Discrimination of Pulp Oil and Kernel Oil from Pequi (Caryocar

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Discrimination of pulp oil and kernel oil from Pequi (Caryocar brasiliense) by fatty acid methyl esters fingerprinting, using GC-FID and multivariate analysis Adelia F. Faria-Machado, Alba Tres, Saskia M. van Ruth, Rosemar Antoniassi, Nilton T. V. Junqueira, Paulo Sergio N. Lopes, and Humberto Ribeiro Bizzo J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.5b03699 • Publication Date (Web): 27 Oct 2015 Downloaded from http://pubs.acs.org on October 31, 2015

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Journal of Agricultural and Food Chemistry

Discrimination of pulp oil and kernel oil from Pequi (Caryocar brasiliense) by fatty acid methyl esters fingerprinting, using GC-FID and multivariate analysis

Adelia F. Faria-Machadoa*, Alba Tresb,1, Saskia M. van Ruthb,c, Rosemar Antoniassia, Nilton T. V. Junqueirad, Paulo Sergio N. Lopese, Humberto R. Bizzoa

a

Embrapa Food Technology, Av. das Américas 29501, Rio de Janeiro, RJ, 23020-470,

Brazil b

RIKILT, Wageningen University and Research Centre, PO 230, 6700 AE

Wageningen, The Netherlands c

Wageningen University, Food Quality and Design Group, PO Box 17, 6700AA

Wageningen, The Netherlands d

e

Embrapa Cerrados, BR 020, km 18, Planaltina, Brasília, DF, 73310-970, Brazil Instituto de Ciências Agrárias, Universidade Federal de Minas Gerais, Av.

Universitária 1000, Montes Claros, MG, 39404-006, Brazil

* Corresponding author. Tel.: +55 21 36229606; Fax: +55 21 36229713; e-mail: [email protected]

1

Current address: Nutrition and Food Science Department – XaRTA – INSA, Universitat de Barcelona, Av. Joan XXIII s/n, E-08028, Barcelona, Spain 1

ACS Paragon Plus Environment


1

Abstract

2

Pequi is an oleaginous fruit whose edible oil is composed mainly by saturated

3

and monounsaturated fatty acids. The biological and nutritional properties of pequi oil

4

are dependent on its composition, which can change according to the oil source (pulp or

5

kernel). There are few data in the scientific literature concerning the differences

6

between the compositions of pequi kernel and pulp oils. Therefore, in this study

7

different pequi genotypes were evaluated to determine the fatty acid composition of

8

pulp and kernel oils. PCA and PLS-DA was applied to develop a model to distinguish

9

these oils. For all evaluated genotypes the major fatty acids of both pulp and kernel oils

10

were oleic and palmitic acids. Despite the apparent similarity between the analyzed

11

samples, it was possible to discriminate pulp and kernel oils by means of their fatty acid

12

composition using chemometrics, as well as the unique pequi genotype without

13

endocarp spines (CPAC-PQ-SE-06).

14 15

Keywords: pequi oil, fatty acid composition, GC-FID, chemometrics, PCA, PLS-DA,

16

Caryocar brasiliense

17

2


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Introduction

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Caryocar brasiliense Camb. (Caryocaraceae), popularly known as pequi, piqui,

20

or piquiá,1 is an oil-rich fruit widely distributed in the Brazilian Cerrado region, which

21

is commonly used for gastronomic and nutritional purposes, as well as for cosmetic

22

applications and in traditional medicine to treat cold, edema, bronchitis, cough and

23

burns.2 Pequi is a spherical green fruit, presenting 1-4 segments. Its structure is

24

composed by an epicarp (very thin peel), an external pulpy mesocarp (non-edible), an

25

internal mesocarp (light-yellow, pulpy, rich in oil), that involves a layer of thin and rigid

26

endocarp (approximately 2-5 mm large) with spines and a white kernel (also called seed

27

or nut) (see Figure 1S, Supporting Information).1,3,4

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The pulp of pequi has a good quantity of edible oil (36-66 % dry matter),

29

vitamin A and proteins. The nut (or kernel) has also oil, which is applied in cosmetic

30

products such as soaps and skin emulsions. The pequi oil has a high content of lipid-

31

soluble vitamins and saturated and monounsaturated fatty acids.5-10

32

It has been reported that pequi oil presents some biological properties such as

33

wound healing and anti-inflammatory activities, antimicrobial activity, protection

34

against genomic and oxidative damage, among others.11-16 These biological properties,

35

as well as the nutritional and health benefits associated to the pequi oil, are closely

36

related to the oil composition, which can change according to the matrix (pulp or

37

kernel) used as raw material7, and also due to genetic factors, such as genotype or

38

cultivar17, among other factors. Therefore, it is important to evaluate different genotypes

39

when assessing pulp and kernel oils aiming distinguish them based on their

40

composition.

41

Furthermore, it is important to note that each part of the fruit (pulp and kernel) is

42

used for different purposes in the traditional medicine,2,18 which was established 3



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according to the popular knowledge since most studies found in the scientific literature

44

did not compare the biological effects of pulp and kernel oils from pequi. As mentioned

45

before, this difference is probably associated to the different composition of pulp and

46

kernel oils from pequi, reinforcing the importance of distinguishing each oil type.

47

The differentiation of fats and oils based on their composition normally requires

48

a wide physicochemical characterization which can comprise, for instance,

49

determination of fatty acid composition, sterols profile, tocopherols and tocotrienols,

50

refractive index, relative density, among other analyses. Depending on the oil source, it

51

can also be necessary to evaluate carotenoids and/or phenolic compounds.19 On the

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other hand, the application of multivariate analysis enables to distinguish fats and oils

53

using composition data from one or two of these analyses, as performed in previous

54

studies,20,21 reducing time and financial resources spent with chemical analyses.

55

Considering the above, the objective of this study was to determine the fatty acid

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composition of pulp and kernel oils from different pequi genotypes, as well as to

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discriminate pulp oil and kernel oil by chemometric data analysis. As far as we are

58

aware, this is the first time that pulp and kernel oils of several genotypes of Caryocar

59

brasiliense are analyzed for their fatty acid composition, and using chemometrics to

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differentiate them. Based on the scientific literature, there is only one report on the

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differences between the composition of pequi kernel and pulp, where only one genotype

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was assessed, evaluating oil content, fatty acid composition, and the contents of

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phenolic compounds and carotenoids.7

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Regarding the effect on nutritional parameters of consuming either pequi pulp or

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kernel, Aguilar et al.22 reported that both the pequi pulp- and pequi nut-rich diet

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promoted a significant increase in the HDL-cholesterol levels in mice bloodstream,

67

without changing significantly the LDL-cholesterol levels. This effect was attributed to 4


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the higher lipid intake associated to the pequi diets as compared to the standard diet,

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considering the favorable fatty acid composition presented by pequi which is rich in

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monounsaturated fatty acids.22

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Differences between nut (or kernel) and pulp compositions of some other

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oleaginous fruits have been reported, especially regarding to the lipid compounds such

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as fatty acids, triacylglycerols, phytosterols, and tocopherols.23-27 The relative

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percentage of fatty acids, for instance, were different according to the analyzed matrix

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(nut or pulp) for mucajá, buriti, guarirova, and olive.24,25,27 A similar pattern was

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observed for triacylglicerols of olive pulp and kernel oils.27 Phytosterols and

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tocopherols showed different composition in nut or pulp oils from mucajá, buriti and

78

jenipapo.23

79 80

Materials and Methods

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Materials

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Fruits of 16 different conventional pequi genotypes with hard spines originated

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from the inner wall of the endocarp were collected in the Brazilian Cerrado Region

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(Minas Gerais and Goias States) and one genotype without spines (CPAC-PQ-SE-06)

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was obtained from Embrapa Cerrados (Brazil). For each genotype about five samples

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were collected from the same plant. The whole fruits were immediately frozen and sent

87

to the Laboratory of Fats and Oils, at Embrapa Food Technology (Brazil), in order to

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determine the fatty acid composition.

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The fatty acid methyl esters (FAME) standards (purity ≥ 98 %) were purchased

90

from Nu-chek Prep Inc (Elysian, MN). The dichloromethane used for chromatographic

91

analysis was chromatographic grade, and all other reagents were analytical grade.

92 5



93

Oil extraction

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The fruits of each genotype were cut and each part (external mesocarp with the

95

epicarp, internal mesocarp, endocarp and kernel) was separated. The internal mesocarp

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was lyophilized and the kernel was dried in an air-circulating oven at 60 °C.

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Afterwards, the oil of each one of these materials was extracted for 16 hours in Soxhlet

98

apparatus using petroleum ether (30-60 °C) as solvent. The pulp and kernel samples

99

were analyzed with at least two and three repetitions, respectively.

100 101

Chromatographic analysis

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The methyl esters of fatty acids were prepared according to Hartman & Lago28

103

in triplicate from each sample and injected once into the chromatograph. Gas

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chromatography was performed in an Agilent 6890 equipment (Agilent Technologies,

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Santa Clara, CA) fitted with a cianopropylsiloxane capillary column (60 m x 0.32 mm x

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0.25 µm, Quadrex, Woodbridge, CT). Initial column temperature was set to 100 °C and

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held for 3 min, increased to 150 °C at 50 °C/min, further increased to 180 °C at 1

108

°C/min and finally increased to 200 °C at 25 °C/min and held for 10 minutes. Carrier

109

gas used was hydrogen, at 1.4 mL/min (measured at 100 °C). Injection of 1.0 µL of a

110

2% dichloromethane solution of the sample was done into an injector operating at

111

250°C and split mode (1:50). FID detector was kept at 280 °C. Results were expressed

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as weight percent (area normalization). Identification of FAME was based on

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comparison of retention times with those of Nu-chek standards 62, 79 and 87.

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The analysis of fatty acid composition from vegetable and animal fats and oils

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by GC-FID is accredited to ISO/IEC 17025 by the Brazilian National Institute of

116

Metrology, Quality and Technology – INMETRO – since 2007 (accreditation number 6


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CRL 0228). This analysis is regularly evaluated for accuracy with certified reference

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material from NIST (National Institute of Standards and Technology, USA) and BCR

119

(Community Bureau of Reference, Belgium), and the laboratory takes part in

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Proficiency Testing Schemes of FAPAS (Food Analysis Performance Assessment

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Scheme) since 2005.

122 123

Statistical analysis

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Data were analyzed by chemometrics, considering a total of 16 fatty acids (the

125

fatty acids which were not detected in one of the oil types – pulp or kernel – were

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excluded from the statistical analysis). When “tr” values were reported, they were

127

substituted by “0” (zero). Before all modeling, the fatty acid composition data was

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normalized to 100 %. Data matrix consisted on 119 rows (as many rows as samples)

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and 16 columns (variables, fatty acids). First, Principal Component Analysis (PCA) was

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conducted on the fatty acid data of both pulp and kernel oils to detect natural clustering

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of the samples and the presence of outliers. Secondly, Partial Least-Squares

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Discriminant Analysis (PLS-DA) was conducted on the fatty acid data in order to

133

develop a model to classify oil into one of the two categories: pulp or kernel. In the

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model development, 70 % of the samples were used to develop the model and to

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internally validate it by leave 10%-out cross-validation. The lowest Root Mean Squared

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Error of Cross Validation (RMSEcv) was used as a criterion to select the number of

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PLS components in each PLS-DA model. The model was then used to predict the

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identity of the remaining 30% of samples in order to externally validate it. 20,29

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On the other hand, PCA was also conducted on the pulp oil samples only, and a

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PLS-DA model was developed to discriminate between different genotypes of pulp oil 7



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samples. In this case, the PLS-DA model was validated internally by leave 10%-out

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cross-validation.

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The performance of the PLS-DA models was assessed by its accuracy (i.e.,

144

correctly predicted samples divided by the number of samples in the class, as a

145

percentage) in predicting each class correctly. Several data pre-processing techniques

146

were assayed (auto-scaling, log transformations, mean centering) both for PCA and

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PLS-DA models. Software used was Pirouette v 4.5 (Infometrix Inc, Bothell, WA).

148 149

Results and Discussion

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Oil content and fatty acid composition

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The oil content for the evaluated pequi genotypes ranged from 41.6 to 78.5 %

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(dry matter) and from 34.4 to 48.5 % (dry matter) for pulp and kernel, respectively.

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These results are in agreement with those reported for fruits from Caryocar brasiliense

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species, which were 36-66 % and 56 % for oil contents of pulp and kernel,

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respectively.6-8,10

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The fatty acid ranges of pequi pulp and kernel oils found for the evaluated

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genotypes are shown in Table 1. Representative chromatograms for each class of

158

samples and chromatograms of Nu-chek standards (62, 79 and 87) are shown,

159

respectively, in Figures 2S and 3S of Supporting Information. The data for CPAC-PQ-

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SE-06 were separated from the other genotypes because as it will be discussed below

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this genotype presented a different fatty acid composition, as shown by the multivariate

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analysis carried out for discrimination. According to the data in Table 1, both pulp and

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kernel oils contained oleic (C18:1) and palmitic (C16:0) as major fatty acids, with little

164

quantities of stearic acid (C18:0) and also linoleic acid (C18:2) for kernel oil. The

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ranges of C18:1 and C16:0 were, respectively, 48.6-65.9 % and 24.3-46.3 % for pulp oil 8


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and 51.5-60.1 % and 28.1-38.7 % for kernel oil. These results are in agreement those

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reported by other authors for fatty acid composition of pequi pulp and kernel oils.

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Aquino et al.30 found 52.9-54.8 % of oleic acid and 39.6-41.6 % of palmitic acid

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in pequi pulp oil obtained by different extraction solvents. For three different pequi

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samples obtained in the local market of Brasília city (Brazil), Lopes et al.8 reported

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51.6-53.5 % of oleic acid and 39.0-40.2 % of palmitic acid in pulp oil.

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Lima et al.7 compared the fatty acid composition of pequi pulp and kernel oils,

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reporting that both oils showed higher proportion of unsaturated fatty acids (61.4% and

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52.2 % for pulp and kernel oils, respectively) as compared to saturated ones. According

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to these authors, oleic acid was the main fatty acid (55.9 %), followed by palmitic acid

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(35.2 %) in the pulp oil, whereas the kernel oil presented almost the same amount of

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these two fatty acids (43.6 % of oleic acid and 43.8 % of palmitic acid).

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The comparison between the compositions of pulp and kernel from pequi and

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from other oleaginous fruits which have a white oil-rich kernel surrounded by a pulp

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also rich in oil, namely macauba (Acrocomia aculeate) and palm (Elaeis guineensis),

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shows that all these three fruits present oil contents in the same range and high

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quantities of oleic and palmitic acids in the pulp oil.31,32 On the other hand, the fatty

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acid composition of kernel oils are quite different, since palm and macauba kernel oils

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are characterized as lauric oils (the major fatty acids are lauric, C12:0, and myristic,

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C14:0),31,32 while the pequi kernel oil contained oleic and palmitic acids as major fatty

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acids as previously commented.

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Despite the fact that the fatty acid composition of pequi pulp and kernel oils

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analyzed in this study seem to be very similar, it was possible to distinguish them by

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multivariate analysis considering the whole fatty acid composition, as discussed in the

190

next section. 9



191 192

Multivariate analysis

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Pulp oil versus kernel oil

194

Considering the natural variability among genotypes, the ranges of major fatty

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acids showed overlap for some values when comparing pulp and kernel oils. This

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characteristic hampers an accurate classification of unknown pequi oil as being from

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pulp or kernel by looking at the fatty acids one by one. Therefore, using the data of all

198

fatty acids at once a fingerprinting approach was followed to develop a model to

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discriminate these two oil sources. Before building the model, Principal Component

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Analysis (PCA) was conducted on the fatty acid data (after data auto-scaling) from pulp

201

and kernel oil simultaneously, in order to visualize this (highly dimensional) data, to

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detect outliers and to reveal any natural clustering present in the data. Two outlier

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samples (that were kernel oil samples) were detected. They showed C16:0 contents that

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were much higher than the rest of kernel oil samples. Since this could not be attributed

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to any biological reason, they were excluded from further analysis to avoid that they

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would have a high influence on model development. Nevertheless, future work to be

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conducted with respect to pequi oil should bear in mind these particular kernel samples

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in case more samples with this pattern are found because this would be indicative of a

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possible biological reason underlying this pattern. As it can be seen in Figure 1, pulp

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and kernel oils showed consistent differences in fatty acid profiles, resulting in two

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groups of samples, i.e. the pulp oil and the kernel oil samples.

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Since PCA revealed a tendency of samples to cluster according to the pulp or

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kernel source of oil, PLS-DA was conducted on the fatty acid data in order to develop a

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model to classify the oil into one of the two categories: pulp or kernel oil. The PLS-DA

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model on the auto-scaled data achieved very successful results. By an internal 10


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validation, it was able to correctly identify all pulp oil samples (100 % of correct

217

classifications), and 97 % of the kernel oil samples (only one sample did not match the

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kernel category). The model was externally validated by using it to predict the identity

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(pulp or kernel) of the oil samples left in the validation set. All samples (100 %) were

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correctly identified for both pulp and kernel oil.

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Some fatty acids were more important than others for the pulp and kernel oils

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discrimination (Figure 2). A high contribution of linolenic (C18:3) and eicosenoic

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(C20:1) acids for the pulp oil class was evidenced, together with a slight contribution of

224

other monounsaturated fatty acids such as palmitoleic (C16:1) and heptadecenoic

225

(C17:1) acids. On the other hand, linoleic (C18:2) and myristic (C14:0) acids were

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highly contributing to differentiate the kernel oil class.

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It is expected that pequi pulp or kernel oils show different properties when

228

included in the diet,33 since the biological properties and the nutritional and health

229

benefits associated to pequi oil are dependent on the oil composition, which can be

230

different according to the matrix (pulp or kernel) used for the oil extraction.7 Therefore,

231

the differentiation between pulp and kernel oil classes is the first step to be

232

accomplished depending on the intended use for the oil. In a normal way, one should

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make several characterization analyses in order to verify the oil matrix. However,

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according to the results obtained in this study, it is possible to distinguish pequi pulp oil

235

from the pequi kernel oil based only on the fatty acid composition by using the model

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developed with PLS-DA. It should be mentioned that fatty acid composition is one of

237

the most common analyses among those used for oil characterization due to the features

238

of the method (reliability, repeatability, accuracy).

239

According to Tres and van Ruth21 one advantage of fingerprinting classification

240

methods is that they might be updated in the future by including in the model new 11



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authentic samples. When this is performed, more natural variability on oil composition

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can be included in the model, and therefore, the model can be updated if necessary.21

243 244

Genotype (pulp oils only)

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Apart from the clustering of pulp and kernel oils, PCA revealed that pulp oils

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coming from a specific genotype clustered separated from the other pulp oil samples

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(Figure 1). To further explore this fact, PCA was conducted again but only on the pulp

248

oil samples (Figure 3) and it confirmed the separation of this group of samples which

249

corresponded to one genotype (CPAC-PQ-SE-06). This indicates that pulp oil obtained

250

from this pequi genotype is different from pulp oils obtained from other genotypes.

251 252

Classification model: SE pulp oil vs non-SE pulp oil

253

A PLS-DA model (data normalized to 100%, auto-scaled and cross validated by

254

leave 1-out cross validation) was first calculated to classify samples into 16 different

255

genotypes. All samples belonging to the CPAC-PQ-SE-06 were correctly classified, but

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only three samples of other genotypes were correctly assigned to their class. This was

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expected because in PCA clustering had also been observed for samples of the CPAC-

258

PQ-SE-06 genotype. Therefore, a PLS-DA model was built to discriminate between

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CPAC-PQ-SE-06 (SE) pulp oils and pulp oils from the other genotypes (non-SE pulp

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oils). The model was internally validated by leave 10%-out cross-validation (due to the

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low number of samples in the SE class, external validation was not conducted). All SE

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pulp oil samples (100 %) were correctly classified as being SE oils, whereas 97 % of

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samples from other genotypes were correctly classified as well.

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These results are in agreement with the fact that CPAC-PQ-SE-06 genotype

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presented the highest contents of oleic (C18:1) and linoleic (C18:2) acids (average 12


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values 65.9 % and 5.6 %, respectively) and the lowest content (24.3 %, average value)

267

of palmitic acid (C16:0) as compared to other genotypes (Table 1). According to these

268

features, this genotype may be more appropriate for nutritional purposes than other

269

ones. Therefore, a model able to differentiate the pulp oil of this genotype based just on

270

its fatty acid composition is useful to classify unknown pequi pulp oils as from SE or

271

non-SE genotype.

272

In addition, there is another characteristic that distinguishes CPAC-PQ-SE-06

273

genotype from the other ones. SE is the unique genotype whose endocarp does not have

274

spines, which facilitates the separation of the fruit pulp (internal mesocarp) and makes it

275

favorable for consumption of in natura fruits or in gastronomic preparations.

276

In conclusion, both pulp and kernel oils presented oleic (C18:1) and palmitic

277

(C16:0) acids as major fatty acids, with little quantities of stearic acid (C18:0) and in

278

addition for kernel oil, linoleic acid (C18:2). Although the fatty acid composition of the

279

pulp and kernel oils analyzed in this study were similar, it was possible to discriminate

280

both pequi oils by means of their fatty acid composition combined with chemometrics.

281

A PLS-DA model has been built and validated with this purpose, reaching a high

282

success rate. Furthermore, within pulp oil samples, those obtained from the CPAC-PQ-

283

SE-06 genotype, which does not have spines in the endocarp, were clustered separately

284

from all other pulp oils. Due to the low number of samples, these results could be

285

considered a proof of concept study for the discrimination of pequi oil types. This is an

286

important accomplishment, since pulp and kernel oils have different nutritional

287

properties. In addition, the PLS-DA model enabled to discriminate them based only on

288

their fatty acid composition, while without this statistical approach, one must perform

289

complementary chemical analysis (such as composition of sterols, carotenoids, and

290

tocopherols) to properly characterize each type of oil. 13



291 292

Abbreviations

293

FAME: Fatty Acid Methyl Esters

294

PCA: Principal Component Analysis

295

PLS-DA: Partial Least-Squares Discriminant Analysis

296 297

Supporting Information. Figures 1S, 2S and 3S illustrating, respectively, parts of the

298

pequi fruit, representative chromatograms of each class of sample and chromatogram of

299

Nu-chek standards 62, 79 and 87. This material is available free of charge via the

300

Internet at http://pubs.acs.org.

301 302

References

303

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Organization of The United Nations (FAO): Rome, Italy, 1995; 198pp.

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Wickens, G.E. Non-wood Forest Products 5: Edible Nuts. Food and Agriculture

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Ascari, J.; Takahashi, J.A.; Boaventura, M.A.D. Phytochemical and biological

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investigations of Caryocar brasiliense Camb. Bol. Latinoam. Caribe Plant. Med.

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Damiani, C.; Vilas-Boas, E.V.B.; Ferri, P.H.; Pinto, D.M.; Rodrigues, L.J. Volatile

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compounds profile of fresh-cut peki fruit stored under different temperatures. Cienc.

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hyperlipidemic properties. Braz. J. Med. Biol. Res. 2012, 45, 601-609.

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M.A. Influence of Pequi drying (Caryocar brasiliense Camb.) on the quality of the

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oil extracted. Cienc. Tecnol. Aliment. 2009, 29, 354-357.

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Lopes, R.M.; Silva, J.P. da; Vieira, R.F.; Silva, D.B. da; Gomes, I.S.; Agostini-

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Costa, T.S. Composition of fatty acids in pulp of native fruits from the Brazilian

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savanna. Rev. Bras. Frutic. 2012, 34, 635-640.

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Roesler, R.; Catharino, R.R.; Malta, L.G.; Eberlin, M.N.; Pastore, G. Antioxidant

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mixtures. Grasas Aceites 2011, 62, 245-252.

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The authors acknowledge FINEP (Financiadora de Estudos Projetos) and CNPq

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(Conselho Nacional de Desenvolvimento Científico e Tecnológico) for financial

409

support.

410 411

Figure captions

412

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413

Figure 1. PCA scores plot on the fatty acid data (normalized to 100 % and auto-scaled,

414

n = 117). Variance explained: 46 %. Brown, pulp oil; red, kernel oil. Pulp oil samples

415

within the circle correspond to the CPAC-PQ-SE-06 genotype).

416

Figure 2. First two factors of PLS-DA scores (left) and loadings (right) plots of the

417

model built on the fatty acid data of pulp (brown) and kernel (red) oil (training set, n =

418

81).

419

Figure 3. PCA scores plot on the pulp oil samples (n = 73). Colors indicate different

420

genotypes (CPAC-PQ-SE-06 genotype, red). Variance explained: 54 %.

421

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Table 1. Fatty acid ranges (%) of pulp and kernel oils from different pequi genotypes. Pulp Oil Fatty Acid

Kernel Oil a

a

CPAC-PQ-SE-06

Other genotypes

CPAC-PQ-SE-06

Other genotypes

(n = 11)

(n = 62)

(n = 2)

(n = 44)

b

C8:0

nd

0.02 – 0.10

nd – 0.02

nd – 0.14

C10:0

nd

nd – 0.02

nd

nd – 0.04

C12:0

0.03 – 0.06

tr – 0.06

nd – 0.13

nd – 0.18

C14:0

0.16 – 0.29

0.03 – 0.16

0.29 – 0.32

0.22 – 0.52

C15:0

nd

nd

0.04 – 0.07

nd – 0.06

C16:0

23.12 – 24.84

32.52 – 46.28

34.06 – 36.94

28.06 – 38.68

C16:1t

nd – 0.08

nd – 0.12

nd

nd – 0.05

C16:1

0.59 – 0.69

0.54 – 1.26

0.35 – 0.65

0.39 – 0.84

C17:0

0.05 – 0.06

tr – 0.14

0.09 – 0.12

0.08 – 0.10

C17:1

0.06 – 0.07

nd – 0.12

nd

nd – 0.06

C18:0

1.75 – 2.12

1.40 – 3.54

1.50 – 1.68

2.07 – 3.53

C18:1t

nd

nd

nd

nd – 0.55

C18:1

64.66 – 67.59

48.60 – 62.20

49.15 – 53.88

51.46 – 60.13

C18:2

4.97 – 6.02

0.58 – 2.24

8.87 – 10.45

3.88 – 7.26

C18:3

0.47 – 0.58

tr – 0.49

0.14 – 0.18

nd – 0.24

C20:0

0.21 – 0.26

0.14 – 0.30

0.11 – 0.12

0.19 – 0.35

C20:1

0.18 – 0.25

tr – 0.27

tr

nd – 0.14

C22:0

nd

tr

tr

nd – 0.11

C24:0

0.11 – 0.17

nd – 0.11

nd – 0.09

0.07 – 0.18

a

c

“Other genotypes” column presents the ranges of fatty acids obtained for the other 16

genotypes evaluated in this study, but genotype CPAC-PQ-SE-06; traces

20


b

nd: not detected;

c

tr:

Page 21 of 28


Figure 1.

21



Figure 2.

22


Page 22 of 28

Page 23 of 28


Figure 3.

23



Table of contents

24


Page 24 of 28

Page 25 of 28


PCA scores plot on the fatty acid data (normalized to 100 % and auto-scaled, n = 117). Variance explained: 46 %. Brown, pulp oil; red, kernel oil. Pulp oil samples within the circle correspond to the CPAC-PQ-SE-06 genotype). 103x87mm (300 x 300 DPI)



First two factors of PLS-DA scores (left) and loadings (right) plots of the model built on the fatty acid data of pulp (brown) and kernel (red) oil (training set, n = 81). 209x87mm (300 x 300 DPI)


Page 26 of 28

Page 27 of 28


PCA scores plot on the pulp oil samples (n = 73). Colors indicate different genotypes (CPAC-PQ-SE-06 genotype, red). Variance explained: 54 %. 103x87mm (300 x 300 DPI)



Table of Contents Graphic 112x72mm (300 x 300 DPI)


Page 28 of 28

Discrimination of Pulp Oil and Kernel Oil from Pequi (Caryocar

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