Variation in the fruit phytochemical and mineral composition, and phenolic content and antioxidant activity of the fruit extracts of different fennel (Foeniculum vulgare L.) genotypes

Industrial Crops & Products 142 (2019) 111852

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Variation in the fruit phytochemical and mineral composition, and phenolic content and antioxidant activity of the fruit extracts of different fennel (Foeniculum vulgare L.) genotypes

T

Gulsum Yaldiz⁎, Mahmut Camlica Department of Field Crops, Faculty of Agriculture and Natural Sciences, Bolu Abant Izzet Baysal University, 14280 Bolu, Turkey

ARTICLE INFO

ABSTRACT

Keywords: Fennel Essential oil and components Total phenolic contents Antioxidant activities Mineral content

Fennel (Foeniculum vulgare L.) is one of the important culinary spice, which is mainly grown in the tropical and temperate regions of worldwide, and has pharmacological properties like anti-inflammatory, antimutagenic, cardiovascular, chemomodulatory, antitumor, memory enhancing property. Present investigation comprised of fortysix genotypes of fennel was undertaken to characterize the genotypes based on chemical variation of fruit like essential and crude oil composition, mineral content, antioxidant and phenolic effectiveness of ethanol extracts. The dendrogram analysis was also conducted to determine the genetic variability based on essential oil components of fennel genotypes. Results of this study revealed significant variations (0.99–8.65%) in essential oil content. Trans-anethole (18.43–69.69%) was found main component, while estragole (methyl chavicol) 0.27–29.55% was second most important component. Maximum trans-anethole was recorded in PI649464 genotype oil, while highest concentration of estragole were reflected by PI414189 genotype. NSL6409 genotype was found superior in case of phenolic amounts and antioxidant activity as compared with other genotypes. Petroselinic and myristic acids were determined as main fatty acids present in a range of 87.07% in genotype PI649466, 48.84% in Denizli genotype, respectively. Overall, in PI649470 and PI601795 genotypes exhibited the highest potassium and magnesium content. According to the dendrogram analysis, fennel genotypes of the same origin were found in different groups regardless of geographical origin.

1. Introduction Fennel (Foeniculum vulgare L.) is important spice plant of Umbelliferae (Apiaceae) family and is cultivated nearly all parts of world (Damjanovic et al., 2005). Its medicinal importance is well known to World and has been used to cure cough, flatulence, dyspepsia, menstrual disorders and to reduce the griping effect of laxatives (Mimica-Dukic et al., 2003). Its essential oils and plant extracts are also used to control stored food mites (Prajapati et al., 2005; Lee et al., 2006). A good level of antioxidant contents in fennel essential oil increase its importance to use as anti heart diseases and anti cancer (Carbonneau et al., 1998; El-Awadi and Esmat, 2010). By accounting its importance, it is important to take fennel as functional food in routine life (Faudale et al., 2008; Ghasemzadeh et al., 2012). Morever, recent studies comes to know that fennel oil biodisel has beneficial role for engine by reducing vibration and noice (Tuccar, 2018). Yield and quality values can change according to genotypes and environmental conditions. For this reason, it has become necessary to develop the most

⁎

appropriate varieties in terms of efficiency and quality against the changing environmental conditions. The new variant for a breeding area is that it will not fall below average yield even in poor environmental conditions, it must have the stability that it will give high yield (Ozgen, 1994). Assessment of genetic diversity of different originating genotypes is main prerequisite breeding purpose of any crop. Although there have been many advances in biotechnology in breeding programme, breeders still use a wide range of their phenotypic performance to select desired characters, such as agronomic and quality properties, pest and disease resistance. The objective of the present investigation comprised of fortysix genotypes of fennel was undertaken to characterize the genotypes based on chemical characters of fruit like essential oil, chemical composition and mineral content. Moreover, in 13 genotype the antioxidant activity of fruit extract and crude oil components was studied containing higher fruit yield and better essential oils contents. While chemical characters of fennel fruit have been evaluated in local fennel genotypes (MimicaDukic et al., 2003; Telci et al., 2009), such studies have not been

Corresponding author. E-mail address: [email protected] (G. Yaldiz).

https://doi.org/10.1016/j.indcrop.2019.111852 Received 9 August 2019; Received in revised form 26 September 2019; Accepted 7 October 2019 0926-6690/ © 2019 Elsevier B.V. All rights reserved.

Industrial Crops & Products 142 (2019) 111852

G. Yaldiz and M. Camlica

conducted together with United States Department of Agriculture (USDA) and local fennel genotypes. So, this study could be accepted as the first extensive report on their chemical composition, mineral content and antioxidant potentials.

2.2. Isolation of essential oil Dried fruits (200 g) were put to water distillation using a clevengertype apparatus with the TS 8882 method during 3 h. Anhydrous sodium sulfate was used to dry isolated essential oils and was kept at 4 °C until further usage. Essential oil yields was estimated following each sample dried weight.

2. Materials and methods This present study was conducted during growing seasons since 2016 at Bolu Abant İzzet Baysal University, Bolu. The field experimental site was located at research and application area of Agriculture and Natural Sciences Faculty, is between 40° 44′ 45″ N latitude, 31° 37′ 46″ E longitudes with altitude of 752 m. 32 fennel genotypes, received from United States Department of Agriculture (USDA) with 14 local fennels (Erzurum, Aydın, Denizli, Kırşehir, Burdur and Antalya) were used in this study (Table 1). Climatic data were noted as 17.10 °C temperature; 71.18 kg/m2 rainfall; 53.27% humidity in the growing season of 2018 (BMGD- Bolu Meteorology General Directorate, 2019). Experimental area soils are clay-loam, 7.8 value of pH, of 4.7% organic matter content, 10.3 mg/kg phosphorus ratio and 235 mg/kg potassium ratio (SFWRCRI-Soil, Fertilizer and Water Resources Central Research Institute, 2018). These genotypes fruits were sown (14 April 2018) with augmented block design having 3 blocks with 25 entries in each block and having plot size of 11.25 m × 5.0 m with spacing of 45 cm. In the experiment, 6 kg/da diammonium phosphate (DAP) as base fertilizer and 4 kg/da ammonium nitrate (AN) as top fertilizer were applied. All recommended agronomic practices were followed timely for successful raising the crop. The fennel fruits reached a stage of maturity between 5 August and 19 September 2018. The first harvest was made in PI174212 genotype, the last harvest was made PI20029 genotype. Ripe greenish-yellow fennel fruits collected and collected fruits were dried in a shaded area for ten days.

2.3. Isolation of fruit crude oil Fennel genotype fruits were grinded as 5 g and they were extracted at 60 °C by Soxhlet extractor during 8 h, using n-hexan as a solvent. After oil extraction the solvent was removed by a rotary evapor (Tuncturk et al., 2011). 2.4. Gas chromatography-mass spectrometry/flame ionization detection (GC–MS/FID) Essential oils were analyzed using a Agilent Technologies 7890A (Santa Clara, CA, USA) coupled with a flame ionization detection detector and mass spectrometry (model 5975C) and HP-Innowax capillary column (60.0 m × 0.25 mm ×0.25 μm). The isolated essential oils were diluted with hexane (dilution ratio 1:50). GC–MS/FID analysis was carried out using a split mode of 50:1. Injector and detector temperatures were adjusted to 1 μL and 250∘C, respectively. Oven temperature gradually raised from 60 °C to 250 °C at 10 °C /min, held for 20 min and then holding at 250 °C for 8 min. Helium (purity 99.9%) was the carrier gas, at a flow rate of 1 mL/min. Mass scanning was from 35 to 450 amu, and the ionizationmode used was electronic impact mode (70 eV). GC-FID peak areas were used for the electronically obtained relative percentage of the components. WILEY, NIST and FLAVOR libraries were utilized to determination of the essential oil components (SITARC-Scientific Industrial and Technological Application and Research Center, 2018).

2.1. Preparation of fennel fruit extracts Extracts for each genotype were prepared to investigate antioxidant activities. For this reason, 25 g fruit samples were taken and their extraction was performed in 300 mL ethanol (80%) incubating in a water bath at 40 °C during 18 h. Than, rotary evaporator was used to evaporate the extracts and was dissolved in 10 ml distilled water before lyophilized. Resulted extracts were kept at −20 °C until further usage.

2.5. Determination of fatty acid composition Fatty acid methyl esters (FAMEs) were carried out to IUPACInternational Union of Pure and Applied Chemistry (1987). Shimadzu GC-2010 gas chromatograph (Shimadzu Corporation, Tokyo, Japan)

Table 1 Information about fennel genotypes used in the study. No

Plant Accession

Origin Country

No

Plant Accession

Origin Country

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

PI414190 Ames7551 PI649463 Ames20029 Ames30290 Ames30289 PI273660 PI358460 PI288285 PI288477 PI649469 PI649470 PI414191 Ames30693 PI172898 PI174212 PI251085 PI414192 PI174213 PI601795 Ames27588 PI649466 NSL6409

United States, Maryland United States, Illinois China, Shanxi Ukraine Tunisia, Stax Tunisia, Stax Ethiopia, Harer Macedonia India, Rajasthan India Syria China, Yunnan United States, Maryland United States, Oregon Turkey, Mardin Turkey, Şanlıurfa Former Serbia and Montenegro United States Turkey, Şanlıurfa United States, California Italy France, Loire-Atlantique United States, California

24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

PI649465 PI649471 PI414189 PI288283 PI273659 PI649460 Ames23130 PI194892 PI649464 Burdur 1 Burdur 2 Burdur 3 Burdur 4 Burdur 5 Burdur 6 Eskişehir Denizli Antalya 1 Antalya 2 Antalya 3 Erzurum Nazilli Bucak

Uzbekistan Morocco Egyp, Cairo India, Uttar Pradesh Ethiopia Italy, Lotium Italy Ethiopia China, Guangxi Turkey, Burdura Turkey, Burdura Turkey, Burdura Turkey, Burdura Turkey, Burdura Turkey, Burdura Turkey, Eskişehirb Turkey, Denizlic Turkey, Antalyad Turkey, Antalyad Turkey, Antalyad Turkey, Erzurume Turkey, Aydınf Turkey, Burdura

a−f

The local fennel genotypes were collected from farmers in different provinces of Turkey. 2

Industrial Crops & Products 142 (2019) 111852

G. Yaldiz and M. Camlica

was used with a flame ionization detector (FID) and Rtx-2330 capillary column (60 m × 0.25 mm) with the thickness of 0.2 μm. The detector temperature were set at 240 °C. GC oven temperature programmed at 140 °C for 5 min for initial time. Then the temperature was increased up to 260 °C at a rate of 4 °C/min and kept constant at 260 °C for 20 min. For the carrier gas helium was used (1 ml/min). The FAMEs were determined by comparing retention times with reference standarts (mixture FAME Mix, SUPELCO, which included 37 FAMEs). Methyl-undecanote (Sigma Aldrich Chemical Co., St. 129 Louis, MO, USA) was used for FAMEs quantity as the internal standard. The obtained total results from FAMEs were revealed as percentages.

Table 2 Operation conditions of the Ion Chromatography. Operation conditions

Obtained Anion

Obtained Cation

Mobile phase

9 mM Na2CO3

Column

Ionpac AS9-HC (250 × 4 mm) Ionpac AG9-HC (50 × 4 mm) ASRS-4 mm 45 mA Conductance detector 2000-3000 30 °C < 30 μS 1.00 mL/min 500 μL 5.0 Hz 30 min

Metansulfonic acid (20 mM) Ionpac CS12-A (250 × 4 mm) Ionpac CG12-A (50 × 4 mm) CSRS-4mm 65 mA Conductance detector 2000-3000 30 °C 0.5–2 μS 1.00 mL/min 1000 μL 5.0 Hz 15 min

Guard column Supressor Supressor current Detector Pressure (psi) Oven temperature Background conductance Flow rate Injection volume Rate of data transfer Duration

2.6. Determination of total phenolic content The total phenolic content was determined with spectrometric method (Spanos and Wrolstad, 1990). 100 μL sample was put in a tube and added 900 μL distilled water. After this, 5 mL 0.2 N Folin-Ciocalteu solution (diluted ten-fold with distilled water) were added to sample together with 4 mL of saturated sodium carbonate solution (75 g/L). All tubes were vortexed fully and stored during 2 h in dark area. The absorbance was measured after 30 min at 765 nm using an ultraviolet (UV)-visible spectrophotometer (model UV-1800; Shimadzu Corp., Kyoto, Japan). The obtained results were noted as gallic acid equivalent (mgGAE/g) by using standard calibration curve of the phenolic compound.

Table 3 The results of the ERM-CA408 simulated rainwater (low contents).

2.7. Determination of antioxidant activity Antioxidant scavenging activity was determined using 2,2-diphenyl1-picrylhydrazyl (DPPH) method as described Lafka et al. (2007). The antioxidant capacity of the extracts at 515 nm were measured with a UV–vis spectrophotometer (model UV-1800; Shimadzu Corp.). Results were calculated as inhibition capacity (IC50). Inhibition values (%) were calculated by using the Equation:

Element

Certified value (mg/L)

Uncertanity

Aritmetic mean (mg/L)

Standard deviation

Error (%)

NH4+ Mg2+ F− Cl− NO3− SO42−

0.91 0.145 0.194 1.96 2.01 1.46

0.028 0.022 0.008 0.07 0.09 0.04

0.789 0.113 0.187 1.94 1.97 1.49

0.0387 0.0122 0.00481 0.0135 0.0211 0.0291

−13.3 −21.7 −3.15 −0.730 −1.70 2.39

by using the least significant difference (LSD) test at P < 0.05 level. Augmented random block design was carried out to determine the differences for antioxidant activity, total phenolic contents and extract yield among the genotypes. Correlation analysis was carried out to determine the relationships between the inorganic matter contents of fennel genotypes. Dendrogram and biplot analysis were carried out using JMP statistical program.

% Inhibition = [(ADPPH - Aextract) ∕ ADPPH)] × 100 ADPPH: Absorbance of the control reaction, Aextract: Absorbance in the presence of tested extracts. ADPPH: Absorbance value of 0.1 mL of methanol +3.9 mL of DPPH solution. Aekstrakt: Absorbance value of samples after 30 min. Reset solution: Pure methanol. The IC50 values were calculated as the concentration of causing 50% inhibition of DPPH radical (Lafka et al., 2007).

3. Results and discussion 3.1. Essential oil and extracts yields yields (g/100 g) The obtained essential oils from different fennel genotypes were found statistically significant difference (P < 0.05), ranged from 0.99% to 8.65% among the fennel genotypes. In present investigation, the maximum essential oil content was recorded with PI601795 (8.65%) and minimum was in PI414192 (0.99%). There was a difference of approximately eight-fold between the highest and the lowest values. Safaei et al. (2011) indicated the fennel essential oils as 1.86–6.4%, and Mata et al. (2007) as 0.1%. The eesential oil content from different origins was found as between 2.27–5.94% (Bernath et al., 1996). Khammassi et al. (2018) reported the essential yield of 16 wild fennel collected from Tunisian as between 1.2–5.06 %. Our essential oil results were similar with these previous studies (Bernath et al., 1996; Mata et al., 2007; Safaei et al., 2011; Khammassi et al., 2018). By contrast, Anwar et al. (2009) noted the essential oil yield of fennel as 2.81% and Mimica-Dukic et al. (2003) as between 2.82–3.38%. The result of the present study (0.99–8.65%) were higher than Anwar et al. (2009) and Mimica-Dukic et al. (2003). Besides plant genetics, the essential oil yields may be varied based on environmental and agronomic practices (Safaei et al., 2011). It was found that the significant differences were seen among the used fennel genotypes in terms of extract yield at p < 0.05 (Table 6). Maximum extract yield was obtained in Ames30289 genotype (33.33%) and the minimum in PI649466 genotype (16.19%). These results of extract yield with

2.8. Determination of element content The element content of fennel genotypes was determined in 5 g of each sample. The measured samples were soaked with 50 mL sterile distilled water, in ultrasonic water bath through 30 min. After, the solids were filtrated via cellulose acetate filter (0.22 μm) and only the liquid passed into the container for ions concentration analysis. To calibration, as a standart dionex anion and cation mixes were used before sample analysis. All chromatographic analyses were performed using a dionex ICS 1100 with 250 mm analytical column with 50 mm guard column. The obtained results were controled by using the ERMCA408 simulated rainwater. Table 2 showed the operation conditions of the instrument and the percent error was given in Table 3. The element contents analysis results were given as a mean of three repetitions of field trial. 2.9. Statistical analysis The statististical analysis were determined by analysis of variance in accordance with augmented trial design. The statistical analysis were carried out in XLSTAT 2016 program (https://www.xlstat.com) to determination of differences between the means of examined properties 3

EOY (%)a

4.09k 4.89g 5.09f 6.09d 4.09k 7.29b 6.09d 2.75q 3.09p 1.75s 2.75q 3.65n 2.59r 2.99p 2.65qr 2.99p 3.65n 3.65n 0.99u 8.65a 6.65c 7.39b 4.73h 4.73h 5.60e 4.73h 1.76s 3.93l 3.26o 3.93l 3.73mn 1.33t 4.33j 4.00kl 4.50ı 4.00kl 3.00p 3.80m 4.00kl 3.00p 4.00kl 3.33o 4.90g 4.60ı 4.33j

Genotypes

PI414190 Ames7551 PI649463 PI20029 Ames30290 Ames30289 PI273660 PI358460 PI288285 PI288477 PI649469 PI649470 PI414191 Ames30693 PI172898 PI174212 PI251085 PI414192 PI174213 PI601795 Ames27588 PI649466 NSL6409 PI649465 PI649471 PI414189 PI288283 PI273659 PI649460 Ames23130 PI194892 PI649464 Burdur 1 Burdur 2 Burdur 3 Burdur 4 Burdur 5 Burdur 6 Eskişehir Denizli Antalya 1 Antalya 2 Antalya 3 Erzurum Nazilli

2.60P 2.05U 4.16G 5.44D 3.82H 4.95E 6.11B 1.74c 1.64f 2.51Q 1.02m 1.08l 1.38j 0.92n 1.69d 1.82Z 1.46h 2.11T 1.80a 6.16A 3.41K 3.17O 4.66F 3.66I 3.3M 3.34L 5.98C 3.19N 0.80o 1.34k 1.97V 0.18q 1.67e 3.17O 2.48R 0.7p 2.45S 0.71p 1.75c 3.60J 1.59g 1.42ı 1.77b 1.95Y 2.46S

α-pinene 0.21L 0.27J 0.29I 0.51E 0.18M 0.48F 0.59C 0.07RS 0.1P 1.06A 0.05TU 0.05TU 0.03VY 0.02Y 0.04UV 0.09PQ 0.03VY 0.14N 0.07RS 0.68B 0.38G 0.53D 0.39G 0.67B 0.32H 0.13NO 0.48F 0.49F 0.02Y 0.17M 0.12O – 0.04UV 0.09PQ 0.08QR 0.02Y 0.08QR 0.03VY 0.06ST 0.13NO 0.04UV 0.06ST 0.13NO 0.05TU 0.25K

Comphene 1.35I 0.64f 1.03T 0.75b 2.18B 1.42H 0.75b 1.22 N 1.07S 0.93Y 0.60g 0.76b 0.96V 0.63f 0.88Z 1.02T 1.08S 0.93Y 1.16P 1.29K 0.82a 1.46G 1.27L 1.63E 1.22 N 2.04C 1.65D 1.35I 0.66e 0.69d 1.56F 0.08ı 1.24M 2.04C 1.64DE 0.46h 1.64DE 0.67e 1.31J 2.32A 1.10R 0.98U 1.12Q 1.24M 1.19O

Sabinene

Table 4 Variation of the essential oil yields and essential oil components of fennel genotypes.

1.23L 1.89G 1.33K 1.47J 2.2E 2.59C 2.61C 0.85PQR 0.87P 1.73H 0.44Y 0.56V 0.61TU 0.34Z 0.66S 0.65ST 0.81R 1.27L 0.85PQR 3.34A 2.27D 2.84B 2.24DE 2.27D 1.55I 1.97F 2.6C 1.97F 0.56V 1.11N 1.12 N 0.05a 0.82QR 1.03O 1.23L 0.3Z 1.18M 0.58UV 0.84PQR 1.72H 0.86PQ 1.1N 1.71H 0.82QR 1.34K

Myrcene 0.34S 0.75JK 0.72L 1.65D 0.76IJ 1.03G 1.29E 0.39R 0.22YZ 0.07d 0.06de 0.14b – – 0.21Z 0.14b 0.23VY 0.32T 0.21Z 1.89C 0.77HI 0.78H 1.08F 0.74K 2.31A 0.59N 1.93B 0.67M – – 0.21Z 0.01f 0.16a 0.21Z 0.28U 0.05e 0.56O 0.16a 0.16a 0.42Q 0.45P 0.24V 0.45P 0.14b 0.42Q

a-phellandrene 11.42h 9.46o 9.27p 9.15q 14.80F 12.34Y 7.43s 10.92k 12.00d 13.16S 10.80l 14.00J 12.13Z 11.60g 13.52P 11.28j 12.02c 13.83L 17.59A 10.61m 12.14Z 12.94U 14.62G 12.04b 8.27r 15.53E 9.59n 12.00d 13.72 N 13.40R 11.96e 2.84t 13.8M 13.43Q 14.13I 11.32ı 12.44V 14.23H 15.80D 13.88K 16.04C 16.07B 12.99T 11.63f 13.63O

Limonene 1.80b 1.84a 2.02Y 2.21R 2.94H 3.79C 1.75c 1.51d 1.38f 1.37f 2.72J 2.19S 1.83a 2.04UV 1.23ı 3.57F 2.64K 2.49M 1.04k 3.75D 2.91I 2.05U 3.39G 3.68E 4.03B 2.30P 3.78C 2.65K 2.05U 1.25h 2.55L 0.11m 1.41e 2.32O 2.03VY 0.52l 4.16A 1.34g 2.15T 2.40N 1.38f 2.32O 2.23Q 1.95Z 2.15T

Cymene 0.99L 0.47cd 0.77R 0.42f 2.09B 0.51b 0.46de 0.95M 0.80Q 1.95C 0.26h 0.62VY 0.79Q 0.58Z 0.54a 0.74S 0.90O 0.86P 0.80Q 0.62VY 0.63V 2.1B 1.05K 1.82E 1.60H 2.86A 1.86D 1.51I 0.65U 0.73S 1.77F 0.10ı 0.62VY 0.93N 1.23J 0.31g 1.24J 0.55a 0.48c 1.64G 0.45e 0.68T 1.06K 0.61Y 0.90O

Eucalyptol

(continued on next page)

1.31Z 2.07N 3.31J 2.00O 2.39M 6.45A 2.93K 1.65T 0.69ı 1.00c 0.59k 3.44H 1.04b 0.77f 0.72h 1.12a 3.50G 2.64L 0.62j 5.91B 3.41I 0.90e 1.91P 5.59C 5.00E 1.50V 5.02D 4.91F 1.41Y 0.94d 1.69S 0.07p 0.39m 0.90e 0.12o 0.31n 1.77Q 0.77f 1.74R 1.01c 0.93d 1.05b 1.57U 0.74g 0.46l

gama-terpinene

G. Yaldiz and M. Camlica

Industrial Crops & Products 142 (2019) 111852

4

EOY (%)a

4.00kl

4,07 0.128 1.58

α-terpinolene

0.21KLM 0.27H 0.20LMN 0.20LMN 0.28H 0.26HI 0.33G 0.17OP 0.14QR 0.23JK 0.07UV 0.14QR 0.18NOP 0.12RS 0.22JKL 0.09TU 0.40F 0.17OP 0.24IJ 0.45E 0.40F 0.39F 0.23JK 0.65B 0.21KLM 0.39F 0.50D 0.32G 0.16PQ 0.17OP 0.21KLM 0.01Y 0.1ST 0.14QR 5.29A 0.06V 0.19MNO 0.11ST 0.16PQ 0.53C 0.07UV

Genotypes

Bucak RT (min)b Average LSD (5%)c CV (%)d

Genotypes

PI414190 Ames7551 PI649463 PI20029 Ames30290 Ames30289 PI273660 PI358460 PI288285 PI288477 PI649469 PI649470 PI414191 Ames30693 PI172898 PI174212 PI251085 PI414192 PI174213 PI601795 Ames27588 PI649466 NSL6409 PI649465 PI649471 PI414189 PI288283 PI273659 PI649460 Ames23130 PI194892 PI649464 Burdur 1 Burdur 2 Burdur 3 Burdur 4 Burdur 5 Burdur 6 Eskişehir Denizli Antalya 1

Table 4 (continued)

9.07R 10.77M 9.48Q 14.23A 7.48a 9.62P 14.06C 5.61f 6.07d 11.80K 5.62f 5.20h 6.60c 3.26q 4.69k 7.73Z 8.53U 10.45N 5.06ı 12.79E 12.32I 14.08B 8.62S 12.91D 12.46H 7.10b 12.06J 12.64F 4.14n 12.49G 8.56T 0.61s 3.57o 4.35m 0.17t 4.54l 5.25g 4.79j 3.40p 5.75e 3.56o

α-fenchone

1.08l 11.29 2.53 0.019 0.38

α-pinene

0.46O 0.93J 0.55N 1.29D 0.33S 0.67M 1.12F 0.22Y 0.19Za 6.45B 0.15b 0.15b 0.30T 0.1cd 0.16b 0.24V 0.39R 0.42P 0.46O 1.20E 0.96I 1.36C 0.79L 1.30D 1.00H 0.26U 1.04G 0.86K 0.11c 0.34S 0.4QR 0.01e 0.11c 0.15b 11.62A 0.15b 0.18a 0.15b 0.11c 0.20Z 0.1cd

Camphor

0.05TU 11.93 0.22 0.019 9.22

Comphene 0.71c 12.73 1.15 0.045 0.55

0.66S 13.03 1.33 0.045 1.74

Myrcene

11.62f 10.31l 8.32t 8.33t 26.24B 10.11m 9.57q 12.71T 11.93e 9.71o 12.46Y 16.54G 13.64O 14.43L 25.28C 12.26a 12.84R 10.46j 13.69N 8.87s 10.76ı 9.65p 10.44k 9.08r 16.51H 29.55A 19.89D 12.01d 16.20I 15.24J 13.54P 12.10c 16.59F 10.81h 0.27u 14.09M 14.77K 13.13Q 12.49V 12.75S 12.14b

Methyl chavicol

Sabinene

0.40QR 0.51N 0.29VY 1.04D 0.48O 0.58K 0.97F 0.22ab 0.30V 0.64HI 0.29VY 0.56L 0.38ST 0.39RS 1.26B 0.41Q 0.27Z 0.43P 0.53M 0.48O 0.43P 1.16C 0.38ST 1.01E 9.39A 0.61J 0.28YZ 1.03D 0.23a 0.38ST 0.63I 0.17c 0.29VY 0.30V 0.1d 0.36U 0.48O 0.63I 0.57 K L 0.84G 0.37TU

Fenchyl acetete

0.09c 13.67 0.51 0.020 2.84

a-phellandrene

1.44L 1.25P 0.92Z 0.90a 0.74c 0.71d 0.81b 1.53J 1.38N 1.17S 1.08T 1.07T 1.64H 1.44L 1.01V 1.25P 1.38N 1.2R 1.00V 0.91Za 1.23Q 1.70F 1.26P 1.39N 2.99A 1.03U 0.75c 1.57I 1.04U 0.81b 1.85D 0.58e 1.52J 1.26P 1.76E 1.67G 1.64H 1.91C 2.08B 1.53J 1.42M

Anethole

12.09a 14.44 12.34 0.016 0.05

Limonene

31.26h 28.79l 25.48p 27.83m 15.56t 26.14o 31.23ı 38.88R 41.12J 26.58n 41.04K 40.26M 42.79G 43.93F 33.63d 41.51H 39.84N 37.28V 40.55L 31.26h 35.80Y 33.26e 37.99T 30.97j 19.44r 18.43s 23.79q 32.37g 44.21D 39.70O 34.93c 69.69A 39.07Q 35.03b 39.70O 48.63B 35.38Z 44.50C 41.29I 32.43f 44.01E

trans-anethol

1.16j 14.65 2.23 0.017 0.34

Cymene

4.99T 3.1h 3.09ı 2.18n 0.53t 2.94l 1.21q 6.18M 4.51Z 0.46u 6.93I 3.19f 5.8O 7.62E 3.58e 7.52F 4.84V 5.65P 3.8b 2.74m 3.72c 3.68d 3.95a 3.68d 1.15r 1.00s 2.07o 3.03k 5.33Q 3.05j 8.94B 1.55p 8.17D 8.61C 7.36G 6.79K 6.91J 7.21H 6.70L 9.29A 3.18g

1.11a 15.38 1.94 0.015 0.63

80.70 75.37 71.23 79.60 83.00 84.59 83.22 84.82 84.41 80.82 84.18 89.95 90.10 88.19 89.32 91.44 91.16 90.65 89.47 92.95 92.36 92.05 94.27 93.09 90.75 88.63 93.27 92.57 91.29 91.81 92.01 88.16 89.57 84.74 89.49 90.28 90.32 91.46 91.09 90.44 87.69

Total

gama-terpinene

(continued on next page)

Anisaldehyde

0.42f 14.93 0.95 0.016 0.77

Eucalyptol

G. Yaldiz and M. Camlica

Industrial Crops & Products 142 (2019) 111852

5

Industrial Crops & Products 142 (2019) 111852

90.44 91.87 69.20 88.83 88.21

ethanol (33.33%) significantly higher than the findings of Oktay et al. (2003) who reported 10.95% yield of fennel fruit extracts with absolute ethanol. Likewise, Conforti et al. (2006) reported cultivated and wild fennel fruit extracts with methanol contained 10.95% and 15.78% extract yields, respectively.

5.06S 5.26R 6.07N 4.96U 4.56Y 23.98 4.61 0.003 0.08

3.2. Chemical composition of the essential oil

39.46P 38.38S 29.46k 35.26a 37.46U 23.64 35.77 0.014 0.01

The chemical composition of essential oils of fortysix fennel genotypes were analyzed by GCeMS, and obtained results were summarized in Table 4. The essential oil components of investigated fennel genotypes were statistically different (P < 0.05). Seventeen components were found, representing 71.23–94.27% of the total oil. Three groups of essential aromatic compounds were detected in the analyzed extracts: oxygenated, hydrocarbons and unknown. All the recorded data were given in Table 4. The pharmaceutical effects of the essential oil are mainly due to its content of oxygenated compounds. The major components of aromatic oxygenated monoterpenes were trans-anethole (15.56–69.69%), aphenylpropanoid, estragole (methyl chavicol) in the group of oxygenated monoterpenes (0.27–29.55%), followed by limonene in the group of hydrocarbons (2.84–17.59%), αfenchone in the group of aromatic hydrocarbons (0.17–14.23%), anisaldehyde (0.46–9.29%) in the group of oxygenated monoterpenes, gama-terpinene in the group of hydrocarbons (0.12–6.45%), α-pinene in the group of hydrocarbons (0.18–6.16%) were obtained in the essential from different fennel genotypes. The percentage components of the remaining 10 compounds varied from 0.01 to 11.62%. Trans-anethole was detected at the highest level (69.69%) in PI649464 genotype oil, but fenchone, limonene, α-pinen, cymene, anethol, and camphor compounds were in lower concentrations (0.6%, 2.84%, 0.18%, 0.11%, 0.58%, 0.01% respectively) in the PI649464 genotype oil than the other genotypes. Based on trans-anethole content (Table 4), PI649464 originating from China is the best genotype, which is the different from the other genotypes. So, this genotype is suitable for production of transanethole used in food, cosmetic, and liqueurs industries, also has economical value for grower (Telci et al., 2009). The PI414189 genotype contained the highest concentration (29.55%) of methyl chavicol compared with other genotypes but anisaldehyde (1%) was in lower concentrations in this oil than in the other genotypes except Ames30290 (Table 4). Fenchone was higher concentration in PI20029 genotype than the other genotypes while the Burdur 3 genotype gave the lowest α-fenchone (0.17%) and the PI649464 gave the lowest content (0.61%). For quality fennel essential oil, fennel essential oil should content less than 10% methyl chavicol or 7.5% fenchone (Bilia et al., 2002). Therefore, the amount of methyl chavicol and fenchone in Burdur, Erzurum genotpe’s have low concentration estragol and fenchone content, which also had desired limits for estragole and fenchone in this study. Fenchyl-acetete, cymene and anethole were higher concentrations (9.39%, 4.16%, 2.99% respectively) in PI649471 genotype oil than the other genotypes while trans-anethole was the lowest in this genotype’s oil. The pharmaceutical effects of the essential oil are mainly due to its content of oxygenated compounds (Osman and El-Wahab, 2009). Acoording to our study, the USDA genotypes were higher in its content of oxygenated compounds in compare with the local genotypes. The minor components of the fennel oil were α-pinene, α-phellandrene, sabinene, camphor, α-terpinenole, fenchyl acetate, comphene, myrcene, cymene, eucalyptol and gama-terpinene. The minor constituents in the fennel essential oil from our experiments were similar to other studies (Barazani et al., 1999; Kruger and Hammer, 1999; Bernath et al., 1996). The results of the present study were closely related to earlier studies results reported by Viuda-Martos et al. (2010) who determined the major components of Egyptian fennel as trans-anethole (65.59%), estragole (13.11%), limonene (8.54%) and fenchone (7.76%). Similarly, Telci et al. (2009) reported that trans-anethole (84.12%), estragole

a

A−u

Any means in the same column followed by different letters are significantly (p < 0.05) different by Least Significant Difference test. Essential Oil Yield. b Retention Time. c Least Significant Difference. d Coefficient of Variation.

1.41M 1.46K 0.98Y 1.33O 1.00V 22.36 1.30 0.016 0.41 0.49O 0.65H 0.21b 0.60J 0.30V 21.75 0.70 0.013 1.16 11.56g 12.64U 9.95n 12.34Z 19.20E 20.71 13.20 0.019 0.06 0.22Y 0.41PQ 0.09d 0.42P 0.26U 19.93 0.83 0.013 0.51 0.19MNO 0.27H 0.17OP 0.18NOP 0.14R 16.34 0.34 0.020 1.45 Antalya 2 Antalya 3 Erzurum Nazilli Bucak RT (min)b Average LSD (5%)c CV (%)d

8.13V 9.77O 3.14r 10.94L 7.94Y 17.8 7.86 0.016 0.11

α-terpinolene Genotypes

Table 4 (continued)

α-fenchone

Camphor

Methyl chavicol

Fenchyl acetete

Anethole

trans-anethol

Anisaldehyde

Total

G. Yaldiz and M. Camlica

6

7

a

Retention Time.

Crude oil (%) Petroselinic acid (C18:1 n12) Capric acid-(C10:0) Lauric acid-(C12:0) Myristic acid-(C14:0) cis-10-pentadecanoic acid-(C15:1) Palmitic acid-(C16:0) Palmitoleic acid-(C16:1) Heptadecanoic acid(C17:0) cis-10-heptadecanoic acid-(C17:1) Stearic acid-(C18:0) Elaidic acid-(C18:1n9t) Oleic acid-(C18:1n9c) Linoleic acid(C18:2n6c) Arachidic acid-(C20:0) gama-linolenic acid(C18:3n6) Linolenic acid(C18:3n6) Heneicosanoic acid(C21:0) cis-4.7.10.13.16.19docosahexaenoic acid-(C22:6n3)DHA Total (%) 0.22

94.58

2.76 – –

1.29

– 3.23 – 3.87

– –

–

4.7

–

97.58

17.32 18.25 19.26

20.18

21.01 21.93 21.97 23.49

24.49 25.14

26.58

26.84

34.59

–

–

0.28 0.19

0.91 20.13 1.95 4.78

–

1.72 – –

3.08 24.48 6.53 –

– – 3.82 –

7.61 9.74 13.51 16.3

1.88 30.32

Ames30290 (%)

1.38 77.9

Ames7551 (%)

4.71

RTa (min)

92.31

0.44

0.21

–

0.21 0.19

0.68 10.35 1.24 3.60

–

1.50 – 1.44

1.38 3.68 36.44 –

1.44 30.95

Ames30289 (%)

Table 5 Variation of the crude oil and fatty acid components of 13 fennel genotypes.

99.53

–

–

–

– 1.85

5.59 11.38 4.58 7.62

–

9.53 – –

– – – –

1.00 58.99

PI414191 (%)

98.82

–

7.36

–

– –

– 1.21 – 2.38

–

– – 1.98

– – – –

0.82 87.07

PI649466 (%)

94.82

–

–

–

0.51 –

0.89 17.62 – 3.37

–

1.49 – –

1.42 0.77 24.96 –

1.22 43.8

NSL6409 (%)

94.34

–

–

–

– 4.61

2.63 – 2.92 –

–

– 0.86 0.97

– – – 1.41

1.32 80.95

PI649465 (%)

99.44

–

–

–

– 2.05

12.75 3.56 6.55 –

8.05

– – –

– – – 5.16

0.76 61.32

PI414189 (%)

95.48

0.24

0.23

–

0.20 0.20

0.99 28.31 2.83 7.38

–

2.59 – 0.40

0.64 0.48 17.31 –

1.76 33.68

PI273659 (%)

99.64

–

–

–

– 2.01

9.07 3.97 6.72 –

9.44

– – –

– – – 4.95

0.62 63.49

Burdur 5 (%)

98.61

1.6

–

3.56

– –

7.81 11.95 – 6.96

–

5.65 – –

– – – –

1.16 61.09

Burdur 1 (%)

89.13

0.39

–

–

– –

0.38 7.18 – 1.55

–

0.59 – 1.71

1.24 3.44 48.84 –

2.36 23.84

Denizli (%)

99.8

1.29

4.65

–

1.48 2.03

6.65 11.56 4.18 9.53

1.27

5.99 – –

– – 2.15 –

1.94 49.03

Erzurum (%)

G. Yaldiz and M. Camlica

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G. Yaldiz and M. Camlica

component in PI649466 genotype, followed by 80.95% in PI649465 genotype. Amount of petroselinic acid observed in the genotypes originating from Uzbekistan, France, United States were more than those in other fennel origins. These genotypes were also characterized by a low content of elaidic acid and absence of lauric acid. Considerable amount of myristic acid (C14:0) was also identified in all the genotypes ranged from 2.15% in Erzurum genotype to 48.84% in Denizli genotype. Significant quantity of elaidic acid (C18:1 n9t) was found all genotypes ranged from 1.21% in PI649466 to 28.31% in PI273659. In present study in fatty acid composition was observed significant genetic variation. Other fatty acids such as cis-10-heptadecanoic acid was detected only in Burdur (9.44%), PI414189 (8.05%), Ames7551 (1.29%) and Erzurum (1.27%) genotypes. Oleic acid was found as 1.24–6.72% in all genotypes. The highest value was obtained in Burdur and PI414189 (6.55%), and the lowest Ames30289 (1.24%) and Ames30290 (1.95%). Similarly, linoleic acid ranged from 2.38 to 9.53%. The highest value was obtained in Erzurum genotype, followed by PI414191 (7.62%) and PI273659 (7.38%), and the lowest was obtained PI649466. Also, linolenic acid was detected only in Burdur genotype (3.56%). Fatty acids and phytosterols obtained from fennel oil have industrial utilization (Barros et al., 2010; Moser et al., 2014). According to previous studies, Bettaieb Rebey et al. (2016) reported that petroselinic acid was the major compound (75.43%) followed by linoleic (8.04%) and oleic acids (7.56%). Similarly, petroselinic acid was found between 70–80% (Reiter et al., 1998). Najdoska-Bogdanov et al. (2015) reported that the major fatty acid as petroselinic and oleic acid (75.0–82.8%), linoleic acid (10.8–16.2%), palmitic (4.3–6.9%), stearic (1.2–1.7%) and myristic acid (0–2.9%). Our results is compatible with the other researchers results.

Table 6 Variation of the total phenolic contents, antioxidant activities and extract yield of 13 fennel genotypes. Genotypes

Total phenols (mgGAE/g)

Antioxidant activity (IC50) (g/gDPPH)

Yield (%)a

Ames30289 Ames30290 Ames7551 NSL6409 PI273659 PI414189 PI414191 PI649465 PI649466 Burdur1 Burdur5 Denizli Erzurum Average LSD (5%)b CV (%)c

27.78d 22.31g 24.13e 40.48a 33.00b 16.85ı 17.32h 32.56c 22.79f 16.60ıj 16.56j 14.82l 15.33k 23.07 0.27 0.69

4.99j 6.92g 5.44ı 3.27m 3.90k 9.91b 8.32f 3.83l 6.73h 9.93a 8.92e 9.61c 9.02d 6.98 0.008 0.068

33.33a 21.11g 25.78c 20.90h 19.61l 23.91d 22.90e 19.68k 16.19m 20.20j 20.47ı 21.59f 27.05b 22.52 0.08 0.02

a−m

Any means in the same column followed by different letters are significantly (p < 0.05) different by Least Significant Difference test. a weight of extract(g) / 20 g of powdered plant sample × 100. b Least Significant Difference. c Coefficient of Variation.

(4.19–5.53%), limonene (2.96–4.69%) and fenchone (1.17–2.65%) of sweet fennel cultivated in Turkey. Furthermore, Mimica-Dukic et al. (2003) indicated the major components of Foeniculum vulgare Mill. as trans-anethole (74.18%), fenchone (11.32%), estragole (5.29%), limonene (2.53%) and α-pinene (2.77%). However, Napoli Edoardo et al. (2010) indicated that in wild Sicilian fennel the main constituents were determined as estragole and fenchone. Cavaleiro et al. (1993) also, reported that the major components of different populations in central Portugal were fenchone (6.8–30.8%), methyl chavicol (2.6–36.3%) and (E)-anethole (44.2–74.0%). These differences can be dependent on climatical, seasonal, geographical conditions of the regions (DiazMaroto et al., 2006), different genotypes, harvest time and extraction methods (Telci et al., 2009).

3.4. Antioxidant activity Antioxidants reduce the risk for chronic diseases including cancer and heart disease. Primary sources of naturally occurring antioxidants are whole fruits, grains and vegetables (Vinson et al.,1998). Table 6 showed the antioxidant content of fennel fruit extract. The values of antioxidant activities varied between 3.27 and 9.93 g/gDPPH. NSL6409 genotype originating from United States had the highest antioxidant activity (3.27 g/gDPPH) followed, respectively, by PI649464 (3.831 g/ gDPPH), PI273659 (3.90 g/gDPPH) and Ames30289 (4.99 g/gDPPH) (P < 0.05). Burdur I genotype had the lowest DPPH radical scavenging activity. Among the 13 genotype that were compared, excluding the PI414189 and PI414191, all genotypes exhibited significantly higher DPPH scavenging activity compared with the local genotypes (Table 6). Based on data obtained from this study, especially USDA genotypes showed high antioxidant properties that may protect body cells against damage caused by oxidative stress (Scalbert et al., 2005). As reported by Ahmed et al. (2019) Egyptian fennel seed extract included higher radical scavenging activity (6.34 mg/g) than Chinese fennel seed extract (IC50 = 7.17 mg/g). Anwar et al. (2009) found that Pakistan

3.3. Total crude oil and its composition Crude oil content and fatty acid compositions of the fruits of 13 different fennel genotypes were detected and the results are shown in Table 5. The crude oil content ranged from 0.62% to 2.36%. In present investigation, the maximum crude oil content was recorded with Denizli genotype and minimum was in Burdur genotype. There was a difference of approximately 4-fold between the highest and the lowest values. In fennel fruit oil, 18 fatty acids have been determined and given in Table 5. Petroselinic acid (87.07%) was found as the major Table 7 Correlation analysis of fennel genotypes (mg/g).

Cl− PO43− SO42− Na+ NH4+ K+ Mg2+ Ca2+

Cl−

PO43−

SO42−

Na+

NH4+

K+

Mg2+

Ca2+

1

0.423** 1

0.394** 0.775** 1

0.292* 0.397** 0.381** 1

0.062 0.217 0.188 0.133 1

0.228 0.247 0.098 0.607** 0.228 1

0.106 0.297* 0.213 0.232 0.716** 0.417** 1

0.017 0.22 0.286 −0.068 0.511** 0.009 0.755** 1

* P < 0.05. ** P < 0.01.

8

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G. Yaldiz and M. Camlica

Table 8 Variation of the mineral content of fennel genotypes (mg/g).

LODa LOQb R2 Linearity PI414190 Ames7551 PI649463 PI20029 Ames30290 Ames30289 PI273660 PI358460 PI288285 PI288477 PI649469 PI649470 PI414191 Ames30693 PI172898 PI174212 PI251085 PI414192 PI174213 PI601795 Ames27588 PI649466 NSL6409 PI649465 PI649471 PI414189 PI288283 PI273659 PI649460 Ames23130 PI194892 PI649464 Burdur 3 Burdur 2 Burdur 1 Antalya 3 Burdur 4 Burdur 6 Burdur 5 Antalya 2 Antalya 1 Bucak Erzurum Eskişehir Denizli Nazilli Average LSD (5%)b CV (%)d

Cl−

PO43−

SO42−

Na+

NH4+

K+

Mg2+

Ca2+

0.00643 0.02145 0.9928 0.1-20 0.88J 0.78L 0.49Y 0.09u 1.46D 0.34g 0.92H 1.17F 0.19r 0.17s 0.39c 0.38e 0.28n 0.57T 0.59R 0.66O 0.80K 0.24o 0.02v 0.45Z 0.32ı 0.23p 0.74N 0.44a 0.75M 1.40E 0.44b 0.17t 0.62Q 0.65P 0.38d 0.29l 0.51V 9.19A 2.52C 0.37f 0.29m 0.34h 0.57S 1.10G 0.89I 0.51U 4.38B 0.30j 0.22q 0.30k 0.84 0.0002 0.0040

0.02052 0.06841 0.9955 0.2-40 18.79J 34.77D 12.44R 2.60t 25.98E 10.71a 22.04G 21.5H 3.32s 4.45r 19.50I 8.96e 7.72j 8.28h 6.31l 11.23Z 13.19P 8.37g 2.13u 10.06c 11.34V 7.18k 22.57F 11.8T 36.51C 12.98Q 6.09n 4.97q 12.40S 11.69U 10.21b 9.3d 14.25O 18.73K 17.93L 7.84ı 5.79p 5.92o 11.29Y 15.56N 39.63B 17.91M 56.58A 9.31d 6.13m 8.48f 14.02 0.007 0.016

0.03031 0.10103 0.9981 0.1-20 8.38S 9.95K 8.22T 2.16t 19.41C 7.67U 33.83B 7.29Z 1.23u 2.68q 15.19E 7.34Y 3.09n 2.90p 2.30s 5.33e 8.81P 5.81b 0.35v 10.42J 10.99I 5.52d 8.47R 5.01h 11.91H 6.30a 3.30m 2.98o 8.90O 15.51D 5.58c 4.38ı 12.17G 9.57M 9.60L 5.12g 3.75l 4.36j 8.79Q 9.23N 13.34F 7.63V 52.12A 5.26f 2.37r 3.80k 8.66 0.0014 0.00528

0.25664 0.85545 0.9999 0.4-30 0.68R 0.38m 0.81G 0.11s 0.52f 0.43k 0.81H 0.68Q 0.56c 0.43k 0.59a 0.55d 0.76M 0.67S 0.66T 0.62V 0.60Y 0.24r 0.07t 0.50g 0.31p 0.63U 0.30q 0.43l 0.50h 0.56b 0.37n 0.45ı 0.79J 0.44j 0.77L 0.54e 0.85D 0.80I 0.69P 0.60Z 1.26B 0.77K 0.71O 0.83E 1.32A 0.66T 1.20C 0.36o 0.75N 0.82F 0.62 0.0010 0.04472

0.03309 0.1103 0.998 0.4-30 0.16V 0.17U 0.24J 0.03k 0.03j 0.20Q 0.17T 0.18S 0.10e 0.07f 0.19R 0.32C

0.64089 213.629 0.9999 1-75 33.75G 29.29S 37.43C 3.53u 29.10U 23.80k 22.48p 32.82J 28.55Y 23.38m 31.93M 22.98o 30.25P 35.47E 40.23B 34.48F 29.75R 23.62l 2.45v 21.29r 24.15ı 23.09n 20.62t 29.24T 23.97j 40.60A 25.26h 20.91s 32.93I 21.40q 28.44b 26.57g 30.19Q 32.45K 28.96V 28.49a 28.52Z 27.41e 28.02c 31.11N 33.53H 27.81d 32.13L 27.09f 31.00O 36.03D 27.75 0.019 0.025

0.31395 104.649 0.9999 0.5-37.5 3.90D-J 5.16ABC 5.37AB 0.61R 2.17OPQ 3.84D-J 3.92D-J 2.93J-P 2.37M-Q 2.04PQ 2.64K-P 5.38A 3.41F-M 2.63K-P 3.00J-P 2.59L-P 3.12J-O 4.56A-E 0.57R 4.40A-G 4.75A-D 2.61K-P 3.76D-J 3.68E-K 3.44F-M 5.2ABC 2.12OPQ 2.60L-P 2.92J-P 4.3B-H 3.34G-M 1.31QR 3.56E-L 3.51E-L 3.48F-L 3.40F-M 3.30H-N 2.27N-Q 2.60K-P 4.43A-F 4.21C-I 3.63E-L 3.31H-N 3.18I-O 4.30B-H 3.14I-O 3.32 1.074 12.05

0.65647 218.822 0.9999 1-75 8.00N 12.14F 11.25G 1.64r 6.38V 6.29Z 14.86C 5.22f 4.50k 6.50U 3.37o 16.78A 6.53T 4.66ı 5.42e 3.90m 5.71d 9.26K 1.00s 15.75B 9.29J 8.24M 10.83I 7.95O 11.21H 12.25E 7.00R 8.72L 4.58j 14.58D 7.17P 1.85q 6.37Y 6.21a 6.63S 4.06l 4.95g 2.72p 3.90m 7.06Q 6.07b 5.97c 6.49U 3.85n 6.49U 4.91h 7.14 0.01 0.073

0.23L 0.01m 0.03ı 0.23N 0.35B 0.45A 0.05h 0.24J 0.25H 0.26G 0.23K 0.32D 0.21O 0.16a 0.23M 0.13d 0.13b 0.07g 0.02l 0.30F 0.31E 0.16Y 0.13c 0.16Z 0.21P 0.25I 0.18 0.0001 2.6E-02

a

Limit of Detection. Limit of Quantification. c Least Significant Difference. d Coefficient of Variation. A−v Any means in the same column followed by different letters are significantly (p < 0.05) different by Least Significant Difference test. b

fennel seed extract had good scavenging activity (IC50 = 23.61 μg/ mL). Conforti et al. (2006) reported the IC50 values for methanol extracts of wild and cultivated fennel seeds from Italy was determined as 31 and 83 μg/mL, respectively. Mata et al. (2007) also reported the IC50 values for ethanol extracts from Portugal had higher than the synthetic antioxidant. Variability of antioxidant activitiy between these finding and previous studies can be explained by extraction conditions and methods, different genotypes, ecological conditions, cultivation techniques (Bozin et al., 2006).

3.5. Total phenolic contents The phenolic compounds from natural sources possess antioxidant activity which can be neutralizing for the reactive oxygen species associated diseases (Tlili et al., 2013). Total phenolic contents of fennel genotype extracts are reported in Table 6. The total phenolic content changed between 14.82–40.48 mgGAE/g for fruit extracts. NSL6409 genotype originating from United States had the highest total phenolic values, which was significantly higher than the other genotypes (p < 0.05). Also, the PI273659, PI649465 and Ames30289 genotypes contained the highest 9

Industrial Crops & Products 142 (2019) 111852

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concentration (33 mgGAE/g, 32.56 mgGAE/g, 27.78 mgGAE/g respectively) of total phenolics compared with other genotypes. The lowest values were recorded for Denizli genotype, followed by the Erzurum (15.33 mgGAE/g), Burdur 5 (16.56 mgGAE/g) and Burdur 1 (16.60 mgGAE/g) genotypes (Table 6). The results for total phenolic content indicated that the local genotypes contained lower phenolics than USDA genotypes. Ahmed et al. (2019) indicated the Egyptian fennel seeds contained higher content of total phenolic content with value (42.24 mg PE/g) than Chinese fennel seed extract (30.94 mg PE/ g). Mata et al. (2007) found the total phenolic content in ethanol extract of Portugal fennel seed as 63.1 mg/g (pyrogallol equivalents). Agarwal et al. (2018) reported that total phenolic content in methanolic extract of Hisar Swarup genotype as 6.18 mg GAE/gm, AF101 genotype contained 6.04 mg GAE/gm. Anwar et al. (2009) reported that ethanol extract (80%) of the fennel seed extracts included good values of total phenolic contents (627.21–967.50 GAE, mg/100 g). Many researchers reported that plant extracts have positive correlation between total phenolic content and antioxidant activity (Ahmed et al., 2019; Tlili et al., 2013). The observed differences in the concentrations of total phenolic across countries may be a result of different environmental, genetic factors and harvest time.

fennel fruits while the least sulfate amount occurred PI174213 genotype. The highest PO43− and SO42- amounts were found in the Erzurum genotype originating from Turkey. Potassium (K+) concentrations of fennel fruit varried between 2.45–40.60 mg/g. PI414189 and PI172898 genotypes had the highest K+ amounts and these genotypes were significantly higher than other genotypes. K is responsible for many biological process such as action of muscles, nerve impulse transmission, and arrangement osmotic pressure (Yaldiz et al., 2019). So, especially PI414189 and PI172898 genotypes are important for the quality of fennel fruit. The concentration of magnesium (Mg2+) changed between 0.57–5.38 mg/g. PI649470 genotype had the highest value and PI174213 genotype had the lowest value (Table 8). Mg concentrations of the fruits were significantly different among the all different genotypes. Calcium (Ca2+) concentration of fennel fruits varied between 1.00 and 16.78 mg/g. The highest Ca amounts were obtained in PI649470, and followed by PI601795 (15.75 mg/g), PI273660 (14.86 mg/g), which were significantly different from other genotypes. The least Ca amount was found in the PI174213 genotype (Fig. 1). The highest Ca and Mg amounts were found in the PI649470 genotype originating from China. In addition, there was a high correlation between Ca and Mg concentrations in the fruit of all genotypes (Table 7). Ca and Mg are involved in the regulation and dilation of blood vessels and a regular heartbeat (Agarwal et al., 2011), so this genotype is important for the quality of fennel fruit. Comparison of the means of different genotypes on the content of the element in the fennel fruits had a significant difference among the genotypes according to the Chloride (Cl−) content. The highest chloride amount was observed in Burdur 2 (9.19 mg/g) genotype, followed by Erzurum (4.38 mg/g) and Burdur 1 (2.52 mg/g) genotypes, the least chloride amount was observed in PI174213 (0.02 mg/g), PI20029 (0.09 mg/g) genotypes. The highest concentration level of Na (1.32 mg/ g) was found in Antalya genotype, followed by Burdur 4 (1.26 mg/g) and Erzurum (1.20 mg/g), which are originated from local genotypes, while PI174213 (0.07 mg/g) have the lowest Na content. Furthermore, Cl, SO4, Na levels were found the higher in local genotypes than USDA genotypes. NH4+ concentration was higher Ames27588 (0.45 mg/g) and PI601795 (0.35 mg/g) than other genotypes. The lowest NH4 level was found in PI174212 (0.01 mg/g) originating from Turkey. Ca was found as 23.90 μg/g (Kumar et al., 2007), 10.80 μg/g (Basgel and Erdemoglu, 2006), 6.75 μg/g (Ozcan and Akbulut, 2007), and Mg was found as 5.11 μg/g (Kumar et al., 2007) in India, 2.77 μg/g (Basgel and

3.6. Nutrient composition of different fennel genotypes Correlations analysis (Table 7) showed that the highest positive correlation coefficient was found between PO43− and SO42− (r = 0.775). It was also seen that other highest positive correlations were observed between Mg2+-Ca2+ (r = 0.755), NH4+-Mg2+ (r = 0.716), K+-Na+ (r = 0.607), NH4+-Ca2+ (r = 0.511), CI−-PO43− (r = 0.423), CI−-SO42- (r = 0.394), K+-Mg2+ (r = 0.417), PO43−-Na+ (r = 0.397), and SO42--Na+ (r = 0.381). CI- was correlated with Na+ (r = 0.292) and PO43− was correlated with Mg2+ (r = 0.297) as positively. There was not found any important negative correlation among the inorganic matters of fennel genotypes. Table 8 shows that element content of fennel fruits were significantly changed among the all genotypes (P < 0.05). The concentration of phosphorus (PO43−) ranged from 2.13 to 56.58 mg/g. The highest PO43− content was found from Erzurum genotype and followed by Antalya 1 and PI649471 genotypes compared with other genotypes. The lowest PO43− value was determined from PI174213 and PI20029 genotypes (Table 8). Sulfate (SO42-) concentrations of fennel fruit varried between 0.35–52.12 mg/g. The highest SO42- amount was obtained from the Erzurum genotype and followed by PI273660 genotype in the

Fig. 1. Inorganic matters of 46 fennel genotypes. 10

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Fig. 2. Biplot analysis of 46 fennel genotypes based on 17 essential oil components.

Erdemoglu, 2006) in Turkey, 3.40 μg/g (Ozcan and Akbulut, 2007) in Turkey. Ozcan et al. (2008) determined that Ca, K, Mg and P concentrations in F. vulgare L., in Taiwan was found as 5118.2, 10145.48, 2432.6 and 10145.48 mg/kg, respectively. Ullah et al. (2012) reported that, a relatively high concentration of Ca (70 mg/kg) was found in F. vulgare and followed by Mg 34 mg/kg, Cl 23.1 mg/kg, SO4 21.4 mg/kg. The mineral contents of different fennel genotypes were slightly different when compared with previously reported (Endalamaw and Chandravanshi, 2015; Ullah et al., 2012). These differences may be

occurred under different growth conditions, cultural applications or genetic factors (Guil et al., 1998; Ozcan and Akgül, 1998). 3.7. Biplot and PCA analysis of some fennel genotypes Biplot analysis has an important statistical program using plant breeding and agricultural research. Biplot analysis represented 52.22% of the total trait variation between the fennel genotypes (Fig. 2). The biplot proved that the distribution of the genotypes in essential oil

Fig. 3. PCAbiplot analysis of 13 fennel genotypes based on 18 fatty oil components. 11

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Fig. 4. Dendrogram of 46 fennel genotypes with essential oil components using Euclidean coefficient and WARD methods.

components based biplot was focused on four groups (Fig. 2). Group 1 included the 16 genotypes. The genotypes of the first group were widely distributed on the positive sides of the F1. Group 2 had only two genotypes as Denizli and Burdur 5. These genotypes were closely grouped on the positive side of the F1. Group 3 included only one genotype (Burdur3) and distrubuted on the negative side of F1. Group 4 included most of the genotypes and most of them distrubuted negative side of the F1 and F2. The 12 vectors of the essential oil components were located on the positive side of the PC1 and five vector located negative area. The biplot analysis showed no particular pattern of grouping according to the geographical origins of the genotypes, and were divided into different groups based on origins. The PCAbiplot analysis was conducted to comparision of 13 fennel genotypes with regard to fatty acid

compositions. This analysis explained PC1 with 73.97% and PC2 with 14.54%. Totaly, it showed 88.51% based on fatty acid components of 13 fennel genotypes and 5 genotypes located in positive side of PC1 and 8 genotypes took part in negative side of PC1. For this reason, the PCA analysis also showed that major fatty acid compositions (petroselinic acid) of the fennel genotypes distrubuted on the negative side of the PC2. Local fennel genoytpes (Erzurum, Denizli, Burdur 1 and Burdur 5) located in different part of the PCAbiplot analysis (Fig. 3). 3.8. Dendrogram analysis based on the essential oil components The dendrogram analysis of the 46 fennel genotypes based on the UPGMA method and using the 17 essential oil components led to 12

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grouping the genotypes into two main group (A and B) and 18 cluster (C) with a Euclidean distance (Fig. 4). Group I (A) included the two main subgroup (A1 and A2). A1 had only one genotype (PI649471) and one cluster. A2 had 15 genotypes with eight clusters. Group II (B), was composed of 14 local genotypes and 16 genotypes of belonging to the fennel genotypes regardless of geographical origin for local genotypes. The Group II divided to 2 sub-group (B1 and B2). B1 sub-group had only one genotype as Burdur3 with one cluster. The sub-group B2, as the most hight-populated genotypes and cluster, contained 13 local genotypes and 16 different genotypes with 8 cluster. Therefore, unlike the group A, the group B responded significantly to geographical distribution. All local fennel genotypes took part in B group. The first group (Group A including A1 and A2) was characterized by trans-anethole, anisaldehyde, α-pinene, α-phelladrane and myrecene. The first group was characterized by USDA genotypes. The second group (Group B including B1 and B2) was formed by α-phelladrane, anethole and comphane. All local fennel genotypes were found in this group. Only Burdur 3 genotype was found in group B1 beacuse of including the lowest gama-terpinene, α-fenchone, methyl-chavicol, and fenchylacetate and having the highest camphor, and α-terpinolene. PI649464 had the highest trans-anethole content and had the lowest essential oil components except methyl-chavicol and anisaldehyde. So, this genotype was found in group B2 and it was found only C11. α-phelladrane, fenchyl-acetete, and anethole components were found as the highest in PI 649471 and this genotype was seen alone in Group A (sub-group A1) and in C1. The dendrogram analysis was formed depending on αphelladrane to divide two main groups (Fig. 4). Compared with dendrogram and biplot analysis, only Burdur 3 genotype was seen in group B1 cluster 10 in dendrogram and it was also seen in group 3 in biplot analysis. Denizli and Burdur 5 was seen in cluster 12 and group 3 in biplot analysis. PI194892 and Burdur 2 was found the same place with Denizli and Burdur 5 in dendrogram analysis. This situation can be explained depending on their similar αphelladrane values of these genotypes (Table 4). The obtained results from dendrogram, local genotypes took place same group, but same origin genotypes took part in different group. Camlica and Yaldiz (2019) reported that the same origin genotypes may take place in different groups depending on the adaptation conditions of them.

Acknowledgments This study was financially supported by Grant No: 2018.10.07.1349 of the Scientific Research Project Fund, Faculty of Agriculture and Natural Sciences, Bolu Abant Izzet Baysal University, Turkey. The authors would like to thank to the The United States Department of Agriculture (USDA) for supplying fennel genotypes. References Agarwal, A., Khanna, P., Baidya, D.K., Arora, M.K., 2011. Trace elements in critical illness. J. Endocrinol. Met. 1, 57–63. Agarwal, D., Saxena, S.N., SharmaL, K., Lal, G., 2018. Prevalence of essential and fatty oil constituents in fennel (Foeniculum vulgare Mill) genotypes grown in Semi Arid Regions of India. J. Essent. Oil Bear. Pl. 21 (1), 40–51. Ahmed, A.F., Shi, M., Liu, C., Kang, W.Y., 2019. Comparative analysis of antioxidant activities of essential oils and extracts of fennel (Foeniculum vulgare Mill.) seeds from Egypt and China. Food Sci. Hum. Wellness. 8, 67–72. Anwar, F., Ali, M., Hussain, A.I., Shahid, M., 2009. 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4. Conclusion Significant differences were found among the fennel genotypes from different origins based on the chemical characters of fruit like essential and crude oil composition, mineral content, antioxidant and phenolic effectiveness of ethanol extracts. The USDA genotypes were higher in its content of antioxidant activities in compare to the local genotypes. The fennel fruit extract from NSL6409 genotype showed higher content of total phenolic contents and exhibited good DPPH radical scavenging activity than other genotypes. Moreover, the highest essential and crude oil components were obtained from USDA genotypes compare to the local genotypes. Trans-anethole was detected at the highest level in PI649464 genotype oil. Petroselinic acid was the major fatty acids found in genotype PI649466 and genotype PI649465. In PI649470 and PI601795 genotypes contained higher concentrations of Ca, K and Mg. This study supported the utilizition of fennel as tea or functional food, and traditional treatments for antioxidants and/or nutraceuticals. Dendrogram analysis showed differences among the fennel genotypes in terms of essential oil components. PI649471 genotype was found different among the fennel genoytpes based on essential oil compositions. The local fennel genotypes were found in the same group but in different cluster. It also put forth that same origin genotypes were found in the different groups. The results of the present research are also promising that the genetic variation found among different genotypes of fennel supports the idea of domestication and improvement of this crop for sustainable crop production systems. 13

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