Recent Analytical Techniques Advances in the Carotenoids and Their

Subscriber access provided by - Access paid by the | UCSB Libraries

Recents analytical techniques advances in the carotenoids and their derivatives determination in various matrices Daniele Giuffrida, Paola Donato, Paola Dugo, and Luigi Mondello J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b00309 • Publication Date (Web): 13 Mar 2018 Downloaded from http://pubs.acs.org on March 16, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 21

Journal of Agricultural and Food Chemistry

Recent analytical techniques advances in the carotenoids and their derivatives determination in various matrices

Daniele Giuffrida† *, Paola Donato†, Paola Dugo§, ¶, ‡ and Luigi Mondello§, ¶, ‡ †

Dipartimento di Scienze Biomediche, Odontoiatriche e delle Immagini Morfologiche e Funzionali, University of Messina, Via Consolare Valeria - 98125 Messina, Italy

§

Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, - Polo Annunziata - viale Annunziata, 98168 – Messina, Italy ¶

Chromaleont s.r.l., c/o Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, Polo Annunziata, University of Messina, viale Annunziata - 98168 Messina, Italy ‡

Department of Medicine, University Campus Bio-Medico of Rome, via Álvaro del Portillo 21, 00128 Rome, Italy

*Corresponding author: Tel. +39-090-3503996; E-mail: [email protected] ORCID 0000-0002-0636-4345

ACS Paragon Plus Environment

1


Page 2 of 21

1

ABSTRACT

2

In the present perspective different approaches to the carotenoids analysis will be discussed

3

providing a brief overview of the most advanced both monodimensional and bidimensional liquid

4

chromatographic methodologies applied to the carotenoids analysis, followed by a discussion on the

5

recents advanced supercritical fluid chromatography x liquid chromatography bidimensional

6

approach with photo-diode-array and mass spectrometry detection. Moreover a discussion on the

7

online supercritical fluid extraction-supercritical fluid chromatography with tandem mass

8

spectrometry detection applied to the determination of carotenoids and apocarotenoids, will also be

9

provided.

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

KEYWORDS: Carotenoids analysis, mono- and multi-dimensional chromatography, LC-PDA-MS, Supercritical fluid extraction-supercritical fluid chromatography-MS ACS Paragon Plus Environment

2

Page 3 of 21


27

INTRODUCTION

28

Carotenoids are widely distributed natural pigments produced mainly by plants and microorganisms

29

commonly found in many foods and food products.

30

colorants, but recently their importance has grown due to the beneficial health properties that have

31

been ascribed to them1. Chemically they belong to the tetraterpene family and their structure is

32

usually based on a hydrocarbon C40 skeleton (carotenes) having a long unsaturated system which

33

acts as the chromophore; some carotenoids derivatives, like the apocarotenoids and norcarotenoids

34

or longer carotenoids with 45 or 50 carbon are not tetraterpenes. Quite often also oxygen atoms are

35

present in their structure commonly as hydroxyl, epoxy or keto groups giving rise to various

36

xanthophylls structures (Figure 1), although other oxygen containing functions might sometime also

37

be present. Moreover, when the hydroxyl function is present, it is often esterified with fatty acids;

38

in fact, the esterification provides greater stability to the molecule. The long π conjugated system

39

present in the carotenoid chemical structure is very sensitive to light, heat and oxygen and

40

carotenoids isomers and degradative products may easily be produced, therefore great care should

41

be taken in the carotenoids analysis to avoid analytical errors.

42

Carotenoids oxidative and enzymatic cleavage products called apocarotenoids are also widely

43

distributed in plants where they act as bioactive molecules2 (Figure 2); apocarotenoids are generated

44

by cleavage of a fragment from one side from the usual C40 carotenoid structure. Recently their

45

occurrence in food has gained interest due to the health related properties that have been attributed

46

to them3,4.

47

Carotenoids analyses have usually been performed after a saponification step which removed

48

chlorophylls and undesirable lipids and provided an easier chromatographic compounds separation,

49

but recently the trend is towards the study of the native carotenoids composition which was lost if

50

the saponification step was carried out in the matrix before the chromatographic analysis, thus

51

possibly leading to analytical errors 5.

Historically they have been used as food


3


Page 4 of 21

52

Guides to carotenoid analyses in foods are available in the literature5-11. Open Column

53

Chromatography (OCC), Thin Layer Chromatography (TLC) and High Performance Thin-Layer

54

Chromatography (HPTLC) are still used in separations of carotenoid extracts, using acetone as the

55

most traditional solvent for carotenoid extraction followed by partition solvents. High-performance

56

liquid chromatography (HPLC) can nowadays be considered the most commonly used methodology

57

for carotenoid separations12,13; in particular, the C30 columns have become the most prevalent

58

selection

59

to

60

chromatography is not sufficient for an optimal carotenoids separations in tricky samples and a

61

proposed alternative was also the use of multidimensional separation mechanisms19-21. Although

62

lately, supercritical fluids have been used for both the carotenoids separations (SFC – Supercritical

63

Fluid Chromatography) and the carotenoid extraction (SFE –Supercritical Fluid Extraction)

64

only very recently the direct online extraction and determination of carotenoids, by a supercritical

65

fluid

66

methodology was reported25 and a supercritical fluid chromatography-triple quadrupole/mass

67

spectrometry approach for the apocarotenoids determination was also recently reported26. In the

68

present perspective the different approaches to the carotenoids analysis above described will be

69

discussed providing a brief overview of the most advanced both monodimensional and

70

bidimensional liquid chromatographic methodologies applied to the carotenoids analysis, followed

71

by a discussion on the recents advanced supercritical fluid chromatography x liquid

72

chromatography bidimensional approach with photo-diode-array (PDA) and MS detection, and by a

73

discussion on the online supercritical fluid extraction-supercritical fluid chromatography with

74

tandem mass spectrometry (MS/MS) detection applied to the determination of carotenoids and

75

apocarotenoids.

one

14-16

. The serial connection of more then one column has been proposed as an alternative

single

column

liquid

extraction-supercritical

chromatography

fluid

(LC)17,18.

chromatography-mass

Sometime,

spectrometry

monodimensional

22-24

,

(SFE-SFC-MS)

76 77 ACS Paragon Plus Environment

4

Page 5 of 21


78

CAROTENOIDS SEPARATIONS BY MONODIMENSIONAL CHROMATOGRAPHY

79

High-performance liquid chromatography (HPLC) can nowadays be considered the most commonly

80

used methodology for carotenoid separations and identification with photo-diode-array (PDA) and

81

mass spectrometry detection (MS)

82

and particles size of 5 µm or 3 µm.

83

Many types of stationary phase have been used, including normal phase (NP) and reversed phase

84

(RP) materials. Normal-phase HPLC of xanthophylls is commonly performed using silica or silica-

85

based nitrile-bonded column and the mobile phase usually consists of an apolar hydrocarbon

86

solvent to which a more polar solvent is added as modifier.

87

column has also been broadly used for carotenoids because of the hydrophobic interactions taking

88

place and for the solvent and polarity range suitability with the carotenoids.

89

Carotenoids chromatography on reversed-phase C18 columns is frequently performed using

90

acetonitrile and methanol with the addition of a stronger less polar solvent as modifier, such as

91

methyl-tert-butyl ether (MTBE).

92

using ultra high-performance liquid chromatography (UHPLC) have recently been reported

93

17

94

particles (sub-2-micron stationary phase thickness) and mobile phase delivery systems operating at

95

high pressure; in fact in UHPLC systems the back-pressure can reach up to 103.5 MPa, much

96

higher then the back-pressure usually obtained in conventional HPLC systems which is around 35-

97

40 MPa. UHPLC features over conventional HPLC are quicker run times, higher sensitivity and

98

lower mobile phase waste. However, reversed-phase C30 columns are nowadays the preferred

99

alternative for carotenoids analysis.

12-15

, with column dimension usually of 250 mm x 4.6 mm i.d.,

Reversed-phase separation on C18

Better performances in carotenoids separations on C18 column 9,10, 13,

. This technology make use of narrow-bore columns (2.1 mm i.d.) packed with very small

The higher hydrophobicity of the C30 stationary phase

100

compared with the C18 one, has provided an improved resolution for carotenoids. Triacontyl-

101

bonded (C30) stationary phases has for example successfully been used in the separation of a

102

standard mixture of epoxycarotenoids isomers, employing a gradient elution of methanol, methyl-

103

ter-butyl ether (MTBE) and water16. Serial connection of more than one column has been suggested ACS Paragon Plus Environment

5


Page 6 of 21

104

in the separation of carotenoids in saponified red orange essential oil17. The advantages of coupling

105

two C30 columns to increase the peak capacity was shown; in fact, a peak capacity of 79 was

106

reached with two C30 coupled columns, in comparison to 61 obtained using a single column. This

107

novel overtures was also employed in the characterization of the carotenoids in orange juice 18. The

108

use of this methodology afforded the identification of 44 different carotenoids. Among them,

109

several violaxanthin diesters have been directly identified in orange juice for the first time.

110

As far as the general carotenoids detection is concerned in the carotenoids analyses in HPLC and

111

UHPLC, the UV-vis instruments have been the most common detectors, having the carotenoids

112

very characteristic UV-vis spectra, considering the position of the absorption maxima (λ max) and

113

the shape (spectral fine structure %III/II), and, eventually, the presence of a cis band in the

114

spectrum which enables the differentiation among trans (E) and cis carotenoids isomers (Z)

115

(spectral fine structure %AB/AII). In the carotenoids analysis it should be taken into consideration

116

that two pigments with different structure but identical chromophore will have the same UV-vis

117

spectra and therefore it sometime occurs that, for example, two carotenoids show the same UV-vis

118

spectra but have different molecular ion (m/z) values or the opposite might also occur, therefore a

119

great help in the carotenoids identifications has been the online use of both detection systems (PDA

120

and MS) coupled to the chromatography system.

121

structural features, enormously contribute in the carotenoids characterization providing information

122

on their molecular mass and their fragmentation pattern. The use of atmospheric pressure chemical

123

ionization (APCI) for the carotenoids analysis has rapidly grown; in fact, it efficiently ionize not

124

only xanthophylls and carotenes but also carotenoids esters. The possibility of a rapid switchover

125

between positive and negative ionization modes in the APCI probe during the same analytical run,

126

allows the collection of a greater number of qualitative information about a sample in a single run

127

and this is of great help especially for the carotenoids esters identification; in fact, in the negative

128

mode the quasi-molecular ion species is dominating the MS spectrum, whereas fragment ions are

129

mainly occurring in the APCI positive mode due to in source fragmentation. Thus positive and

Mass detectors giving information about


6

Page 7 of 21


130

negative APCI ionization modes are providing complementary information that can greatly help for

131

example in the identification of carotenoid esters regioisomers

132

sensitivity provided by tandem mass spectrometry (MS/MS) brings advantages in the carotenoids

133

analyses; the use of specific multiple reaction monitoring (MRM) experiments in which specific

134

transition are monitored offers not only qualitative information but also allows for the individual

135

quantifications of carotenoids in very low concentration, compared to the spectrophotometric

136

methods commonly used for the carotenoids quantifications, normally carried out by external

137

calibration with the respective standard 9,10, 28.

138

CAROTENOIDS SEPARATIONS BY BIDIMENSIONAL CHROMATOGRAPHY

139

Carotenoids separation by comprehensive liquid chromatography (LC x LC)

140

Multidimensional liquid chromatography (MD-LC) can be considered as a possible alternative for a

141

superior compounds separation in those cases where monodimensional systems show limitation21.

142

Comprehensive 2-D chromatography systems are characterized by the fact that the entire sample to

143

be analysed is subjected to two on-line diverse chromatographic separation steps, thus increasing

144

very much the overall separation power and peak capacity. All compounds eluting from the first

145

dimension (1D) separation are sequentially transferred into the second dimension (2D), for a further

146

separation. The columns of the first and second dimension analysis are connected via an automated

147

switching multiport valve system that is able to transfer subsequently small aliquots eluting from

148

the first column into the second column, and of which technical aspects are beyond the scope of this

149

perspective. The second dimension analysis should be completed, before the successive transfer

150

from the first column occurs. The best performances of comprehensive system take place when the

151

two separation mechanisms operating in the two different dimensions have complementary

152

selectivity, so-called “orthogonal” systems. The most orthogonal set up could be considered the

153

normal phase (NP) x reversed phase (RP) one. The final visualization of the comprehensive analysis

154

is a 2-D contour plot in which the separated compounds are scattered over the plane and each one is


9,10, 18, 27

. The high selectivity and

7


Page 8 of 21

155

represented by an ellipse-shaped peak, defined by double-axis retention time coordinates; moreover,

156

the software normally allows also for a 3D visualization. The first development of a comprehensive

157

liquid chromatography (LC x LC) methodology for the study of the native carotenoid composition

158

in a very complex matrix was applied to a sample of red orange essential oils19. Free carotenoids

159

and carotenoid esters were characterized. In this study a comprehensive NP-LC x RP-LC-

160

PDA/APCI-MS methodology was set up using a cyano microbore column (250 mm x 1.0 mm i.d.,

161

5 µm particle size) in the first dimension (NP) and a monolithic C18 column (4.6 mm i.d.) in the

162

second dimension (RP), that were coupled by a two positions 10-port switching valve. Compounds

163

were separated in the first dimension (1D) according to their polarity, from hydrocarbons to free

164

xanthophylls; the analytes were separated in the second dimension (2D) according to their

165

hydrophobicity, the elution order being largely dependent on the fatty acid chain esterified to the

166

xanthophyll so, specifically, retention increased with chain length. 40 different carotenoids were

167

characterized and among them, 16 carotenoid monoesters and 21 carotenoid diesters were identified

168

in the native carotenoid composition of the red orange essential oil.

169

application of liquid comprehensive chromatography to the native carotenoids analysis was

170

achieved by combining normal phase separation in the first dimension and reversed phase ultra high

171

performance liquid chromatography (UHPLC) in the second dimension for the study of the native

172

carotenoids composition in an other very complex matrix like a red chilli peppers carotenoid extract

173

20

174

mm i.d.) cyano column for the first dimension separation, interfaced by two six-port, two position

175

switching valves to two serially coupled C18 column packed with fused-core particles (30 mm ×

176

4.6 mm i.d., 2.7 micron particle size) in the second dimension. The fused-core technology provides

177

a packing material with particles having an overall size of 2.7 µm, consisting of a silica nucleus

178

encircled by a thin (0.5 µm) porous shell of stationary phase. This was the first work that reported

179

the use of UHPLC conditions in the second dimension performed on octadecylsilica columns

180

packed with 2.7 micron particles. Thirty-three components belonging to ten different chemical

A further step in the

. In this study, a novel NP-LC × RP-LC application has been worked out, using a micro-bore (1.0


8

Page 9 of 21


181

classes were identified by this methodology (Figure 3, A). The application of the UHPLC

182

technology in this study has shown great potential in resolution and rapidity for the second

183

dimension

184

chromatography will probably come from the development of new stationary phases, new

185

automated systems with reduced dead volumes, higher pressure check valves, and compatibility

186

with hyphenation of different detectors.

187

Carotenoids separation by comprehensive supercritical fluid chromatography x liquid

188

chromatography (SFC x LC)

189

As it has been previously described, NP x RP set up in comprehensive liquid chromatography is

190

considered to be one of the most powerful combination because it greatly enhances the

191

orthogonality of the system. However, this combination is not free from some drawbacks like the i)

192

immiscibility of the mobile phases between the two dimensions that has been partially overcome by

193

the use of a microbore column and very slow flow rate in the order of 10 µL/min in the first

194

dimension, ii) the peak focusing at the head of the secondary column, that has also been in part

195

circumvented by employing a low flow rate in the first dimension iii) the long analytical time and

196

iv) the relatively high solvent consumption. A feasible option is to replace the first (1D) NP-LC

197

dimension by supercritical fluid chromatograpgy (SFC); this combination lessens the solvent

198

immiscibility problems and brings many advantages that are characterizing the use of supercritical

199

fluid carbon dioxide, like a fast rate of separation and high resolution together with a high

200

orthogonality towards RP-LC. Supercritical CO2 is considered particularly suitable for carotenoids

201

separation because of its low polarity; in SFC quite often a proportion of an organic solvent is

202

added to the mobile phase as modifier, in order to widen the affinity of the mobile phase for the

203

different compounds and also little variation in the density of the fluid are achieved by small

204

changes in its pressure or temperature which can further ameliorate the separation. Moreover,

205

additional benefits in SFC compared to LC, are the use of a much more ecological mobile phase

chromatographic

step.

Future

improvements


in

comprehensive

2-D

liquid

9


Page 10 of 21

206

with the reduction of organic solvent utilization and costs. An on-line SFC×RP-LC comprehensive

207

separation system was developed for the characterization of native carotenoids in a red chilli pepper

208

extract, with photodiode array and quadrupole time-of-flight (Q ToF) mass spectrometry (MS)

209

detection, for the first time, by using a cyano microbore column (250 mm x 1.0 mm I.D., 5.0 µm

210

particle size) in the first dimension SFC separation (1D), and a C18 column (50 mm x 2.1 mm i.d.,

211

1.7 µm particle size) for the second dimension (2D) UHPLC separation (author unpublished work).

212

In this work two fully automated 2-position six-port switching valves equipped with two packed

213

octadecyl silica cartridges for effective trapping and focusing of the analytes after elution from 1D

214

were used with the addition of a water make-up flow to the SFC effluent prior to entering the loops

215

that permitted to efficiently focus the solutes on the sorbent material and to reduce interferences of

216

expanded CO2 gas on the second dimension separation. Compared to the previously described NP

217

x RP-LC approach 20, the SFC x RP-LC platform afforded an higher identification power; in fact up

218

to fifty components belonging to fifteen different chemical classes were successfully identified in

219

the sample tested. Moreover, the SFC x RP-LC system greatly reduced the organic solvent

220

consumption both in the first and second dimension by respectively half and about an eleventh, and

221

the analysis time also by half (Figure 3, B). It is predictable that the use of supercritical fluids in

222

comprehensive approachs will be further exploited by the academic community.

223

CAROTENOIDS

224

SUPERCRITICAL FLUID CHROMATOGRAPHY-MASS SPECTROMETRY (SFE-SFC-

225

MS)

226

Although lately, supercritical fluids have been used for both the carotenoids separations (SFC) and

227

the carotenoid extraction (SFE)22-24, only very recently the direct online extraction and

228

determination of carotenoids, by a supercritical fluid extraction-supercritical fluid chromatography-

229

mass spectrometry (SFE-SFC-MS) methodology was reported25.

230

(CO2) offer peculiar features, like low viscosity, high density and high diffusion coefficient that

SEPARATION

BY

SUPERCRITICAL


FLUID

EXTRACTION-

Supercritical carbon dioxide

10

Page 11 of 21


231

makes it suitable for both the supercritical fluid extraction and chromatography. The recently

232

developed supercritical fluid extraction-chromatography-mass spectrometry methodology25,

233

allowed for the determination of targeted native carotenoids in red habanero pepper. 21 analytes

234

were extracted and identified by the developed methodology in less than 17 minutes, including free

235

carotenoids, carotenoids monoesters and carotenoids diesters, in a very fast “green” and efficient

236

way.

237

separation were performed on a novel fused-core Ascentis Express C30 column, (150 mm × 4.6

238

mm I.D. and 2.7 µm particles) having a sub-2-micron stationary phase, in an approach that could be

239

considered as a ultra-high performance supercritical fluid chromatography (UHPSFC)

240

methodology.

241

In Figure 4 is reported a schematic representation of this novel SFE-SFC-MS system, which

242

operates in three different modes (A), (B), and (C). A) Static extraction mode: during this mode the

243

total flow is splitted between the analytical column and the extraction vessel. B) Dynamic

244

extraction mode: during this step another valve diverts the total flow into the extraction vessel (in

245

opposite direction compared to the static extraction) in order to transfer the extracted analytes into

246

the analytical column. C) Analysis mode: during this step the total flow is entirely directed into the

247

analytical column.

248

traditional solid-liquid extraction and conventional LC, which required much longer analytical time

249

and solvent waste; moreover, being completed automated, drastically reduces the possible operator

250

errors to occur and the possible analytes losses. Also very recently the same system was used for

251

the SFC-APCI (+/-)/QqQ/MS investigation on the apocarotenoids presence in red habanero chilli

252

peppers26, which had been previously determined in some food and biological matrices by liquid

253

chromatography

254

Monitoring) of their radical anions generated in the negative ionization mode and, for the free

255

apocarotenoids, also by comparison with the different generated standards mixtures.

256

transitions used in the MS/MS experiments, were selected on the basis of the Product Ion Scan

The online SFE-SFC conditions were optimized using CO2 and MEOH and the SFC

The reported methodology was extremely innovational confronted to the

29,30

.

The different apocarotenoids were detected by SIM (Selective Ion


The

11


Page 12 of 21

257

(PIS) experiments carried out on the various available standards using various collision energies

258

both in positive and negative modes, before the MRM (Multiple Reaction Monitoring) experiments

259

were made, in order to further confirm the reported compounds identifications. In this study, 25

260

different apocarotenoids were identified, 14 were free apocarotenoids and 11 were apocarotenoids

261

fatty acids esters. The methodology allowed for all the separations to occur in less then five

262

minutes.

263

capsorubinal and Apo-10’-zeaxanthinals fatty acid esters had not been previously identified in any

264

Capsicum species and, to the best of the authors knowledge, in any food matrix. The reported

265

highly sensitive hyphenated system could be regarded as a convenient tool for a rapid

266

apocarotenoids detection, and could be applied to the study on the occurrence of these important

267

metabolites in different food, food products and biological fluids.

268

Abbreviations used

269

OCC, Open Column Chromatography; TLC, Thin Layer Chromatography; HPTLC, High

270

Performance Thin-Layer Chromatography; HPLC, High Performance Liquid Chromatography; LC,

271

Liquid chromatography; SFC, Supercritical Fluid Chromatography; SFE, Supercritical Fluid

272

Extraction; MS, Mass Spectrometry; PDA, Photo-Diode-Array; LC x LC, Comprehensive Liquid

273

Chromatography; UHPLC, Ultra High Performance Liquid Chromatography; Q ToF, Quadrupole

274

Time of Flight; MS/MS, tandem mass spectrometry; QqQ/MS, Triple Quadrupole Mass

275

Spectrometry; N P, Normal Phase; R P, Reversed Phase.

276

Notes

277

The author declare no competing financial interest.

The detected Apo-10’-, Apo-14’- and Apo-15- capsorubinals and different Apo-8’-

278 279 280 281


12

Page 13 of 21


282

REFERENCES

283

(1) Britton, G.; Liaaen-Jensen, S.; Pfander, H.

284 285 286 287 288

Carotenoids. Vol. 5: Nutrition and Health;

Birkhauser: Basel, Switzerland, 2009. (2) Hou, X.; Rivers, J.; Leon, P.; McQuinn, R. P.; Pogson, B. J. Synthesis and function of apocarotenoid signals in plants. Trends in Plant Sci., 2016, 21, 792-803. (3) Eroglu, A.;Harrison, E. H. Carotenoid metabolism in mammals, including man: formation, occurrence, and function of apocarotenoids. J. Lipid Res., 2013, 54, 1719-1730.

289

(4) Kopec, E. R.; Schwartz, S. J. Carotenoid cleavage dioxygenase and presence of apo-carotenoids

290

in biological matrices. In Carotenoid Cleavage Products; Winterhalter P., Ebeler S. E., Eds.;

291

ACS Symposium Series 1134. Oxford University Press: Washington, DC, 2013, pp 31-41.

292

(5) Mercadante A.Z.; Rodrigues D.B.; Petri F.C.; Mariutti L.R.B. Carotenoid esters in foods – A

293

review and practical directions on analysis and occurrence. Food Res. Int., 2017, 99, 830-850.

294

(6) Schiedt, K.; Liaaen-Jensen S. Isolation and Analysis In Carotenoids. Vol. 1A Isolation and

295

Analysis, Britton, G., Liaaen-Jensen, S., Pfander, H. Eds.; Birkhauser: Basel, Switzerland, 1995, pp

296

81-107.

297

(7) Khachik, F. Analysis of carotenoids in nutritional studies. In Carotenoids. Vol. 5

298

and Health, Britton, G.; Liaaen-Jensen, S.; Pfander, H. Eds.; Birkhauser: Basel, Switzerland, 2009,

299

pp 7-44.

300

(8) Britton, G.; Khachik, F. Carotenoid in Food. In Carotenoids. Vol. 5

301

Britton, G.; Liaaen-Jensen, S.; Pfander, H. Eds.; Birkhauser: Basel, Switzerland, 2009, pp 45-66.

302

(9) Rivera, S. M.; Canela-Garayoa R. Analytical tools for the analysis of carotenoids in diverse

303

materials. J. Chromatogr. A, 2012, 1224, 1-10.

304

(10) Amorim-Carrilho, K. T.; Cepeda, A.; Fente, C.; Regal, P. Review of methods for analysis of

305

carotenoids. Trends Anal. Chem., 2014, 56, 49-73.

Nutrition

Nutrition and Health,

306 ACS Paragon Plus Environment

13


Page 14 of 21

307

(11) Rodriguez-Amaya, D. B. Food carotenoids, Chemistry, Biology and Technology IFT Press,

308

Wiley Blackwell: Chichester, West Sussex, UK, 2016.

309

(12) Pfander, H.; Riesen, R. Chromatography: Part IV. High-Performance Liquid Chromatography.

310

In Carotenoids. Vol. 1A Isolation and Analysis, Britton, G., Liaaen-Jensen, S., Pfander, H. Eds.;

311

Birkhauser: Basel, Switzerland, 1995, pp 145-190.

312

(13) Bijttebier S.; D’Hondt E.; Noten B.; Hermans N.; Apers S.; Voorspoels S. Ultra high

313

performance liquid chromatography versus high performance liquid chromatography: Stationary

314

phase selectivity for generic carotenoid screening. J. Chromatogr. A, 2014, 1332, 46-56.

315

(14) Sander, L. C.; Sharpless, K. E.; Craft, N. E.; Wise, S. A. Development of engineered stationary

316

phases for the separation of carotenoid isomers. Anal. Chem., 1994, 66, 1667-1674.

317

(15) Sander, L. C.; Sharpless, K. E.; Pursch, M. C30 Stationary phases for the analysis of food by

318

liquid chromatography. J. Chromatogr. A, 2000, 880, 189-202.

319

(16) Melendez-Martinez, A. J.; Escudero-Gilete M. L.; Vicario, I. M.; Heredia, F. J. Separation of

320

structural, geometrical and optical isomers of epoxycarotenoids using triacontyl-bonded stationary

321

phases. J. Sep. Sci., 2009, 32, 1838-1848.

322

(17) Herrero, M.; Cacciola, F.; Donato, P.; Giuffrida, D., Dugo, G.mo; Dugo, P.; Mondello, L.

323

Serial coupled columns reversed-phase separations in high-performance liquid chromatography.

324

Tool for analysis of complex real samples. J. Chromatogr. A, 2008, 1188, 208-215.

325

(18) Dugo, P.; Herrero, M.; Giuffrida, D.; Ragonese, C.; Dugo, G.mo; Mondello, L.

326

Analysis of native carotenoid composition in orange juice using C30 columns in tandem.

327

J. Sep. Sci., 2008, 31, 2151- 2160.

328

(19) Dugo, P.; Herrero, M.; Giuffrida, D.; Kumm, T.; Dugo, G; Mondello, L. Application of

329

comprehensive two-dimensional liquid chromatography to elucidate the native carotenoid

330

composition in red orange essential oil. J. Agric. Food Chem., 2008, 56, 3478-3485.


14

Page 15 of 21


331

(20) Cacciola, F.; Donato, P.; Giuffrida, D.; Torre, G.; Dugo, P.; Mondello, L. Ultra high pressure

332

in the second dimension of a comprehensive two-dimensional liquid chromatographic system for

333

carotenoid separation in red chili peppers. J. Chromatogr. A, 2012, 1255, 244-251.

334

(21) Francois, I.; Sandra, K.; Sandra, P. Comprehensive liquid chromatography: fundamental

335

aspects and practical considerations – a review. Anal. Chim. Acta, 2009, 641, 14-31.

336

(22) Li, B.; Zhao, H.; Liu, J.; Liu, W.; Fan, S.; Wu, G.; Zhao, R. Application of ultra-high

337

performance supercritical fluid chromatography for the determination of carotenoids in dietary

338

supplements. J. Chromatogr. A, 2015, 1425, 287-292.

339

(23) Jumaah, F.; Plaza, M.; Abrahamsson, V.; Turner, C. A fast and sensitive method for the

340

separation of carotenoids using ultra-high performance supercritical fluid chromatography-mass

341

spectrometry. Anal. Bioanal. Chem., 2016, 408, 5883-5894.

342

(24) Durante, M.; Lenucci, M.S.; Mita, G. Supercritical carbon dioxide extraction of carotenoids

343

from pumpkin (Cucurbita spp.): a review. Int. J. Mol. Sci., 2014, 15, 6725-6740.

344

(25) Zoccali, M.; Giuffrida, D.; Dugo, P.; Mondello, L. Direct online extraction and determination

345

by supercritical fluid extraction with chromatography and mass spectrometry of targeted

346

carotenoids from Habanero peppers (Capsicum chinense Jacq.). J. Sep. Sci., 2017, 40, 3905-3913.

347

(26) Giuffrida, D.; Zoccali, M.; Giofrè, S.V.; Dugo, P.; Mondello, L.

348

determination in Capsicum chinense Jacq. cv Habanero, by supercritical fluid chromatography-

349

triple-quadrupole/mass spectrometry. Food Chem., 2017, 231, 316-323.

350

(27) Mellado-Ortega, E. Hornero-Méendez D. Isolation and identification of lutein esters, including

351

their regioisomers, in tritordeum (x Tritordeum Ascherson et Graebner) grains: Evidence for a

352

preferential xanthophyll acyltransferase activity. Food Chem., 2012, 135, 1344-1352.

Apocarotenoids

353 354


15


Page 16 of 21

355

(28) Gentili, A.; Caretti, F.; Ventura, S.; Pérez-Fernàndez, V.; Venditti, A.; Curini, R. Screening of

356

carotenoids in tomato fruits by using liquid chromatography with diode array-linear ion trap mass

357

spectrometry detection, J. Agric. Food Chem., 2015, 63, 7428-7439.

358

(29) Kopec, R. E.; Rield, K. M.; Harrison, E. H.; Curley, R. W.; Hruszkewycz, D. P.; Clinton, S.

359

K.; Schwartz, S. J., Identification and quantification of apo-lycopenals in fruits, vegetables, and

360

human plasma, J.Agric. Food Chem., 2010, 58, 3290-3296.

361

(30) Fleshman, M. K.; Lester, G. E.; Riedl, K. M.; Kopec, R. E.; Narayanasamy, S.; Curley, R. W. ;

362

Schwartz, S. J. (2011).

363

Cucumis melo melons: determination of β-carotene bioaccessibility and bioavailability. J. Agric.

364

Food Chem., 2011, 59, 4448-4454.

Carotene and novel apocarotenoid concentrations in orange-fleshed

365 366

Figure captions

367

Figure 1. The chemical structures of four common carotenoids. Hydrocarbon carotenoids:

368

Lycopene, β-Carotene; Oxygenated carotenoids: Zeaxanthin and Violaxanthin.

369

Figure 2. The different positions of eccentric zeaxanthin oxidative cleavages sites leading to

370

different apozeaxanthinals.

371

Zeaxanthinal; 4. Apo-8’-Zeaxanthinal.

372

Figure 3. A summary representation indicating the improvements in terms of compounds

373

identification, solvents and time saving in going from a comprehensive NP-LC x RP-LC set up (A)

374

to a SFC x RP-LC approach (B) in the separation of carotenoids in chilli peppers. * Data from

375

reference n. 20. ** Authors unpublished work.

376

Figure 4. The SFE-SFC-MS system: (A) Static extraction mode, (B) Dynamic extraction mode,

377

(C) Analysis mode. Reprinted with permission from reference n. 25.

1. Apo-14’-Zeaxanthinal; 2. Apo-12’-Zeaxanthinal; 3. Apo-10’-


16

Page 17 of 21


Figure 1


17


Page 18 of 21

Figure 2


18

Page 19 of 21


Figure 3


19


Page 20 of 21

Figure 4


20

Page 21 of 21


Graphic for Table of Contents Only

SFC x LC-MS LC x LC SFE-SFC-MS

LC


21

Recent Analytical Techniques Advances in the Carotenoids and Their

Recommend Documents