Lycopene in Tomatoes: Chemical and Physical Properties Affected by Food Processing

Critical Reviews in Food Science and Nutrition
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Lycopene in Tomatoes: Chemical and Physical

Properties Affected by Food Processing
John Shi & Marc Le Maguer
To cite this article: John Shi & Marc Le Maguer (2000) Lycopene in Tomatoes: Chemical and
Physical Properties Affected by Food Processing, Critical Reviews in Food Science and Nutrition,
40:1, 1-42, DOI: 10.1080/10408690091189275
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Critical Reviews in Food Science and Nutrition, 40(1):1–42 (2000)
Lycopene in Tomatoes: Chemical and Physical

Properties Affected by Food Processing
John Shi*
Southern Crop Protection and Food Research Center, Agriculture and Agri-Food Canada,
Guelph, Ontario N1G 2W1 Canada
Marc Le Maguer
Department of Food Science, University of Guelph, Guelph, Ontario N1G 2W1 Canada
* Author to whom correspondence should be addressed. E-mail: ShiJ@EM.AGR.CA; Fax: (519)837-9472
Referee: Yukio Kakuda, Ph.D., Food Science, University of Gyelph, Guelph, Onterio, Canada N1G2W1
ABSTRACT: Lycopene is the pigment principally responsible for the characteristic deep-red
color of ripe tomato fruits and tomato products. It has attracted attention due to its biological and
physicochemical properties, especially related to its effects as a natural antioxidant. Although it
has no provitamin A activity, lycopene does exhibit a physical quenching rate constant with
singlet oxygen almost twice as high as that of β-carotene. This makes its presence in the diet of
considerable interest. Increasing clinical evidence supports the role of lycopene as a micronutri-
ent with important health benefits, because it appears to provide protection against a broad range
of epithelial cancers. Tomatoes and related tomato products are the major source of lycopene
compounds, and are also considered an important source of carotenoids in the human diet.
Undesirable degradation of lycopene not only affects the sensory quality of the final products,
but also the health benefit of tomato-based foods for the human body. Lycopene in fresh tomato
fruits occurs essentially in the all-trans configuration. The main causes of tomato lycopene
degradation during processing are isomerization and oxidation. Isomerization converts all-trans
isomers to cis-isomers due to additional energy input and results in an unstable, energy-rich
station. Determination of the degree of lycopene isomerization during processing would provide
a measure of the potential health benefits of tomato-based foods. Thermal processing (bleaching,
retorting, and freezing processes) generally cause some loss of lycopene in tomato-based foods.
Heat induces isomerization of the all-trans to cis forms. The cis-isomers increase with tempera-
ture and processing time. In general, dehydrated and powdered tomatoes have poor lycopene
stability unless carefully processed and promptly placed in a hermetically sealed and inert
atmosphere for storage. A significant increase in the cis-isomers with a simultaneous decrease in
the all-trans isomers can be observed in the dehydrated tomato samples using the different
dehydration methods. Frozen foods and heat-sterilized foods exhibit excellent lycopene stability
throughout their normal temperature storage shelf life.
Lycopene bioavailability (absorption) can be influenced by many factors. The bioavailability
of cis-isomers in food is higher than that of all-trans isomers. Lycopene bioavailability in
processed tomato products is higher than in unprocessed fresh tomatoes. The composition and
structure of the food also have an impact on the bioavailability of lycopene and may affect the
release of lycopene from the tomato tissue matrix. Food processing may improve lycopene
bioavailability by breaking down cell walls, which weakens the bonding forces between lycopene
Copyright© 2000, CRC Press LLC — Files may be downloaded for personal use only. Reproduction of this material
without the consent of the publisher is prohibited.
1
and tissue matrix, thus making lycopene more accessible and enhancing the cis-isomerization.
More information on lycopene bioavailability, however, is needed. The pharmacokinetic prop-
erties of lycopene remain particularly poorly understood. Further research on the bioavalability,
pharmacology, biochemistry, and physiology must be done to reveal the mechanism of lycopene
in human diet, and the in vivo metabolism of lycopene.
Consumer demand for healthy food products provides an opportunity to develop lycopene-
rich food as new functional foods, as well as food-grade and pharmaceutical-grade lycopene as
new nutraceutical products. An industrial scale, environmentally friendly lycopene extraction
and purification procedure with minimal loss of bioactivities is highly desirable for the foods,
feed, cosmetic, and pharmaceutical industries. High-quality lycopene products that meet food
safety regulations will offer potential benefits to the food industry.
KEY WORDS: bioactivity, bioavailability, degradation, isomerization, lycopene, oxidation,

processing, tomato.
I. INTRODUCTION jelly-like parenchyma cells that surround the

seeds. Tomatoes normally contains 5 to 10%
The red color of many kinds of fruits is dry matter, of which about 75% is soluble,
due to the presence of lycopene and other and about 1 to 3% of which consists of skin
carotenoids. Lycopene is a natural pigment and seed. Nearly half of the total dry matter
synthesized exclusively by plants and mi- is reducing sugars, and about 10% is organic
croorganisms. One of the functions of lyco- acid, principally citric and malic acids. More
pene and related carotenoid species is to than 80% of processed tomatoes are con-
absorb light during photosynthesis, thereby sumed in the form of tomato juice, paste,
protecting plants against photosensitization. puree, catsup, sauce, and salsa (Gould, 1992).
Lycopene is among the most widespread and Tomatoes and tomato-based foods are
important natural pigments. Inasmuch as considered healthy foods for several reasons.
lycopene and other carotenoids are photo- They are low in fat and calories, cholesterol-
synthesized by plants and microorganisms, free, and a good source of fiber and protein.
they constitute the main source of all animal In addition, tomatoes are rich in vitamins A
carotenoids. Sometimes the brilliant colors and C, β-carotene, potassium, and lycopene.
of lycopene are masked by the green The characteristic deep-red color of ripe to-
chlorophyllic pigments (i.e., in green veg- mato fruits and tomato-based foods, which
etables and leaves). In a number of cases, the serves as a measure of total quality, is mainly
chlorophyll content decreases as plants ma- due to lycopene. Tomatoes and tomato foods
ture, leaving the lycopene and other caro- are the major sources of lycopene and are
tenoids responsible for the bright colors of considered to be important contributors of
most fruits (pineapple, orange, lemon, grape- carotenoids to the human diet. Other sources
fruit, strawberry, tomato, paprika, rose hip) of lycopene include watermelon, guava,
and many flowers (Eschscholtzia, Narcis- rosehip, papaya, and pink grapefruit (Gross,
sus). Carotenoids also contribute to the col- 1987, 1991; Mangels et al., 1993) (Table 1).
ors of some birds (flamingo, canary), in- Lycopene is an important natural color in-
sects, and marine animals (shrimp, lobster, gredient in food formulations. The wide-
and salmon). spread use of tomato paste as a colorant
Tomatoes are an important agricultural makes lycopene a commercially important
commodity worldwide. The tomato fruit is natural pigment. However, Llcopene under-
comprised of skin, pericarp, and locular con- goes degradation via isomerization and oxi-
tents. The locular cavities are filled with dation during tomato processing, which has
2
TABLE 1
Lycopene Content of Fruits and Vegetables
Lycopene content
Material (mg/100 g wet basis)
Fresh tomato fruit 0.72–20

Watermelon 2.3–7.2
Guava (pink) 5.23–5.50
Grapefruit (pink) 0.35–3.36
Papaya 0.11–5.3
Rosehip puree 0.68–0.71
Carrot 0.65–0.78
Pumpkin 0.38–0.46
Sweet potato 0.02–0.11
Apple pulp 0.11–0.18
Apricot 0.01–0.05
Data from Beerh and Siddappa, 1959; Gross, 1987, 1991;

Mangels et al., 1993.
a direct impact on the food sensory quality 9.27 mg/100 g. Some deep-red varieties con-
and health benefit. Degradation of lycopene tain more than 15 mg per 100 g, whereas the
not only affects the sensory quality such as yellow varieties contain only about 0.5 mg
color of final products, but also their health per 100 g (Hart and Scott, 1995). Liu and
benefits to consumers. Therefore, it is im- Luh (1977) reported that the harvest matu-
portant to study the effects of food process- rity affected carotenoids in tomato paste.
ing on the lycopene stability in tomato prod- Lycopene increases as tomatoes mature. Ellis
ucts and bioavailability of lycopene in and Hammer (1943) also found that there
tomato-based foods. was a greater concentration of lycopene and
other carotenoids in the stem than in the
II. LYCOPENE DISTRIBUTION IN blossom end of the fruit, the transverse seg-
TOMATO FRUITS ments having intermediate contents. Edwards
and Reuters (1961) examined the lycopene
A. Lycopene in Tomato Fruits contents of 11 commercial varieties of toma-
toes differing appreciably in variety and
Lycopene is the most abundant caro- maturity factors. Heinonen et al. (1989) re-
tenoid in ripe tomatoes, comprising approxi- ported that the lycopene concentration in
mately 80 to 90% of those pigments present. tomatoes was higher in summer (from June
Other carotenoids (α-carotene, β-carotene, to August) and lower in winter (from Octo-
lutein, and β-cryptoxanthin) are negligible ber to March). Tomato fruits grown in the
(Curl, 1961). The amount of lycopene in greenhouse either in summer or winter are
fresh tomato fruits depends on variety, lower in lycopene content than fruits pro-
maturity, and the environmental conditions duced outdoors during summer, and fruits
under which the fruit matured. Normally, picked green and ripened in storage are sub-
tomatoes contain about 3 to 5 mg lycopene stantially lower in lycopene than vine-rip-
per 100g of raw material (Hart and Scott, ened fruits (Gould, 1992). Furthermore, Lurie
1995). Higher amounts are found in some et al. (1996) reported that relatively high
tomato varieties. Recently, Tonucci et al. temperatures (38°C) inhibited lycopene pro-
(1995) reported that lycopene content duction while low temperatures inhibited
in whole tomato fruit was more than both fruit ripening and lycopene production.
3
Lycopene formation occurred about 2 days can be found among the thylakoid mem-
earlier if tomato fruits were treated with eth- branes in the photosynthetic pigment-pro-
ylene (Jeffery et al., 1984). It was reported tein complex (Bouvier et al., 1998; Akhtar et
that lycopene synthesis in the rin mutant was al., 1999). In the early stages of tomato fruit
enhanced by high O2 in the presence of 10 maturation, the dominant pigment in the
ppm ethylene (Frenkel and Gurrison, 1976). chloroplasts is green chlorophyll. As the
On the other hand, ethanol inhibited ripen- chlorophyll degrades, the color change from
ing and the synthesis of lycopene in toma- green to white. When chlorophyll in the
toes (Sahveit and Mencarelli, 1988). Addi- chloroplasts is reduced, lycopene is bio-
tionally, Sheehy et al. (1988) found that a synthesized with concomitant changes in the
reduction in polygalacturonase did not af- ultrastructure of the fruit, which results in
fect synthesis of lycopene. Lampe and the color change from white to red (Harris,
Watada (1971) and Mohr (1979) indicated 1970; Khudairi, 1972; Matienco and Yedalty,
that the lycopene content in tomato fruits 1973). The final stage of chromoplast devel-
may be enhanced by improved techniques in opment is the formation of lycopene crystals
fertilizer, harvest time, and variety selection. that occupy a large portion of chromoplast
Table 2 shows the lycopene content in to- and appear as volumnous red sheets in the
mato fruits of different varieties, growing chromoplasts (Laval-Martin, 1974). The larg-
locations, and maturity. est concentrations of lycopene are found in
McCallum (1955) studied the distribu- the pericarp (Simpson et al., 1977). The bio-
tion of lycopene and other carotenoids in the synthesis of lycopene and other carotenoids
tomato and found that the outer pericarp was in tomatoes has been studied extensively with
highest in lycopene and total carotenoids, the use of 14C tracers (Porter and Anderson,
and the locule was the highest in carotene 1967; Buggy et al., 1969). Mevalonic acid,
(Table 3). According to Al-Wandawi et al. believed to be a precursor, is converted step
(1985), tomato skin contains 12 mg lyco- by step by a loss of hydrogen in each step, to
pene/100 g skin (wet basis) lycopene, while produce lycopene. Dehydrogenation is most
whole mature tomato contains only 3.4 mg likely involved in each step. Thus, lycopene
lycopene/100 g (wet basis). Therefore, the exists as small globules, that is, in the chro-
concentration of lycopene in tomato skin is moplasts, which are suspended in the tomato
about three times higher than in whole ma- pulp throughout the fruit. Lycopene appears
ture tomatoes. D’Souza et al. (1992) also as solid microcrystals and thus the light re-
found that the skin and the pericarp of to- flected from them gives the tomato its typi-
mato fruits were rich in lycopene. Sharma cal bright red color.
and Le Maguer (1996) found that skins were
a rich source of lycopene, as they contained
about five times more lycopene (53.9 mg/ III. CHEMICAL AND PHYSICAL
100 g) than the whole tomato pulp (11 mg/ PROPERTIES OF LYCOPENE
100 g). This indicates that most of the lyco-
pene is found attached to the insoluble fiber Carotenoids are widely distributed in
portion of the tomatoes. fruits and vegetables, and more than 600
carotenoids, mainly cis-trans isomers, have
been characterized in vegetable products that
B. Lycopene Biosynthesis in Plant humans consume. Chemically, carotenoids
Cells can be divided into two major classes. Caro-
tenoid species in the first class are the highly
At the cellular level, lycopene is local- unsaturated hydrocarbon carotenoids such
ized in the chloroplasts of tomato fruits, and as lycopene, α-carotene, β-carotene, γ-caro-
4
TABLE 2
A Survey of Lycopene Content in Some Tomato Cultivars
Lycopene
(mg/100 g
Material wet basis) Sources
Juice from ripe tomatoes 3.71 Beerh and Siddappa, 1959

Juice from green tomatoes 0.171
Juice from partially ripe, yellowish-red tomatoes 0.240
(in India)
VT-145-7879 Liu and Luh, 1977
Pink 12.18
Medium red with some orange spots 20.71
Full red ripe 30.16
(in Davis, CA, U.S.A.)
Ec61747 3.65 Madaiah et al., 1986
V687 3.61
Ec130046 2.57
Labonita 2.31
Dryzbha 2.58
Selection-4 4.45
Ogasta 3.47
Selection-22 3.41
Ec154892 1.58
(in the Bangalore area of India)
Fresh tomato (June–August) 3.8–6.6 Heinonen et al., 1989
Fresh tomato (October–March) 2.6–3.1
(in Finland)
Fresh tomato 0.723 Tee and Lim, 1991
(in Malaysia)
Fresh tomato (Solanum Lycopersicum, Mill) Granado et al., 1992
Common type 1.54–2.69
Canary Islands type 1.32–1.88
Pear type 54.33–70.21
(in Spain)
Tomato juice 1.09–5.13 Tavares and Rodriguez–
(in Campinas, Brasil) Amaya, 1994
Fresh tomato
(in U.S.A.) 8.25–10.29 Tonucci et al., 1995
Red varieties: Hart and Scott, 1995
Cherry 3.780
‘Large’ 2.270
‘Salad’ 2.547
Flavourtop 5.653
Tigerella 1.582
Ida F1 hybrid 1.711
Shirley F1 2.347
Craig 3.907
Moneymaker 4.255
Allicanti 4.037
Beefsteak 4.833
Yellow varieties:
Sungold 0.528
Gold sunrise 0.021
(in U.K.)
Ohio-8245 9.65–10.21 Sharma and Le Maguer, 1996
92-7136 7.72–7.80
92-7025 6.23–6.59
H-9035 10.22–10.16
CC-164 10.64–10.76
(in Canada)
5
TABLE 3
Carotenoids of Regions of Tomato at Different Ripe Stage
Number of days ripened
Region of fruit 4 8 12 16 20
Total carotenoids (mg/100 g)
Outer pericarp 4.40 7.84 8.64 8.64 8.40

Inner pericarp 2.96 4.40 4.40 4.00 4.40
Locular contents 4.80 4.16 4.00 6.56 6.32
Carotene (mg/100 g)
Outer pericarp 0.23 0.23 0.18 0.18 0.26

Inner pericarp 0.22 0.12 0.15 0.18 0.39
Locular contents 0.69 0.71 0.60 0.57 0.55
Total carotenoids/carotene
Outer pericarp 15 34 47 47 23
Inner pericarp 14 37 30 22 11
Locular contents 7 6 7 12 12
Data from McCollum, 1955.
tene, and ξ-carotene. These contain no oxy- lycopene takes the form of elongated, needle-
gen and are usually orange and red in color. like crystals that are responsible for the typi-
Carotenoid species in the second class are cal bright-red color of ripe tomato fruits.
the xanthophylls (e.g., β-cryptoxanthin, Lycopene is more soluble in chloroform,
lutein, and zeaxanthin), which are oxygen- benzene, and other organic solvents than in
ated derivatives and contain one or more water.
oxygenated group substituents at particular
sites on the terminal rings. The two classes
of carotenoids share common structural fea- B. Chemical Structure
tures, such as polyisoprenoid structure and a
series of centrally located conjugated double The chemical structures of some princi-
bonds. In tomato fruits, more than 21 pig- pal carotenoid species in tomatoes are shown
ments in the carotenoid class have been iden- in Figure 1. Lycopene, a polyene hydrocar-
tified and quantified. Lycopene is the princi- bon, an acyclic open-chain unsaturated caro-
pal hydrocarbon carotenoid in tomatoes with tenoid having 13 double bonds, of which 11
lesser amounts of α-carotene, β-carotene, γ- are conjugated double bonds arranged in a
carotene, ξ-carotene, phytoene, phytofluene, linear array, has a molecular formula of
neurosporene, and lutein (Gould, 1992). The C40H56. Two central methyl groups are in the
distribution of main the carotenoid species 1,6 position, while the remaining methyl
in tomato fruits is listed in Table 4. groups are in the 1,5 position relative to each
other. A series of conjugated double bonds
A. Physical Properties constitutes a chromatophore of variable
length. Color and antioxidant activities of
The physical properties of lycopene are lycopene are a consequence of its unique
outlined in Table 5. In ripe tomato fruits, structure, an extended system of conjugated
6
TABLE 4
The Contribution of Carotenoid Species in Tomato Fruits
Carotenoid Conjugated Abs. ␭max (nm)

species Composition % double bonds In ring in hexane
Lycopene 80–90 11 — 472(457, 485, 519)

α-carotene 0.03 9 1 444(319, 348, 366)
β-carotene 3–5 9 2 450(427, 450, 477)
γ-carotene 1–1.3 7 — 450(432, 461, 490)
ξ-carotene 1–2 7 — 400(378, 400, 425)
Phytoene 5.6–10 3 — 290(275, 286, 297)
Phytofluene 2.5–3.0 5 — 350(331, 348, 366)
Neurosporene 7–9 9 — 450(415, 438, 468)
Lutein 0.011–1.1 10 — 442(424, 446, 473)
Data from Gross, 1987.
TABLE 5
Physical Properties of Lycopene
Molecular formula C40H56

Molecular weight 536.85 Da
Melting point 172–175°C
Crystal form Long red needles from a mixture of carbon
disulfide and ethanol
Powder form Dark reddish-brown
Solubility Soluble in chloroform, hexane, benzene, carbon
disulfide, acetone, petroleum ether
Insoluble in water, ethanol, methanol
Sensitivity Light, oxygen, high temperature, acids
double bonds. Lycopene owes its ruby color C. Biochemical Properties

to its extensively conjugated polyene struc-
ture. In nature, lycopene exists in all-trans Lycopene, with its acyclic structure, large
form and seven of these bonds can isomerize array of conjugated double bonds, and ex-
from the trans-form to the mono or poly-cis treme hydrophobicity, exhibits many unique
form under the influence of heat, light, or and distinct biological properties, including
certain chemical reactions. Lycopene has no as an antioxidant. Lycopene is among the
provitamin A activity due to the lack of a most efficient singlet oxygen quenchers of
β-ionone ring structure. Conversion of lyco- the natural carotenoids (Di Mascio et al.,
pene to β-carotene by chloroplasts was indi- 1989; Conn et al., 1991). There are consid-
cated by Hill and Rogers (1969). Stereoiso- erable differences in the quenching rate con-
meric forms of lycopene were described with stants (Kq) for various carotenoid species
special reference to the properties of light (Table 6). Comparison of the structures of
absorption in relation to their molecular struc- lycopene, γ-carotene, β-carotene reveals that
tures (Zechmeister, 1962). Lycopene is also the opening of the β-ionone ring increases
very sensitive to light, heat, oxygen and ac- its quenching ability. The antioxidant activi-
ids in degradation, and some metallic ions ties of lycopene and other carotenoids are
such as Cu2+, Fe3+ catalyze its oxidation. highlighted by their singlet oxygen quench-
7
FIGURE 1. Molecular structures of carotenoid species in tomato fruits.
8
TABLE 6
Comparison of Antioxidant Activities of Carotenoids: Singlet
Oxygen Quenching, Kq (m–1 s–1)
Lycopene
Singlet oxygen quenching, 109 × Kq (m–1 s–1) 31
Radical scavenging (Trolox equivalents) 2.9
Reaction of carotenoid radical anions with O2, 2
108 × k (m–1 s–1)
Other carotenoids’ singlet oxygen quenching
(109 × Kq (m–1 s–1)
γ-carotene 25
α-carotene 19
β-carotene 14
Lutein 8
Astaxanthin 24
Bixin 14
Canthaxanthin 21
Zeaxanthin 10
Data from Di Mascio et al., 1989, 1991; Conn et al., 1991, 1992;
Miller et al., 1996.
ing properties and their ability to trap peroxyl 1996). The cis-isomers of lycopene contrib-
radicals (Foote and Denny, 1968; Burton ute more than 50% to total lycopene in hu-
and Ingold, 1984). The quenching activity of man serum and tissue (Krinsky et al., 1990).
carotenoid species depends on the number The structures of some cis-isomers of lyco-
of conjugated double bonds and is influ- pene are shown in Figure 2. In general, cis-
enced to a lesser extent by carotenoid end isomers are more polar than their all-trans
groups or the nature of substituents in caro- counterparts and are less prone to crystalli-
tenoids containing cyclic end groups (Foote zation due to their kinked forms. The cis-
and Denny, 1968; Stahl et al., 1993). isomers are also more soluble in oil and
Lycopene is known to exist in a variety hydrocarbon solvents than all-trans isomers.
of geometric isomers, including all-trans, The potency of bioactivity of cis-isomers is
mono-cis, and poly-cis forms. The all-trans changed, compared with the all trans-iso-
isomer of lycopene is the most predominant mers, because of the changes in structural
geometrical isomer in fresh tomatoes and is shapes.
the most thermodynamically stable form. Most stability studies on lycopene in food
However, lycopene can undergo trans-to-cis systems concern degradation. Lycopene may
isomerization during tomato processing and be partially destroyed in processed tomato
storage. In various tomato-based foods, the products by heating in the presence of metal-
all-trans isomer is comprised of 35 to 96% lic ions (Cu2+, Fe3+, etc.) or oxygen. Lyco-
of total lycopene (Schierle et al., 1996). The pene, as a conjugated polyene, may be ex-
5-cis, 9-cis, and 15-cis isomers of lycopene pected to undergo at least two changes during
have been identified in various tomato-based tomato processing, isomerization and oxida-
foods and human tissues by NMR spectros- tion. Lycopene isomerizations have been
copy (Zumbrunn et al., 1985). The propor- shown to take place both in tomato products
tion of 5-cis-isomer in tomato-based foods and in pure lycopene forms and can take
was 4 to 27%, with considerably lower place during processing. On the other hand,
amounts of other isomers (Schierle et al., the conversion of cis-isomer to trans-form is
9
FIGURE 2. The chemical structures of cis-isomers of lycopene.
10
another reaction that can occur during the a preventative agent for cancers. Three ma-
product storage. Cis-isomers are in the un- jor directions of research have emerged: (1)
stable, whereas trans-isomers are in the stable epidemiological studies with patients with
ground state. various malignancies, (2) experiments study-
Lycopene as an efficient antiox- ing the direct effect of lycopene on tumor
idant quenches highly reactive singlet oxygen proliferation in cell lines and in animal mod-
(O2·–) and traps peroxyl radicals (ROO.). Ly- els, (3) studies on the putative biochemical
copene-oxygen radical interactions can be or immunological mechanisms of lycopene
considered as second-order rate reaction. Ly- action (Levy et al., 1995). Recent interest in
copene is less efficient and electron transfer the consumption of lycopene-rich foods as a
is observed in both directions (Conn et al., means of reducing the risk of cancer has
1992). The potential reduction is related to prompted researchers to investigate the level
the formation of the superoxide radical an- of lycopene in foods frequently consumed
ion, O2.– (Palozza, 1998). by people. Although it has no provitamin A
activity, lycopene is able to function as an
L–C + ROO·– → L–C· + ROOH antioxidant and exhibits a physical quench-
L–C + ROO·– → L–ROO–C·– ing rate constant with singlet oxygen in vitro.
The quenching constant of lycopene was
It is also possible to form peroxyl radical found to be more than double that of
capable of acting as a prooxidant and under- β-carotene and 10 times more than that of
goes autoxidation. The proposed degrada- α-tocopherol, which makes its presence in
tion pathway of lycopene is shown in the diet of considerable interest (Di Mascio
Figure 3A,B. The oxygen functions seem to et al., 1989, 1991; Conn et al., 1991;
be introduced by reactions of two main types: Devasagayam et al., 1992; Ribaya-Mercado
(1) substitution of a methyl or methylene et al., 1995). The ability of lycopene to func-
group, and (2) addition to a carbon-carbon tion as an antioxidant may contribute to a
double bond. Apparently, oxidative degra- reduction in disease risk (Sies et al., 1992).
dation can also occur at both ends of the Increasing clinical evidence supports the role
normal C40-carbon skeleton. On the basis of of lycopene as an important micronutrient,
widely accepted nomenclature rules, a de- because it appears to provide protection
graded product that does not retain the C20 against prostate cancer, lung cancer, and a
and C20' methyl groups of the original C40 broad range of epithelial cancers (Micozzi et
structure is no longer a carotenoid. While al., 1986; Olson, 1986; Levy et al., 1995).
lycopene degradation occurs, the final prod- The serum level of lycopene and the
ucts obtained are the results of direct oxida- dietary intake of tomatoes has been inversely
tive scission at the sites of double bonds in correlated with the incidence of cancer
the molecules. (Helzlsouer et al., 1989; Van Eenwyk et al.,
1991). A study in Italy with 2706 cases of
cancer of the oral cavity and pharynx, esopha-
IV. IMPORTANCE OF LYCOPENE IN gus, stomach, colon, and rectum matched
THE HUMAN DIET with 2879 controls showed that protection
for all sites of digestive-tract cancers was
A. Benefit for Human Health– associated with an increased intake in to-
Clinical Case Studies mato-based food (Franceschi et al., 1994).
The correlation between consumption of to-
There has been a growing interest in matoes and the diminished cancer risk was
investigating the ability of lycopene to act as related to an increased supply of lycopene.
11
A
FIGURE 3. Schematic of proposed reaction pathways of lycopene degradation. (A) Proposed pathways of
lycopene degradation. (Modified from Karrer and Jucker, 1950.) (B) Proposed pathway of the formation of apo-
6-lycopenal and 2-methyl-2-hepten-6-one from lycopene during photosensitization. (Modified from Ukai et al.,
1994.)
12
The intake of lycopene has been found to be having lower lycopene levels in their body.
associated with a reduced risk of cancers of In the study of Goodman et al. (1998) in-
other sites, such as the digestive tract, pan- volving 147 confirmed cervical cancer pa-
creas, and bladder (Gerster, 1997). A study tients and 191 noncancerous subjects, only
released by the University of Milan sug- lycopene was found to be significantly lower
gested that people who ate at least one serv- in cancerous patients. Kanetsky et al. (1998)
ing of a tomato-based product per day had a studied non-Hispanic, black women, involv-
50% less chance of developing digestive tract ing 32 women with cervical cancer and 113
cancer than those who did not eat tomatoes noncancerous women and measured the mi-
(Franceschi et al., 1994). A study conducted cronutrient levels in the blood. It was found
at the Harvard University found that older that women with higher levels of blood lyco-
Americans who regularly eat tomatoes were pene had consumed higher levels of lyco-
less likely to die from all forms of cancer pene and vitamin A and had one-third less
(Colditz et al., 1985). A scientific report from chance of developing cervical cancer.
Harvard School of Public Health suggested Riso et al. (1997) concluded that the
that men who ate 10 or more servings per consumption of tomato-based foods may
week of tomato products, including toma- reduce the susceptibility of lymphocyte DNA
toes, tomato sauce, and pizza sauce, were up to oxidative damage. Lycopene has a pre-
to 34% less likely to develop prostate cancer ventive effect on atherosclerosis by protect-
(Giovannucci et al., 1995). This study moni- ing plasma lipids from oxidation. Lower
tored dietary habits and the incidence rate of blood lycopene levels were also associated
prostate cancer in 48,000 men for 4 years with increased risk of coronary heart disease
and assessed over 46 different fruits and according to studies with Lithuanian and
vegetables and related products on the basis Swedish people (Kristenson et al., 1997).
of their consumption frequency. Tomato Kohlmeir et al. (1997) measured the rela-
sauce was most strongly associated with a tionship between antioxidant levels and acute
lower risk of prostate cancer. The protective heart disease in a case study of people from
effects were even stronger when the analysis 10 different European countries. It was found
focused on the risk of more advanced or that the consumption of lycopene in fruits
aggressive prostate cancer. and vegetables may reduce the likelihood of
Lycopene has been reported to increase developing heart disease. Lycopene prevents
the survival rate of mice exposed to X-ray oxidation of low-density lipoprotein (LDL)
radiation (Forssberg et al., 1959). Ribaya- cholesterol and reduces the risk of develop-
Mercado et al. (1995) reported the protec- ing atherosclerosis and coronary heart dis-
tive effects of lycopene toward oxidative ease (Agarwal and Rao, 1998). Rao and
stress-mediated damage of the human skin Agarwal (1998) suggested daily consump-
after irradiation with UV light. Peng et al. tion of tomato products providing at least 40
(1998) examined the levels of different caro- mg of lycopene was enough to substantially
tenoids, including lycopene, and vitamins A reduce LDL oxidation. This lycopene level
and E in plasma and cervical tissues ob- can be achieved by drinking just two glasses
tained from 87 women subjects (27 cancer- of tomato juice a day.
ous, 33 precancerous, and 27 noncancerous). Inhibition of cancer cell growth by lyco-
Women with cancer had lower plasma levels pene has been demonstrated extensively in
of lycopene, other carotenoids, vitamin A tissue culture experiments. Wang et al. (1989)
and E compared with pre- and noncancerous studied an in vivo model of glioma cells
women. The results indicate that women who transplanted in rats and showed that lyco-
have high levels of lycopene are less likely pene was as effective as β-carotene in inhib-
to suffer from cervical cancer than those iting the growth of the glioma cells. Tissue
13
samples taken from the Breast Cancer Se- ological functions and for metabolic pro-
rum Bank in Columbia, Missouri, were ana- cesses (Macrae et al., 1993; Jackson, 1997).
lyzed to evaluate the relationship between The U.S. FDA definition of bioavailability
carotenoid level (including lycopene), sele- of a drug is “the rate and extent to which the
nium, and retinol and breast cancer (Dorgan active substances or therapeutic moiety is
et al., 1998). Only lycopene was found to absorbed from a drug product and becomes
reduce the risk for developing breast cancer. available at the site for action” (Benet and
Other carotenoids did not reduce the risk of Shiner, 1985). The concept of bioavailability
breast cancer. In cell culture studies, of a nutrient has a close relationship with the
lycopene’s activities in inhibiting breast estimate of bioavailability of pharmaceuti-
cancer tumors were compared with those of cal compounds. The absorption of lycopene
α- and β-carotene using several human can- in the human diet is reported to be highly
cer cells (Levy et al., 1995). It was found variable and can be affected by a number of
that the cell cultures that were enhanced with dietary factors and food properties. These
lycopene had inhibited growth of breast can- factors include molecular linkage, amount
cer cells (MCF-7), and that α- and β-caro- of lycopene consumed in a meal, food ma-
tene were far less effective growth inhibitors trix in which the lycopene is incorporated,
than lycopene. co-ingestion of high amounts of dietary fi-
From mechanistic studies, two possible ber, co-ingestion of fat as a delivery me-
functions of lycopene have been proposed. dium, effects of absorption and bioconver-
Lycopene is recognized to be the most effi- sion, interaction of lycopene with other
cient singlet oxygen quencher among bio- carotenoids and nutrient components, dietary
logical carotenoids (Di Mascio et al., 1989, protein content, xanthophyll and chlorophyll
1991). Antioxidant functions are associated contents, the particle size of the material,
with lowering DNA damage, malignant trans- and genetic factors (Deshmukh and Ganguly,
formation, and reducing biological oxida- 1964; Kemmerer et al., 1974; Jayaarahan et
tive damage of proteins, lipids, and other al., 1980; Rock and Swendseid, 1992; Bowen
cell components in vitro. Lycopene has also et al., 1993; Erdman et al., 1993; Olson,
been found to increase gap-junctional com- 1994; De Pee et al., 1996; Parker, 1996;
munication between cells and to induce the Castenmiller and West, 1998; Dimitrov et
synthesis of connexin-43 (Zhang et al., 1992). al., 1988). Other characteristics that can in-
Loss of gap-junctional communication may fluence lycopene absorption are lycopene
be important for malignant transformation, location in the food matrix (lycopene-pro-
and its restoration may reverse the malig- tein complexes of cell chloroplasts vs. the
nant process. Further studies are required to crystalline form in chromoplasts) and the
gain a better understanding of the role of presence of factors that interfere with proper
lycopene in human health. micelle formation (Rock and Swendseid,
1992; Erdman et al., 1993).
B. Lycopene Bioavailability
(Absorption) in Foods 1. Effect of Trans and Cis-Isomer
Forms
In addition to knowing the amount of
lycopene present in a food, it is important to Lycopene is the most predominant caro-
know the bioavailability with respect to the tenoid in human plasma and has a half-life
absorption in the human body. Bioavailability of about 2 to 3 days in the human body
is defined as the fraction of an ingested nu- (Stahl and Sies, 1996). In human plasma,
trient that is available to the body through lycopene is an isomeric mixture containing
absorption for utilization in normal physi- 50% of the total lycopene as cis-isomers.
14
There are some indications of in vivo trans release of lycopene from the tomato tissue
to cis isomerization reactions (Sakamoto et matrix. Cooking or fine grinding of foods
al., 1994). Very little is known about the in could increase the bioavailibility of lyco-
vivo metabolism of lycopene. Boileau et al. pene by disrupting or softening plant cell
(1999) demonstrated that cis-isomers of ly- walls and disrupting lycopene-protein com-
copene are more bioavailable than trans- plexes (Hussein and El-Tohamy, 1990).
form probably because cis-isomers are more Giovannucci et al. (1995) compared the
soluble in bile acid micelles and may be differences in lycopene bioavailability from
preferentially incorporated into chylomi- fresh tomatoes with processed tomato
crons. It was suggested that cis-isomers of products, and found the lycopene serum con-
lycopene may be better absorbed than their centration was greater when consuming heat-
all-trans parent structure (Britton, 1995; Stahl processed tomato-based foods than un-
and Sies, 1996). This may be the result of processed tomatoes. It was also found that
greater solubility of cis-isomers in mixed 20 to 30% of total lycopene consisted of cis-
micelles, possibly preferential incorporation isomers when tomatoes were heated at 100°C
into chylomicrons, and a lower tendency of for 1 h (Stahl and Sies, 1992). Gartner et al.
cis-isomers to aggregate. Lycopene from (1997) found that lycopene bioavailability
heat-processed tomato juice (cis-isomers) is from paste and processed tomato juice was
absorbed more easily than lycopene from significantly higher than from unprocessed
unprocessed juice (trans-isomers). With the fresh tomatoes. This fact could be attributed
different geometrical isomers of lycopene, to a lower availability of lycopene from the
the cis-isomers (5-cis, 9-cis, 13-cis, 15-cis) raw material where it is probably bound in
are better absorbed than the all-trans form the matrix. Thermal processing such as cook-
by the human body (Stahl and Sies, 1992). ing and mechanical texture disruption such
Cis-isomers are less likely to crystallize, are as chopping are convenient ways to enhance
more efficiently solubilized in lipophilic bioavailability by breaking down sturdy cell
solutions, and are more readily transported wall structures, disrupting chromoplast mem-
within cells or in the tissue matrix. Although branes, and reducing cellular integrity, thus
processed tomato products (juice, paste, soup, making lycopene more accessible. The food
ketchup, or dehydrated tomato slices) origi- matrix (i.e., the lipid and other constituents
nally contained a low percentage of cis-iso- of chromoplasts as well as the fiber con-
mers, the concentration of cis-isomers, can tained within the tomato fruits) may contrib-
be increased by processing. Lycopene exists ute greatly to the stability of the all-trans
in both human and animal tissues as 50% form of lycopene in the fruits. This is sup-
cis-isomers because this mixture is the most ported by the observation that when whole
stable and represents an equilibrium between tomatoes are heat processed, and isomeriza-
trans- and cis-isomers (Boileau et al., 1999). tion is noted. For example, tomato sauce and
Heat treatment promotes isomerization of tomato paste contain about 90% trans-iso-
lycopene in foods, from trans to cis isomeric mers (Clinton et al., 1996; Nguyen and
forms. The degree of isomerization is di- Schwartz, 1998). The food matrix that sur-
rectly correlated with the intensity and dura- rounds lycopene when it is present within
tion of heat processing (Schierle et al., 1996; the tomato seems to prevent this isomeric
Shi et al., 1999). equilibrium from occurring.
2. Effect of Food Matrix 3. Effect of Oil Medium
The composition and structure of food Lycopene bioavailability from tomato-

have an impact on the bioavailability (ab- based food is significantly higher than from
sorption) of lycopene, which may affect the fresh tomatoes when co-ingested with oil.
15
Ingestion of tomato juice cooked in an oil (Johnson, 1997). Lycopene can undergo an
medium resulted in a two- to threefold in- in vivo isomerization mechanism. Van Vliet
crease in lycopene serum concentrations 1 et al. (1996) carried out the dioxygenase
day after ingestion, but an equivalent con- assay with β-carotene as substrate both alone
sumption of unprocessed tomato juice caused and together with increasing amounts of
no rise in plasma concentration (Stahl and lutein or lycopene and found that lutein low-
Sies, 1992). This indicated that thermal treat- ered retinal formation from β-carotene, while
ment and an oil medium are required to ex- lycopene had no effect. Prince et al. (1991)
tract lycopene into the lipophilic phase. It reported a strong decrease in serum lyco-
was assumed that heating tomato juice in the pene levels after high-dose β-carotene supple-
presence of corn oil for 1 h converts lyco- mentation, whereas another high-dose
pene from trans to cis form, thereby increas- supplementation study found a decrease in
ing its absorption by the body (Stahl and LDL lycopene content (Gaziano et al., 1995).
Sies, 1996). Evidence for carotenoid interactions during
absorption has been reported in ferrets, in
which either canthaxanthin or lycopene re-
4. Effect of Dietary Fibers duced the 0 to 24 h plasma β-carotene re-
sponse when compared with the administra-
Various types of dietary fiber were found tion of β-carotene alone (White et al., 1993;
to reduce the bioavailability of carotenoids Kostic et al., 1995). The importance and
in foods (Erdman et al., 1986). Matrix ef- mechanism of carotenoid interactions need
fects were proposed as an explanation for to be better characterized.
the lack of improvement in vitamin A status
in Indonesian women fed green leaf veg-
etables compared with a manufactured wa- 6. Enhancement of Lycopene
fer containing a similar amount of carotene Bioavailability
in oil solution (De Pee et al., 1995). Rock
and Swendseid (1992) tested the inhibitory Lycopene plasma levels increased sig-
effect of pectin, a typical dietary fiber, and nificantly in human serum when processed
their results showed that this type of dietary juice was consumed, compared with unproc-
fiber affected the absorption of dietary caro- essed tomato juice. Boiling for 1 h in the
tenoids in humans. High-methoxyl pectin is presence of 1% corn oil increased the
especially associated with the hypo- bioavailability of lycopene from tomato juice
cholesterolemic effect of dietary fibers and significantly (Stahl and Sies, 1992). The
low absorption of lycopene because of pro- bound chemical form of lycopene in toma-
moting high-viscosity conditions toes is converted by the temperatures during
processing, which makes it more easily ab-
sorbable by the body. These results suggest
5. Carotenoid Interaction that food processing may improve the avail-
ability of lycopene in tomato-based foods
In principle, interactions between caro- for absorption. Gartner et al. (1997) pointed
tenoids might occur at various stages of the out that heat treatment can improve the
absorption process, especially in high-dose bioavailability of lycopene without signifi-
conditions. Absorption of lycopene seemed cantly changing the cis-isomer composition
to be more efficient at lower dosages, and of the heat-treated foods. The lycopene
lycopene ingested with β-carotene was ab- bioavailability from tomato-based foods may
sorbed more than when ingested alone be enhanced in two ways: extraction of lyco-
16
pene from the food matrix into the lipophilic of the bonding forces between lycopene and
phase (Brown et al., 1989; Zhou et al., 1996), tissue matrix, dissociation or weakening of
and thermal processing and mechanical dis- protein-carotenoid complexes, the dissolu-
ruption of tomato tissue cells. Heat treat- tion or dispersion of crystalline carotenoid
ment leads to an increased bioavailability of complexes, and heat-improved extraction of
vegetable carotenoids after cooking. Stahl lycopene into the oily phase of the mixture,
and Sies (1992) reported that heat treatment using oil as vehicle. The effect of food pro-
of tomato juice at 100°C for 1 h resulted in cessing on lycopene bioavailability is shown
20 to 30% cis-isomers in the serum of hu- in Table 7.
mans who drank the juice. They also con- Current information on lycopene bio-
cluded that the cis-isomers were absorbed availability is limited. The pharmacokinetic
slightly better or were metabolized to a lesser properties of lycopene remain especially
extent than all-trans lycopene. It has now poorly understood. The lack of the knowl-
been generally accepted that lycopene in a edge of how lycopene functions in the hu-
lipid medium is more bioavailable than in man body and inadequate indicators have
fresh tomatoes. Cooking and reduction of made it difficult to establish a clear and sound
particle size by grinding or homogenization bioavailibility pattern of lycopene in foods.
can also reduce the matrix effect. However, At the present time, there are few validated
because thorough destruction of the matrix, methods for the quantitative assessment of
for example, by extensive cooking, could bioavailability of lycopene and other caro-
also destroy lycopene, optimum processing tenoids from food sources. The use of plasma
technology parameters should be found to density fractions enriched in chylomicrons
maximze destruction of the matrix and mini- may be useful in determining the relative
mize the destruction of lycopene. Taking efficiency of the absorption of carotenoids,
into account the disintegration of tomato tis- particularly if low doses can be accommo-
sue and induction of trans-to-cis isomeriza- dated and proportionality between the dose
tion during processing, possible mechanisms and response is demonstrated (Parker, 1996).
include the release of lycopene by thermal Further research on the bioavalability, phar-
processing that induces the disruption of the macology, biochemistry, and physiology
tomato tissue structure and cell walls, change need to be done to reveal the mechanism of
TABLE 7
Comparation of Lycopene Absorption after Ingestion of Fresh Tomatoes and Tomato
Paste (␮mol.h/l)
Fresh tomatoes Tomato paste
AUC (0–12 h) Cmax AUC (0–12 h) Cmax Gartner et al., 1997
Total lycopene 28.4 ± 1.7 11.0 ± 3.6 109.3 ± 26.6 27.9 ± 9.3
All-trans-isomers 22.6 ± 11.1 7.5 ± 2.0 79.5 ± 18.8 20.1 ± 6.1
Cis-isomers 7.3 ± 4.9 3.4 ± 2.8 29.9 ± 8.5 7.8 ± 3.4
AUC (0–104 h) AUC (0–104 h) Porrini et al., 1998
Total lycopene 38.6 31.6

All-trans-isomers 24.8 22.5
Cis-isomers 13.7 9.1
Note: AUC, area under curve response, Cmax, peak concentrations in chylomicrons after ingestion.
17
lycopene in the human diet, and the in vivo color is closely related to visual perception
metabolism of lycopene. in tomatoes (Shewfelt et al., 1988). Edwards
et al. (1983) correlated the lycopene content
of pericarp disks with the ratio of reflectance
V. ANALYSIS OF LYCOPENE FROM at 550 and 650 nm for pericarp puree. The
TOMATO SAMPLES nondestructive measurement of chromatic-
ity values with a colorimeter would be use-
The determination of the lycopene con- ful if it could accurately estimate lycopene
tent in tomatoes and tomato-based foods can concentration of tomato samples after har-
be carried out by physical and chemical vest and processing. It can provide a quick,
methods. Physical methods are based on the precise, nondestructive, on-line technique to
relation of color parameters with lycopene determine the lycopene content in tomato
concentration of the samples. In chemical products for tomato processing industry ap-
analysis, lycopene is extracted from the to- plications. D’Souza et al. (1992) developed
mato tissue and quantified. regression equations to describe the rela-
tionship between chromaticity values deter-
mined nondestructively and lycopene con-
A. Nondestructive Measurement: centration in tomato skin disks and pericarp
Color Index Method plugs. Although their model did not predict
lycopene concentrations accurately enough
Color evaluations of processed tomatoes to substitute entirely for chemical extraction
traditionally has been presented as Hunter analysis, it may be useful for estimating ly-
L*, a*, b* values. Yeatman (1969) indicated copene concentration, especially on-line
that the value b*L*/a* provided a high linear quality monitoring during the tomato pro-
correlation with visual color scores of processing.
cessed tomato products. Deep-red tomato
fruits are processed into some products with
a high degree of color, which contain high B. Extraction of Lycopene for
concentrations of lycopene. Because color is Chemical Analysis
an important quality factor, color measure-
ment has been a convenient means to de- Because lycopene is liposoluble, it is
scribe the quality of tomato products. The usually extracted with organic solvents such
deterioration in color quality may be due to as chloroform, hexane, acetone, benzene,
loss of natural pigment or the introduction of petroleum ether, or carbon disulfide, prior to
off-shades as a result of nonenzymic brown- chemical analysis for quantitative determi-
ing, which affects the final color of tomato nation. In cases where solvent extraction may
products. The effect of these changes is a be slow and incomplete, the efficient me-
lessening of visible color intensity. There chanical grinding of the tomato material can
are relatively few studies that examine the be used to facilitate complete extraction.
effects of processing conditions on the quali- Dehydrated material may be extracted with
tative and quantitative distribution of lyco- water-immiscible solvents. Moistening of
pene that may be used as major quality in- dehydrated material prior to solvent extrac-
dexes in tomato processing. tion is often necessary to get complete ex-
Nondestructive, external measurement of traction. However, the extraction processing
tomato fruit color provides a less tedious is more commonly carried out with moist
method for assessing ripening than the chemi- samples or fresh material. Extraction meth-
cal analysis of pigments. Measurement of ods for lycopene in general tend to be time-
18
consuming procedures and prone to error the OD at 460 to 470 nm (Lovric et al., 1970;
due to oxidation and losses in extraction. Mencarelli and Saltveit, 1988; Tan and
The conjugated double bonds of lycopene Soderstorm, 1988). A pure lycopene sample
cause them to be unstable components, es- is necessary for the preparation of calibra-
pecially sensitive to light, heat, oxygen, and tion curves.
acids. Extractions done in the laboratory
should be carried out in dim lighting, and in
an inert atmosphere. Heating of the lyco- D. HPLC Method
pene solution should be kept to a minimum.
To avoid oxidation and isomerization of ly- Chromatographic separation of lycopene
copene during the extraction process, anti- is the best choice for analysis and identifica-
oxidants such as quinol and neutralizing tion of lycopene, including trans-cis stereoi-
agents such as calcium carbonate, pyridine, someric sets. These methods include column
or dimethylaniline may be added. The ex- chromatography, thin-layer chromatography,
tracted sample should be stored in the dark paper chromatography, gas chromatography,
under nitrogen in the freezer (-20°C). and high-performance-liquid chromato-
After extraction, a saponification step is graphy (HPLC), using several types of
the most effective method of removing un- adsorbents and mobile phases. The widely
wanted lipids, chlorophylls, and other impu- used chromatographic procedure for the de-
rities. This procedure does not affect lyco- termination of lycopene and other carotenoids
pene because it is generally alkali stable. such as the AOAC method (AOAC, 1995)
Further purification of the fractions is car- fails to separate the cis-isomers from all-
ried out, and eventually a crystallizable ly- trans isomers. Both normal phase and re-
copene product can be obtained by fractional versed phase HPLC methods have been used
crystallization from petroleum ether or ac- to separate and quantitate provitamin A caro-
etone at low temperature. Some rapid, effi- tenoids in fruits and vegetables (Chandler
cient extraction methods for lycopene analy- and Schwartz, 1987, 1988; Quackenbush,
sis and identification have been developed 1987; Saleh and Tan, 1988; Godoy and
involving microwave solvent extraction, and Rodriguez-Amaya, 1989). Reversed phase
in pressurized accelerated solvent extraction HPLC methods utilizing C18 stationary phases
technologies in which the lycopene recover- allow for the partial separation and detection
ies from tomatoes ranged from 98 to 99.6% of cis and trans isomers of provitamin A
(Sadler et al., 1990; Benthin et al., 1999). carotenoids. Recently, some rapid, highly
efficient HPLC methods have been devel-
oped and studied extensively to isolate lyco-
C. Spectrophotometer Method pene and its isomers from tomatoes and to-
mato-based foods with minimum oxidation
Traditionally, lycopene concentration in and isomerization (Schwartz and Patroni-
tomatoes have been determined accurately Killam, 1985; Bureau and Bushway, 1986;
in the laboratory by spectrophotometric Daood et al., 1987; Zonta et al., 1987; Craft
measurements. Edwards and Lee (1986) stud- et al., 1990; Sadler et al., 1990, Stahl and
ied two solvents (acetone and methanol) as Sies, 1992; Emenhiser et al., 1995; Clinton
well as several extraction methods and ob- et al., 1996; Schierle et al., 1996; Gartner et
tained great differences in the measured caro- al., 1997; Nguyen and Schwartz, 1998; Shi
tene concentration. Now most experiments et al., 1999). A polymeric C30 stationary phase
use hexane and acetone for the extraction of has been developed that can efficiently sepa-
lycopene from tomato tissue and measure rate the geometric isomers (Sander et al.,
19
20
TABLE 8
Quantitative HPLC Determination of Lycopene in Fresh Tomatoes and Tomato Products
Extraction HPLC Column Mobile phase/detector Ref.
150 g tomato paste with 750 ml 250 × 46 mm Microsorb ODS column, Acetonitrile/methylene chloride/ Tan, 1988
ethanol (95%), filter cake was with a 15 × 32 mm guard column chloroform (70:20:10),
refluxed with petroleum ether for cartridge flow rate 2 ml/min, UV at 450 nm
5 min at 48°C
4 g tomato puree with 100 ml Analytichem C18 (5 µ) column Methanol/tetrahydrofuran/water Sadler et al., 1990
hexane/ethanol/acetone (250 × 4.6 mm) with a Supelguard (67:27:6), flow rate 2 ml/min
(50:25:25) LC-18 guard column UV at 475 nm
5–30 g tomato puree with 100 ml 5-µm column Spheri-5-RP-18 or Acetonitrile/dichloromethane/methanol Granado et al., 1992
of tetrahydrofuran, stabilized with Spheri-5-ODS column, (70:20:10), flow rate 1.8 ml/min
butylated hydroxytoluene (0.01%), (220 × 4.6 mm), with a guard UV at 450 nm
saponified with saturated column of Aquapore ODS type

methanolic potassium hydroxide RP-18 (145 × 3.2 mm, 7 µm)
50 g tomato puree in 500 ml A stainless (250 × 4.6 mm i.d.) Acetonitrile/methanol/dichloromethane/ Khachik et al., 1992
tetrahydrofuran Microsorb C18 (5-µm spherical hexane (45:10:22.5:22.5),
particles) column, with a Brownlee flow rate 0.7 ml/min, UV at 470, 455 nm
guard cartridge (30 × 4.6 mm i.d.)
5 ml tomato juice in 200 ml hexane- 5-µm RP 18 endcapped column Methanol/acetonitrile/dichloromethane/ Stahl and Sies,
dichloromethane solution (5:1) (4 × 250 mm) water (7:7:2:0.16), flow rate 1 ml/min 1992
UV at 460 nm
10 g tomato puree + 300 ml petroleum µ Bondapak C18 column Acetonitrile/dichloromethane/methanol Hakala and
ether (PE) (10 µm, 150 × 19 mm, i.d.) (45:10:45), flow rate 2 ml/min, Heinonen,
and Zorbax ODS (5–6 µm, UV at 470 nm 1994
250 × 4.6 mm, i.d.) column, with a
C18 guard column
(10 µm, 50 × 4.9 mm i.d.)
Tomato puree in 500 ml tetrahydrofuran A stainless steel Microsorb-MV Acetonitrile/methanol/methylene Tonucci et al.,
solvent (10% of tomato puree) C18 column (250 × 4.6 mm i.d.), chloride/hexane (40:20:20:20), 1995
with Brownlee C18 guard column flow rate 0.7 ml/min, UV at 450 nm
Tomato sample containing 2.5 mL Polymeric C30 reversed phase columns Methyl-t-butyl ether/methanol (38:62), Clinton et al.,
of distilled water and ethanol (containing (250 × 4.6 mm) flow rate 1 ml/min, UV at 460 nm 1996
2% butylated hydroxytoluene) was
extracted by addition of 5 ml of 10%
NaOH in methanol (30 min at 60°C)
30 g puree, 30 ml deionized water, 1 g A polymeric 5 µm C30 stationary phase Methanol/methy tert-butyl ether Lessin et al.,
calcium carbonate, 1 g Celite, 25 mL (250 × 4.6 mm i.d.) column, with a (89:11), flow rate 1 ml/min 1997
methanol, homogenized and filtered, self-packed 3 µm C30 guard column UV at 410 nm
then extraction in 25 ml methanol,
filter cake in 50 ml of acetone/hexane
(50:50), repeated
1–2 g tomato concentrate in 30 ml acetone Three 250 × 4.6 mm column packed Hexane/0.15% n-ethyldiisopropylamine, Schierle et al.,
with Nucleosil 300-5 flow rate 1 ml/min, UV at 471 nm 1997
10 g puree mixed with 50 ml methanol, Analytical 3-µm polymeric C30 Methyl-t-butyl ether/methanol (40:60), Nguyen and
1 g CaCO3, and 3.0 g Celite, then column (250 × 4.6 mm i.d.) flow rate 1 ml/min, Schwartz, 1998
extracted with acetone/hexane solution UV at 200–800 nm

(1:1), saponified with 30% KOH for 60 min
2 g tomato sample is extracted with 5 µm Vydac 201 TP 54 C18 column Methanol/tetrahydrofuran (95:5), Porrini et al.,
tetrahydrofuran solution, using butylated (250 × 4.6 mm, i.d.), fitted with C18 flow rate 1 ml/min, UV at 445 nm 1998
hydroxytoluene as antioxidant guard column
Tomato product with hexane/methylene Vydac 201HS54 reversed phase Acetonitrile/methanol/methylene Rao and
chloride solution (5:1), containing 0.015% C18 column chloride/water (7:7:2:0.16), flow rate Agarwal, 1998
butylated hydroxytoluene as antioxidant 1 mL/min, UV at 470 nm
10 g tomato puree in 100 ml 3-µm polymeric C30 column (C30 isocratic Methanol/methl-butyl ether (62:38), Shi et al.,
hexane/acetone/ethanol solution (2:1:1) separation 250 × 4.6 mm, i. d.) flow rate 1 ml/min, UV at 460 nm 1999
21
1994; Emenhiser et al., 1995, 1996; Lessin tomato juice is accelerated by high tempera-
et al., 1997). The main steps of lycopene tures and long treatment (processing and stor-
analysis by HPLC are listed in Table 8. age), due to the degradation of lycopene.
Wiese and Dalmasso (1994) reported an in-
VI. LYCOPENE STABILITY DURING crease in the hue angle of tomato juice after
TOMATO PROCESSING processing and storage, indicating a loss of
red color. The color retention in tomato prod-
More than 80% of tomatoes produced ucts is better at lower temperatures (Sherkat
are consumed in the form of processed prod- and Luh, 1976; Villari et al., 1994).
ucts such as tomato juice, paste, puree, cat- In processed tomato products, oxidation
sup, sauce, and salsa. For processing, toma- is a complex process and depends on many
toes are washed, sorted, and sliced. Sliced factors, such as processing conditions, mois-
tomatoes undergo a hot- or cold-break ture, temperature, and the presence of pro-
method for juice preparation. Juice from to- or autoxidants and lipids. For example, the
matoes is usually obtained using screw or use of fine screens in juice extraction en-
paddle extractors. In the manufacturing of hances the oxidation of lycopene due to the
other tomato products such as pulp, puree, large surface exposed to air and metal. The
paste, and ketchup, tomato juice is concen- use of coarser screens increases the retention
trated with steam coils or vacuum evapora- of color of tomato products (Kattan et al.,
tors. For canned tomatoes, sliced or whole 1956). The amount of sugar, acids, and amino
tomatoes are retorted. For dried tomato slices acids also affects the color of processed to-
and powder, tomatoes undergo a dehydra- mato products by causing the formation of
tion process. Either thermal or mechanical brown pigments (Gould, 1992). The lyco-
treatments are often involved in these pro- pene content of some commercial samples
cesses, which may affect tomato product are listed in Table 9. The deterioration in
quality. Deep-red tomato fruits that contain color that occurs during the processing of
high concentrations of lycopene would be various tomato products results from expo-
processed into products with a dark-red color. sure to air at high temperatures during pro-
However, the lycopene content in concen- cessing causing the naturally occurring all-
trated tomato products is generally lower trans lycopene to be isomerized and oxidized.
than expected, because of losses during to- Coupled with exposure to oxygen and light,
mato processing (Tavares and Rodriguez- heat treatments that disintegrate tomato tis-
Amaya, 1994). The main causes of lycopene sue can result in the destruction of lycopene.
degradation in tomato processing are isomer- These changes are due mainly to heat stress
ization and oxidation. It is widely presumed imposed by the relatively harsh thermal pro-
that lycopene in general undergoes isomer- cesses required to achieve the shelf-life sta-
ization on thermal processing. It was be- bility of processed tomato products. Studies
lieved that the changes of lycopene content on the effect of processing conditions on
and the distribution of trans-cis isomers re- qualitative and quantitative changes of lyco-
sult in the change of biological property pene degradation are necessary to determine
(Zechmeister et al., 1943; Zechmeister, 1944, the engineering parameters of lycopene dur-
1949, 1962). Determination of the degree of ing tomato processing.
lycopene isomerization would provide bet-
ter insight into the potential health benefits A. Effect of Temperature on
of the processed tomato products. The deg- Lycopene Degradation
radation of lycopene and the color loss of
processed tomato products are affected by a As shown in Table 10, heating tomato
number of factors. The loss of color in juice for 7 min at 90°C and 100°C resulted
22
TABLE 9
A Survey of Lycopene Content in Some Commercial Samples
Industrial sample Lycopene (mg/100 g wet basis) Sources
Tomato juice 5.8–9.0 Lindner et al., 1984

(in Israel)
Tomato ketchup 9.9 Heinonen et al., 1989
(in Finland)
Tomato puree 19.37–8.93 Tavares and Rodriguez-Amaya, 1994
Tomato paste 18.27–6.07
Tomato ketchup 10.29–41.4
Tomato juice 61.6
(in Campinas, Brasil)
Tomato soup 8.0–13.84 Tonucci et al., 1995
Tomato juice 9.70–11.84
Tomato paste 51.12–59.78
Tomato puree 16.67
Tomato sauce 6.51–19.45
(in U.S.A.)
Tomato pulp 12.09–12.83 Sharma and Le Maguer, 1996
Pulp thick fraction 41.91–42.82
Pulp thin fraction 3.98–4.08
(in Canada)
TABLE 10
Lycopene Loss Rate in Tomato Juice during Heating
Lycopene loss (%)

Heating
temperature (°C) Heating time 1 min Heating time 3 min Heating time 7 min
90 0.6 0.9 1.1
100 0.9 1.4 1.7
110 2.2 3.2 4.4
115 2.7 4.5 7.0
118 3.7 6.0 9.1
121 4.6 7.3 10.6
124 5.5 8.5 12.5
127 6.5 9.9 14.6
130 7.4 11.5 17.1
Data from Miki and Akatsu, 1970.
in a 1.1 and 1.7% decrease in lycopene con- loss of lycopene increased to 60 and 90%
tent, respectively. At higher temperatures the (almost complete decolorization), respec-
lycopene content decreased even more, and tively, in the presence of small amounts of
losses of 17.1% were observed at 130°C copper. Cole and Kapur (1957a) reported
(Miki and Akatsu, 1970). Temperature af- that the oxidative degradation of lycopene at
fects the nature and extent of lycopene break- 50°C leads to fragmentation of the molecule,
down. In solution, 26.1% of the lycopene giving acetone, methylheptenone, laevulinic
was lost when heated for 3 h at 65°C, and aldehyde, and probably glyoxal as products.
35% was lost when heated for 3 h at 100°C It has also been reported that serious
(Table 11). Copper stearate catalyzes the losses of lycopene can occur when the hold-
oxidation of lycopene. At 65 and 100°C, the ing times at high temperature are long. The
23
TABLE 11
Oxidation of Lycopene Loss in Hexane and Light Petroleum
Solution
Temperature Time Lycopene loss in Copper-catalyzed

(°C) (h) solution (10 mg/l) (%) loss (29 mg/l) (%)
0 0 0
1 15.0 25
65 2 20.0 45
3 26.1 60
0 0 0
1 20.0 40
100 2 28.5 75
3 35.0 90
Data from Cole and Kapur, 1957a.
high temperature and large amount of air C. Effect of Light Density on

dissolved in the tomato juice during the Lycopene Degradation
breaking and straining operations can quickly
destroy substantial amounts of lycopene. Increasing illumination and temperature
During evaporation (especially using a increased the loss of lycopene. The magni-
vacuum), smaller losses were noticed because tude of lycopene destruction by increased
the deaeration that occurred as soon as the lighting is less severe than that by increased
juice entered the evaporating system hindered temperature (Table 13).
oxidative destruction of lycopene. The results
suggest that length of heating is a critical
factor controlling the degradation of lyco- D. Effect of Dehydration Techniques
pene. It appears that the deaeration and “high on Lycopene Degradation
temperature–short duration” heat treatment of
tomato juice can have beneficial effects on The loss of lycopene during the dehy-
the retention of tomato juice quality. dration of tomatoes is an important commer-
cial concern. Total lycopene content in fresh
and dehydrated tomatoes is shown in Table
B. Effect of Oxygen on Lycopene 14. The dehydration of tomato slices is typi-
Degradation cally carried out at high temperatures over
an extended period under vacuum. The gen-
Monselise and Berk (1954) first reported eral tendency of lycopene retention in
the oxidative destruction of lycopene dur- samples decreased slightly during the dehy-
ing the processing of tomato puree. The dration processes. During osmotic dehydra-
most important contributing factor was the tion, lycopene content remains essentially
availability of oxygen. More than 30% of constant. After osmotic-vacuum drying, to-
the lycopene was degraded when heated at tal lycopene retention in tomatoes was greater
100°C in the presence of oxygen, while than in those dehydrated by vacuum drying.
only 5% was lost in the presence of CO2 The probable explanation is that the sugar
(Table 12). solution in osmotic dehydration keeps oxy-
24
TABLE 12
Effect of Oxygen on Rate of Loss of Lycopene on
Heating Tomato Pulp at 100°C
Condition Time of heating (h) Loss (%)
Dark and CO2 0 0

0.5 4.6
1 4.9
2 5.0
3 5.1
Dark and O2 0 0
1 14.0
2 23.7
3 30.1
Daylight and CO2 0 0
1 5.4
2 8.6
3 11.3
Daylight and O2 0 0
1 15.1
2 25.9
3 33.1
Data from Cole and Kapur, 1957b.
TABLE 13
Combined Effect of Illumination and
Temperature on Loss of Lycopene in
Tomato Pulp in Air for 3 h
Condition Lycopene loss (%)
100-ft candles, 60°C 18.9

100-ft candles, 100°C 34.9
150-ft candles, 100°C 38.6
100-ft candles, 110°C 53.9
150-ft candles, 110°C 58.3
Data from Cole and Kapur, 1957b.
gen from tomatoes and reduces the oxidation E. Lycopene Loss during Tomato
of lycopene in the tomato tissue matrix at low Peeling Treatments
operating temperatures. Conventional air dry-
ing decreases lycopene retention in tomato Peeling is an important operation in to-
samples due to the influence of heat and oxy- mato processing. Before tomatoes pass over
gen. Heat treatment disintegrated tomato tis- mechanical peel eliminators to remove skin,
sue and increased exposure to oxygen and they usually undergo a chemical or physical
light, which resulted in the destruction of ly- treatment. Chemical treatments include lye
copene (Shi and Le Maguer, 1999 a, b) peeling in a hot solution of NaOH or CaCl2.
25
TABLE 14
Total Lycopene and Cis-Isomer Content in the Dehydrated Tomato
Samples
Total lycopene Lycopene loss All-trans Cis-isomers

Sample (␮g/g dry basis) (%) isomers (%) (%)
Fresh tomato 755 a 0 100 0

Osmotic treatment 755 a 0 100 0
Osmo-Vac dried 737 b 2.4 93.5 6.5
Vac-dried 731 c 3.2 89.9 10.1
Air-dried 726 d 3.9 84.4 16.6
Note: Data presented as means of triplicate determinations.

Means in a column not sharing common superscript (a–d) are significantly different
(p < 0.01).
Data from Shi and Le Mague., 1999b.
Physical treatments include steam peeling 7.5%. Reis and Stout (1962) reported about
by high-pressure or superheated steam. Some a third of the tomato volume delivered to
new peeling methods have been developed, processing plants can be lost as waste. The
such as cryogenic scalding with liquid nitro- wastes during tomato processing are mainly
gen, liquid air or Freon 12, or infrared peel- seeds, pericarp tissue, and skin residues. The
ing with infrared radiation as a heat source. epidermal area of tomatoes (skin and outer
During lye peeling, the hot solution dissolves pericarp tissue) contains more than 80 to
the epicuticular waxes, penetrates the epi- 90% of the total lycopene in the tomatoes. It
dermis, digests middle lamella, cell walls, is clear that a large quantity of lycopene is
and causes separation of the skin (Gould, normally discarded as tomato processing
1992). The concentration of lye solution and waste. This processing waste can be an im-
temperatures used in the food industry range portant source of lycopene for the food in-
from 8 to 25% and from 60 to 100°C, re- dustry.
spectively, depending on the commodity,
cultivar, and fruit maturity (Floros and
Chinnan, 1989). With the steam scald peel- F. Lycopene Isomerization in Food
ing process, tomatoes are exposed to live Processing
steam long enough to loosen the peel but not
so long as to cause flesh softening or cook- The reduction of lycopene content and
ing. In recent years, the application of high- trans-cis isomerization result in a reduction
pressure steam for short time in combination in biological property (Zechmeister et al.,
with mechanical peel eliminators has be- 1965). Lycopene isomer distribution in some
come accepted in most tomato processing commercial tomato products is listed in Table
operations (Corey, 1986). Both chemical and 15. However, actual determination of the
steam peeling procedures cause relatively degree of isomerization resulting from pro-
high losses of the edible parts of the outer cessing has been limited. The color changes,
pericarp layer of the tomato fruits. Schulte usually used as a quality index, cannot be
(1965) found that peeling tomatoes with the explained by lycopene isomerization to cis-
infrared method produced a peel loss of 5.3%, isomers. It is generally accepted that the all-
while the steam method had a peel loss of trans form of lycopene has the highest sta-
26
TABLE 15
Lycopene Isomers in Various Commercial Tomato Products
Total
lycopene
(mg/100 g All-trans 5-cis 9-cis 13-cis Other cis
Sample wet basis) (%) (%) (%) (%) (%)
Tomato paste
(‘Tomatenmark’, Panocchia, Italy) 52 96 4 <1 <1 <1
Tomato paste
(‘Maracoli’, Kraft, Germany) 3.7 91 5 1 2 <1
Tomato ketchup
(‘Hot Ketchup’, Del Monte, Italy) 9.5 88 7 2 3 1
Tomato ketchup
(‘Hot Ketchup’, Heinz, USA) 3.0 77 11 5 7 1
Instant meal
(‘Eier-Ravioli’, Hero, Switzerland) 0.6 76 8 5 6 5
Sauce
(‘Hamburger Relish’, Heinz, 3.0 93 5 <1 3 <1
The Netherlands)
Sauce
(‘Sauce Bolognaise’, Barilla, Italy) 9.2 67 14 6 5 8
Canned tomatoes
(‘Chris’, Roger Sud, Italy) 7.1 84 5 3 5 3
Data from Schierle et al., 1996.
bility and the cis-isomers have the lowest pene isomers would provide better insight
stability. Bioactivity potency depends on the into the potential nutritional quality and
extent of isomerization and oxidation as well healthy benefit of the processed tomato prod-
as the stability when tomato-based products ucts, and more accurately predict the lyco-
are subjected to processing and storage pene bioactivity than just a total lycopene
(Zechmeister, 1962; Khachik et al., 1992; content with no knowledge of its isomeric
Stahl and Sies, 1992; Emenhiser et al., 1995; composition. Controlling lycopene isomer-
Wilberg and Rodriguez-Amaya, 1995). Thus, ization behavior during production and stor-
isomerization would lead to degradation of age of tomato products can be of benefit in
lycopene. Although the processing of toma- improved product color and quality.
toes by cooking, freezing, or canning does
not usually cause significant changes in total
lycopene content, it is widely assumed that 1. Effect of Thermal Processing on
lycopene undergoes isomerization after ther- Lycopene Isomerization
mal processing. Heat, light, acids, and other
factors have been reported to cause isomer- Lycopene isomers in various thermally
ization of lycopene (Boskovic, 1979; Schierle processed tomato products are listed in Table
et al., 1996; Nguyen and Schwartz, 1998; 16. Lycopene isomerization and the amount
Shi et al., 1999). A true assessment of the of cis-isomers increased as a function of
nutritional quality and healthy benefit of processing time during heating of tomatoes.
processed tomato-based food depends not Heat treatment clearly increased the percent-
only on the total lycopene content, but also age of the cis-isomers. It is obvious from
on the distribution of lycopene isomers. these results that food processing can en-
Characterization and quantification of lyco- hance cis-isomerization in tomato-based
27
TABLE 16
Lycopene Isomers in Various Thermally Processed Tomato
Products
Total lycopene Cis-isomers

Sample (mg/100 g, dry basis) (%)
Peeled tomato 149.89 5.37

Tomato juice (hot-break) 161.23 5.98
Tomato juice (retorted) 180.10 3.56
Tomato (whole, retorted) 183.49 3.67
Tomato paste (concentrated) 174.79 5.07
Tomato paste (retorted) 189.26 4.07
Tomato soup (retorted) 136.76 4.34
Tomato sauce (retorted) 73.33 5.13
Data from Nguyen and Schwartz, 1998.
foods. Heating tomato-based foods in oil had 2. Effect of Dehydration Technology

a bigger effect on lycopene isomerization on Lycopene Isomerization
than heating in water. Therefore, this indi-
cates, that not only the duration and tem- Studies on the effect of dehydration
perature of heat treatment, but also the food methods on lycopene degradation show a
matrix components such as oil or fat influ- significant increase in cis-isomers and a si-
ence the lycopene isomerization (Table 17). multaneous decrease in the all-trans isomers
TABLE 17
Effect of Heating Treatment on Lycopene Isomerization
in Aqueous and Oily Dispersions of Tomato Paste (70°C)
Heating time All-trans 5-cis 9-cis 15-cis Other cis

(min) (%) (%) (%) (%) (%)
In water
0 92.6 4.5 0.9 1.6 0.5
15 92.3 4.4 0.9 1.6 0.5
30 88.1 5.1 2.1 2.3 2.5
60 87.1 5.2 2.2 2.7 3.0
120 86.2 5.5 2.7 2.6 3.1
180 83.4 6.1 3.6 3.2 3.8
In olive oil
0 87.4 4.8 4.4 3.0 0.5
30 85.2 5.8 5.5 2.9 0.5
90 83.5 6.2 5.9 3.3 1.2
120 80.3 7.0 6.9 3.2 2.6
180 76.7 8.1 8.8 3.1 3.3
Data from Schierle et al., 1996.
28
(Table 14). Cis-isomers were not detected in tomato-based products are subjected to pro-
the fresh tomato samples. Chandler and cessing (Zechmeister 1962; Khachik et al.,
Schwartz (1987, 1988) and Rodriguez- 1992; Emenhiser et al., 1995; Wilberg and
Amaya and Tavares (1992) also reported no Rodriguez-Amaya, 1995; Stahl and Sies,
cis-isomers in the fresh tomato samples after 1996). Dehydration and increase of surface
HPLC analysis. The cis-isomers appeared in area, for example, in powdered or lyophilized
processed tomato samples (Figure 4). tomato products, generally leads to very poor
It was observed that fewer cis-isomers stability. Osmotic solution (with sugar) re-
were present in osmotically dehydrated to- maining on the surface layer of tomato pre-
matoes when compared with those directly vents oxygen from penetrating and oxidiz-
air dried and vacuum dried. The highest ing lycopene. Osmotic treatment could reduce
amount of cis-isomers were found in air- lycopene losses compared with other dehy-
dried tomato samples (Shi et al., 1999). Miers dration methods. These results will be useful
et al. (1958) mentioned that the amount of in developing new dehydration techniques
cis-isomers exceeds those present in the ini- and improve product quality (Shi et al., 1999).
tial tomato material and in osmotically treated
tomato samples when dehydrated by con- G. Lycopene Degradation and Color
ventional methods. The cis-isomers were Changes of Tomato-Based Foods
formed in processed tomato samples and
increased with temperature and time during Color parameters measure and the rela-
dehydration. Each sample dehydrated by tion with food quality have been studied
different methods had a negative factor fa- extensively (Francis et al., 1975; Little, 1975;
voring isomerization and/or oxidation of the Clydesdale, 1997). A number of publica-
lycopene (e.g., oxygen permeability, light tions have reported the tendency of lycopene
exposure, and the presence of some metals compounds to isomerize from one form to
in the processing system). A large loss of another with accompanying color changes
lycopene during processing would indicate (Wong and Bohart, 1957). It seems possible
a longer and more drastic procedure, par- that the naturally occurring all-trans lyco-
ticularly in the thermal dehydration steps. pene isomerizes to the less red cis-isomers
Dehydration of tomatoes at a mild tempera- with a corresponding change in absorption
ture does not usually cause significant losses spectra during processing of tomato prod-
in total lycopene content (Nguyen and ucts (Miers et al., 1958). Results of color
Schwartz, 1998), but the conversion of trans- parameters L*, a*, and b* together with the
to cis-isomers always occurred in the dehy- ratio a*/b* and the overall color difference
drated products. In the osmotic treatment, (DE) of the dehydrated tomato products are
the predominating mechanism may be presented in Table 18. Tomatoes with os-
isomerization of lycopene. Because the total motic treatment had more red color than
lycopene content remained almost constant, those treated by air drying and vacuum dry-
only the distribution of all-trans- and cis- ing, which indicated there was more lyco-
isomers was changed. In air drying, isomer- pene in the samples.
ization and oxidation were two strong fac- Wiese and Dalmasso (1994) reported an
tors that simultaneously affected the total increase in the hue angle of tomato juice
lycopene content, distribution of trans- and after processing and storage, indicating a
cis-isomers, and biological potency. The loss of red color. Color retention in tomato
changes in lycopene content and the distri- products is better at lower temperatures
bution of trans-cis isomerization will result (Sherkat and Luh, 1976; Villari et al., 1994).
in a reduction in biological potency when A slightly better color can be observed in the
29
A
FIGURE 4. HPLC chromatograms of trans- and cis-isomers of lycopene in osmotically dehydrated tomatoes(A)
and in air-dried tomatoes (B) (Shi and Le Maguer, 1999b).
samples dehydrated at low temperatures. The trans- to cis-isomers may have caused the
color differences between the samples were a*/b* value to stay at a higher level (Wong
not readily discernible by visual evaluation. and Bohart, 1957). The color quality, a*/b*
There was no significant difference between values, remained essentially unchanged dur-
the Hunter color value a* of the different ing the osmotic treatment, but there were
dehydrated tomatoes. This was attributed to lower values of a*/b* in the conventional
the formation of lycopene crystals in the air-dried sample. Product color showed pro-
tomato tissue matrix after heating in the de- gressive deterioration of overall color qual-
hydration processes. After heating, the spec- ity (DE) in conventional air drying. The
trum did not change significantly. The color average color reflectance reading for osmoti-
measurement did not show the relative com- cally dehydrated fruits had color character-
position of all-trans and cis-isomers. An in- istics close to those of the fresh material.
crease in cis-isomers would indicate a change The L* and a* values decreased for the other
of lycopene bioactivity potency, but would dehydration treatments. The trends in lyco-
not show up as a significant difference in pene degradation and color parameters for
color. Lycopene content and the ratio of the different dehydrated tomato products
30
FIGURE 4B
were not directly correlated (Figures 5 and dessication and packaging in an inert atmo-
6). Tomatoes with the osmotic treatment had sphere (e.g., nitrogen) favored color reten-
more red color than those treated by air dry- tion, which the presence of air caused a loss
ing and vacuum drying, which indicated there of lycopene and color fading by oxidation
was more trans-isomer lycopene in the (Kaufman et al., 1957). Analyses of the stor-
samples. age-study samples for lycopene (Wong and
Bohart, 1957) showed that air-packed
samples retained the lowest lycopene levels,
H. Lycopene Stability during and all air-packed samples showed a pro-
Storage of Tomato-Based Food gressive loss of lycopene throughout the stor-
age period. The most important factor con-
The fate of lycopene in processed to- tributing to degradation is availability of
mato products is influenced by storage fac- oxygen during storage. With careful selec-
tors. The percent retention of lycopene de- tion of storage conditions to protect the prod-
creased at high temperatures and in the ucts from such facts as air by storing in an
presence of oxygen after longer periods in inert atmosphere or under vacuum, it is pos-
storage (Table 19). A study on vacuum-dried sible to retain initial color levels during stor-
tomato powder showed that in-package age.
31
TABLE 18
Color Values of Dehydrated Tomato Samples
Color parameters
Samples and
dehydration condition L* a* b* a*/b* ⌬E L*b*/a*
Fresh material 38.4a 37.7a 16.1a 2.3a 56.2a 16.4a
IM tomatoes
Osmotic dehydration at 25°C 38.4a 37.7a 16.1a 2.3a 56.2a 16.4a
Osmo–Vac drying at 55°C 36.7a 35.2a 16.9a 2.1a 53.6a 17.2a
Vacuum drying at 55°C 34.2a 34.3a 17.4a 1.9a 51.5b 17.4b
Air drying at 95°C 29.9b 33.2b 19.9b 1.7b 48.9c 18.1c
Dehydrated tomatoes
Osmo–Vac drying at 55°C 31.4c 36.4c 18.3b 1.7b 48.1b 18.3c
Vacuum drying at 55°C 28.3d 25.6d 18.2b 1.4b 42.3c 20.1d
Conventional air drying at 90°C 25.6e 23.2e 18.9b 1.2b 39.4d 20.9e
Note: Data presented as means of triplicate determinations.

Means in a column not sharing common superscript (a–e) are significantly different (p < 0.01).
Data from Shi et al., 1999b.
FIGURE 5. Comparison of lycopene degradation in the different dehydration processes (F, fresh tomato,
O.T., osmotic treatment, O.V., osmo-vacuum-drying, V, vacuum-drying, A.D., air drying) (Shi et al., 1999).
I. Antioxidant Application and storage is oxidation. Careful application

of suitable antioxidants (e.g., ethoxyquin,
The mechanism of lycopene destruction ascorbic acid, sodium acid pyrophosphate)
depends on many parameters during food at appropriate levels could have beneficial
processing and storage. The main cause of results (Granado et al., 1992; Clinton et al.,
damage to lycopene during food processing 1996; Porrini et al., 1998). Low storage tem-
32
FIGURE 6. Comparison of color changes in the different dehysdration proceeses (F, fresh tomato, O.T.,
osmotic treatment, O.V., osmo-vacuum drying, V, vacuum drying, A.D., air drying) (Shi et al., 1999).
TABLE 19
Total Lycopene Retention in Tomato Powder Stored in Different
Atmospheres, Temperatures for Different Time Lengths
Storage period (days) Storage conditions Total lycopene retention (%)
Fresh tomato powder 100

30 N2, 2°C 85.5
N2, 20°C 90.0
Air, 2°C 37.0
Air, 20°C 46.3
80 N2, 2°C 66.3
N2, 20°C 78.5
Air, 2°C 11.3
Air, 20°C 28.7
160 N2, 2°C 54.2
N2, 20°C 76.5
Air, 2°C 9.35
Air, 20°C 25.5
210 N2, 2°C 53.3
N2, 20°C 69.8
Air, 2°C 8.55
Air, 20°C 23.0
385 N2, 2°C 53.0
N2, 20°C 65.8
Air, 2°C 8.2
Air, 20°C 21.8
Data from Lovric et al., 1970.
perature, low oxygen content, low light, low VIII. FUTURE DEVELOPMENT
water activity, and low moisture content in
storage will also have a limiting effect on the Lycopene is particularly important be-
oxidation of lycopene. cause it has a dual influence on production
33
and quality as a natural color and nutrient for pene absorption from the diet. The degrada-
the food and pharmaceutical industries. Color tion of lycopene is extremely important to
has a strong influence on the buying behav- tomato-based food industries. Lycopene
ior of consumers. Color also serves as a needs to be protected from excessive heat
measure of total quality for tomato and to- and extreme pH conditions, exposure to light,
mato products. Consumers, researchers, and oxygen, and lipid-degrading enzymes in or-
the food industry have also dramatically in- der to prevent its oxidation and isomeriza-
creased their interest and awareness of the tion. Processing technology should be opti-
health benefits of lycopene from tomatoes. mized to prevent lycopene oxidation and
Lycopene can be considered as “the vitamin isomerization.
of the twenty-first century” because of its Lycopene and other carotenoids have
significant physiological effect on the hu- been accepted as natural colorants for food
man diet. Lycopene can play an important use for a long period of time without toxi-
role in human health and provide protection cological evidence in the same manner as
against a broad range of epithelial cancers. vegetable and fruit products. Lack of sound
It is very important to better understand information regarding toxicology and bio-
the development of the tomato fruit on the availibility data would limit the develop-
plant, that is, both fruit number, size devel- ment of food safety regulations. Further
opment, and the effect on lycopene content. studies will be necessary to provide a tox-
With this knowledge, we will be able to icological evaluation of lycopene and infor-
enhance tomato yield and we will better mation on how lycopene interacts with other
understand what affects the quality of the nutrients.
fruit. It may be that the fruit development Consumer demand for healthful food
processes leading up to fruit maturation may products provides an opportunity to develop
also have an effect on fruit components such a market for food and pharmaceutical-grade
as lycopene. Lampe and Watada (1971) and lycopene products. Industrial production of
Mohr (1979) indicated that lycopene content lycopene from tomatoes is in high demand
was high in tomato fruits that have a high by phamarceutical companies and for func-
pigment concentration index. At present, tional food development. Little information
lycopene content is not a critical factor in on lycopene commercial production is avail-
tomato production research. More efforts are able. At present, a large quantity of skin and
required to produce lycopene-rich tomato outer pericarp tissue are normally discarded
varieties and improve lycopene content as tomato processing waste in the peeling
through proper management and cultural procedure of the tomato processing. Some
practices. The lycopene content in tomato new technologies such as membrane separa-
fruits may be enhanced by improved tech- tion technology, supercritical fluid CO2 ex-
niques in fertilizer, harvest time, and variety traction technology, and solvent extraction
selection. This focus on lycopene may also technology are being applied to scale up the
lead to higher-quality tomatoes produced in lycopene production (Zelkha et al., 1998).
greenhouses during winter. An environmentally friendly extraction and
The availability of lycopene in foods is purification procedure on an industrial scale
influenced not only by its isomeric form, but with minimal loss of bioactivity is highly
also by the food matrix, the presence of suf- desirable for the food, feed, cosmetic, and
ficient bulk lipid for solubilization of re- pharmaceutical industries. High-quality ly-
leased lycopene, and the presence of inter- copene products that meet food safety regu-
fering factors in the lumen such as pectin lations will offer potential benefits to the
and other dietary fibers. These factors should food industry. A successful commercializa-
be evaluated in an attempt to maximize lyco- tion of high-value lycopene production may
34
improve the competitiveness of tomato-based dicinal plants. J. Chromatogr. A. 837, 211–
products and lycopene products in the global 219.
market. 8. Britton, G. 1995. Tructure and properties of
carotenoids in relation to function. FASEB J.,
9, 151–1558.
ACKNOWLEDGMENTS 9. Boileau, A. C., Merchen, N. R., Wasson, K.,
Atkinson, C. A., and Erdman, J. W. 1999.
Suggestions and assistance from Greg Cis-lycopene is more bioavailable than trans-
Poushinsky, Humayoun Akhtar, Don Mer- lycopene in vitro and in vivo in lymph-cannu-
cer, Albert Liptay (Agriculture and Agri- lated ferrests. J. Nut., 129, 1176–1181.
Food Canada), Sam Wang, and Yukio 10. Boskovic, M. A. 1979. Fate of lycopene in
Kakuda (University of Guelph) are appreci- dehydrated tomato products: carotenoid
ated. isomerization in food system. J. Food Sci.,
44, 84–86.
11. Bouvier, F., Backhaus, R. A., and Camara, B.
1998. Induction and control of chromoplast-
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Critical Reviews in Food Science and Nutrition

ISSN: 1040-8398 (Print) 1549-7852 (Online) Journal homepage: http://www.tandfonline.com/loi/bfsn20

Lycopene in Tomatoes: Chemical and Physical

John Shi & Marc Le Maguer

To link to this article: https://doi.org/10.1080/10408690091189275

Published online: 03 Jun 2010.

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Lycopene in Tomatoes: Chemical and Physical

* Author to whom correspondence should be addressed. E-mail: ShiJ@EM.AGR.CA; Fax: (519)837-9472

KEY WORDS: bioactivity, bioavailability, degradation, isomerization, lycopene, oxidation,

I. INTRODUCTION jelly-like parenchyma cells that surround the

Fresh tomato fruit 0.72–20

Data from Beerh and Siddappa, 1959; Gross, 1987, 1991;

Juice from ripe tomatoes 3.71 Beerh and Siddappa, 1959

Number of days ripened

Total carotenoids (mg/100 g)

Outer pericarp 4.40 7.84 8.64 8.64 8.40

Outer pericarp 0.23 0.23 0.18 0.18 0.26

Data from McCollum, 1955.

Carotenoid Conjugated Abs. ␭max (nm)

Lycopene 80–90 11 — 472(457, 485, 519)

Data from Gross, 1987.

Molecular formula C40H56

double bonds. Lycopene owes its ruby color C. Biochemical Properties

2. Effect of Food Matrix 3. Effect of Oil Medium

The composition and structure of food Lycopene bioavailability from tomato-

Fresh tomatoes Tomato paste

AUC (0–12 h) Cmax AUC (0–12 h) Cmax Gartner et al., 1997

AUC (0–104 h) AUC (0–104 h) Porrini et al., 1998

Total lycopene 38.6 31.6

Extraction HPLC Column Mobile phase/detector Ref.

without the consent of the publisher is prohibited.

without the consent of the publisher is prohibited.

Industrial sample Lycopene (mg/100 g wet basis) Sources

Tomato juice 5.8–9.0 Lindner et al., 1984

Lycopene loss (%)

Data from Miki and Akatsu, 1970.

Temperature Time Lycopene loss in Copper-catalyzed

Data from Cole and Kapur, 1957a.

high temperature and large amount of air C. Effect of Light Density on

Condition Time of heating (h) Loss (%)

Dark and CO2 0 0

Data from Cole and Kapur, 1957b.

Condition Lycopene loss (%)

100-ft candles, 60°C 18.9

Data from Cole and Kapur, 1957b.

Total lycopene Lycopene loss All-trans Cis-isomers

Fresh tomato 755 a 0 100 0

Note: Data presented as means of triplicate determinations.

Data from Shi and Le Mague., 1999b.

Data from Schierle et al., 1996.

Total lycopene Cis-isomers

Peeled tomato 149.89 5.37

Data from Nguyen and Schwartz, 1998.

foods. Heating tomato-based foods in oil had 2. Effect of Dehydration Technology