt in percentages of 69.78%, 13.19%, found in modest amounts (3.0%–10.0%) in all samples
12.43%, and 2.44%, respectively, as the major components [3]. The EOs also displayed five chemical groups, includ-
[80]. ing α-phellandrene, methyl chavicol, and trans-anethole;
Significant concentrations of p-cymene (17.5%) and α-pinene, limonene, and trans-anethole; α-phellandrene;
α-pinene (13.4%) were found in the leaf EO, whereas and methyl chavicol and α-pinene [79]. Trans-anethole
limonene (12.9 and 9.5%) and α-phellandrene (14.6 and (36.7%), α-ethyl-p-methoxy-benzyl alcohol, p-anisaldehyde,

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 Biomass Conversion and Biorefinery

Fig. 14  Antifungal activity of EOs from umbels and leaves of fennels against Fusarium oxysporum at several concentrations compared to posi-
tive control (P. control)

carvone, 1-phenyl-penta-2,4-diyne, and fenchyl butanoate vulgare var. vulgare) showed the presence of trans-anethole,
were the primary constituents of the EO extracted from the estragole, fenchone, and limonene as abundant compounds
aerial parts of fennel in Tajikistan [81]. The main ingredi- in all of the examined EOs. The antimicrobial activity was
ents in the EOs recovered from the dried aerial parts of F. comparable across all three cultivars [84]. The EOs of seeds
vulgare growing in Portugal were trans-anethole (31–36%), exhibited significant concentrations of (E)-anethole, methyl-
α-pinene, and limonene, but estragole (79–88%) dominated chavicol, fenchone, and limonene, which had potent anti-
in the fruit EO [11]. Estragole (51.04%), limonene, L-fen- bacterial effects against S. aureus, Listeria monocytogenes,
chone, and trans-anethole were the main ingredients detected P. aeruginosa, Salmonella enteritidis, and E. coli [85]. The
in the essential oil of Egyptian fennel seeds; for Chinese fen- main constituents of the EOs extracted from Moroccan wild
nel seeds, the main components found were trans-anethole and cultivated fennel were discovered to be estragole, anet-
(54.26%), limonene, l-fenchone, and estragole [82]. hole, and fenchone. The cultivated fennel seeds’ EO showed
Seed EO revealed the presence of trans-anethole the highest effectiveness against Salmonella abony, P. aer-
(80.63%), L-fenchone, estragole, and limonene as major uginosa, E. coli, B. cereus, Staphylococcus aureus, and B.
compounds and exhibited potential antibacterial activity subtilis [86].
[13]. Except for Salmonella sp., the EOs from dried aerial Specifically, variations in the chemical makeup of the
parts and fruit have shown very little antimicrobial action EOs, particularly the most prevalent components (estragole,
against Candida albicans, Saccharomyces cerevisiae, Staph- limonene, and fenchone), were the cause of the variations
ylococcus aureus, Listeria monocytogenes, and Bacillus in the antifungal activity of F. vulgare EO [87, 88]. Among
cereus [11]. Trans-anethole, fenchone, and limonene were the constituents of this EO, fenchone has shown a moder-
identified as the main compounds by the EOs from com- ate level of antifungal activity. Penicillium funiculosum and
pletely ripened seeds from Iran, which inhibited the growth Trichoderma viride were more susceptible to the effects
of S. epidermidis, S. aureus, P. aeruginosa, E. coli, and C. of the EO, with a larger percentage of anethol and methyl
albicans [17]. Trans-anethol (69.87%), fenchone, estragole, chavicol (estragole) [87, 89]. The most productive frac-
and limonene were found to be the primary chemicals with tions of F. vulgare EO were especially high in fenchone,
strong action against E. coli, B. subtilis, Aspergillus niger, which may have antifungal properties, and estragole [90].
Fusarium solani, and Rhizopus solani in extract extracted The most efficient EO against gram-positive bacteria was
from Pakistani fennel seeds [18]. one that was high in estragole [84], and both fenchone and
The main compounds found in the EOs extracted from the limonene, which are both contained in the EO, have a posi-
leaves of 12 populations of F. vulgare growing wild in Tuni- tive impact on speeding up the healing, anti-inflammatory,
sia were limonene and methyl chavicol, with the Zaghouan and antimicrobial processes [91]. The effectiveness of fennel
population’s EOs showing the greatest effectiveness against EO rich in estragole would depend on its combination with
Micrococcus luteus and S. aureus [83]. The EOs of three other constituents like limonene, fenchone, and trans-anetole
Egyptian fennel cultivars cultivated organically (Foenicu- [92]. With MIC values of 0.16–0.2–0.25 mg/mL, the EO of
lum vulgare var. azoricum, F. vulgare var. dulce, and F. F. vulgare showed stronger antifungal activity, especially

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Biomass Conversion and Biorefinery

against C. albicans, Aspergillus niger, and A. flavus [93]. Consent for publication Not applicable.
Ocimum basilicum EO, with its estragole (65.9%), showed
Competing interests The authors declare no competing interests.
bioactivity as a natural fungicide to manage diseases caused
by F. oxysporum, R. solani, and A. solani [94].
Open Access This article is licensed under a Creative Commons Attri-
Other studies showed that high concentrations of anethole bution 4.0 International License, which permits use, sharing, adapta-
were reported to be poisonous [95]. The secondary metabo- tion, distribution and reproduction in any medium or format, as long
lites of EOs can freely diffuse through cytoplasmic mem- as you give appropriate credit to the original author(s) and the source,
branes due to their lipophilic characteristics. Cell death via provide a link to the Creative Commons licence, and indicate if changes
were made. The images or other third party material in this article are
apoptosis and necrosis can result from this process, which included in the article’s Creative Commons licence, unless indicated
can also impact membrane fluidity and permeability, trans- otherwise in a credit line to the material. If material is not included in
port, ion balance, and membrane potential [96, 97]. the article’s Creative Commons licence and your intended use is not
permitted by statutory regulation or exceeds the permitted use, you will
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copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
4 Conclusions

The biomass produced from fennel plants (leaves and

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https://​doi.​org/​10.​1016/j.​sajb.​2022.​12.​022

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Biomass Conversion and Biorefinery

Authors and Affiliations

Mamoun S. M. Abd El‑Kareem1 · Mohamed A. Rabbih1 · A. M. Rashad2 · Mervat EL‑Hefny3

1
* Mamoun S. M. Abd El‑Kareem Molecular and Atomic Physics Unit, Experimental Nuclear
[email protected] Physics Department, Nuclear Research Centre, Egyptian
Atomic Energy Authority, Cairo, Inshas, Egypt
* Mervat EL‑Hefny
2
[email protected] Accelerators and Ion Sources Department, Nuclear Research
Centre, Egyptian Atomic Energy Authority, Cairo, Inshas,
Mohamed A. Rabbih
Egypt
[email protected]
3
Department of Floriculture, Ornamental Horticulture
A. M. Rashad
and Garden Design, Faculty of Agriculture (El-Shatby),
[email protected]
Alexandria University, Alexandria 21545, Egypt

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