Beruflich Dokumente
Kultur Dokumente
ilic ,
Arda Serpen,
Vural Gokmen,*
,
and Jelena Vanc etovic
INTRODUCTION
Maize is one of the most diverse grain crops found in nature and
one of the most widely cultivated cereals in the world. Also,
maize and milled maize including meals, flours, and bran have
been integral parts of the diet of all socioeconomic classes world-
wide. Native white and pigmented maize have been cultivated in
South America, mainly in Peru and Bolivia, and have been used
for the preparation of traditional drinks and desserts long before
European settlers arrived. However, multicolored, red, purple,
blue, and black maize kernels are currently produced only in small
amounts for making specialty foods or for use in ornamentation
due to their colorful appearance.
1
Pigmented maize contains many secondary metabolites, such
as phenolic compounds and carotenoids. Phenolic acids and
flavonoids represent the most common form of phenolic
compounds found in whole maize kernel, with a number of
types that exist as soluble free and conjugated or insoluble bound
forms. More than 5000 flavonoids have been identified in
nature.
2
The most significant function of the sap-soluble
flavonoids is their ability to impart color to the plant in which
they occur. Flavonoids are responsible for most orange, scarlet,
crimson, mauve, violet, and blue colors, as well as contributing
much to yellow, ivory, and cream colors.
3
Anthocyanins as a class
of flavonoids are water-soluble glycosides of polyhydroxy and
polymethoxy derivates of 2-phenylbenzopyrylium or flavylium
salts and are responsible for the red, purple, and blue colors of
many fruits, vegetables, and cereal kernels.
4
Simple or acylated
anthocyanin pigments are mainly located in the aleurone layer or
pericarp of the maize endosperm, greatly affecting the color of
the kernel,
5
and could be separated into anthocyanin-rich
fractions for use as functional colorants or functional food
ingredients.
6
In addition to the color that they impart, there is an
intensified interest in anthocyanins, as well as other flavonoids
and phenolic acids, due to their beneficial health effects. The
health beneficial properties of these plant metabolites have been
attributed to their high antioxidant and antiradical activities
but also to many other mechanisms such as antimutagenesis,
anticarcinogenesis, and estrogenic activities, inhibition of
enzymes, and induction of detoxification enzymes.
7
Anthocyanin-
rich foods and anthocyanin pigments have been suggested as
potential agents to reduce the risk of colon cancer by inhibiting
proliferation of human colon cancer cells in vitro.
8
Also, the
tests of Tsuda et al.
9
provide a nutritional and biochemical basis
for the use of the anthocyanins as a functional food factor that
may be beneficial for helping to prevent diabetes and obesity.
More than 600 carotenoid species have been identified in
nature. Carotenoids are localized in subcellular organelles,
chloroplasts, and chromoplasts, where thay are chiefly associated
with proteins and serve as accessory pigments in photosynthesis.
Two classes of carotenoid pigments, carotenes and xanthophylls,
are responsible for the yellow and orange color of maize
endosperm.
10
In general, - and -carotene are the major
carotenes, whereas -cryptoxanthin, lutein, and zeaxanthin make
up the majority of the xanthophylls. In addition to the high
antioxidant activities, - and -carotene and -cryptoxanthin have
provitamin A activities, while lutein and zeaxanthin have attracted
much attention due to the possible role in preventing cataracts
11
and age-related macular degeneration.
12
Structurally, vitamin A
(retinol) is essentially one-half of the -carotene molecule.
13
The present study was conducted to observe the levels of
phenolic compounds, carotenoids, and antioxidant capacity
of 10 different colored maize genotypes and to identify
anthocyanin compositions using liquid chromatographymass
Received: October 26, 2011
Revised: December 18, 2011
Accepted: January 16, 2012
Published: January 16, 2012
Article
pubs.acs.org/JAFC
2012 American Chemical Society 1224 dx.doi.org/10.1021/jf204367z | J. Agric.Food Chem. 2012, 60, 12241231
spectrometry (LC-MS) as a tool. Identifying maize genotypes
with naturally rich pigments would promise a potential for
the development of functional foods and/or functional food
colorants.
working
solution at 525 nm was 1.0 0.05 AU. Maize flour (10 mg) was mixed
by adding 20 mL of ABTS
+
or DPPH
. ZPP-2 selfed,
ZPL-7, and ZPP-1 selfed maize genotypes have light blue, dark
blue, and dark red kernel colors, respectively, containing the
highest levels of total phenolics, anthocyanins, and antioxidant
capacity of the genotypes tested. According to the obtained data,
it could be said that a higher content of phenolic compounds in
the maize kernel contributes to their higher antioxidant activity.
These results are in well accordance with literature data.
25
Also,
from our data, it can be concluded that a darker colored maize
has more antioxidant capacity. Lopez-Martinez et al.
32
also
found that pigmented black, purple, red, and blue maize showed
relatively higher radical scavenging activity than nonpigmented
samples. The differences in the antioxidant capacity among red,
blue, and purple colored maize genotypes are possibly related to
the specific composition of anthocyanin derivatives such as
simple or acylated glycosides of cyanidin, pelargonidin, or
peonidin.
39
The radical scavenging capacity of different antho-
cyanins depends mainly on the number of hydroxyl groups and
their position on the molecule. Additionally, glycosylation of the
anthocyanidins may modulate the antioxidant capacity depend-
ing on the aglycons.
40
No significant positive correlation was
found between ABTS radical scavenging activities and lutein and
-carotene contents. In the genotypes with no anthocyanin
pigment accumulation that shows various kernel colors ranging
from white to orange, the intensity of maize kernel coloration
was closely related to antioxidant capacity. The genotypes
had ABTS radical scavenging activities with the following
descending order: orange > yellow > lemon yellow > white
(ZPL-4 > ZPL-3 > ZPL-2 > ZPL-1). It can be assumed that the
antioxidant capacity of studied carotenoids was disguised with
strong antioxidant capacity of anthocyanins in the samples of
different red and blue maize. However, significant positive
correlation coefficients between -carotene and antioxidant
capacity (r
2
= 0.70) and lutein and antioxidant capacity
(r
2
= 0.87) determined only among the no anthocyanin maize
confirm that the carotenoids influenced the capacity of ABTS
+
scavenging. Terao
41
reported that the presence of nine or more
double bonds and oxo groups at the 4(4)-position in the
-ionone ring in the carotenoid structure greatly enhanced the
singlet oxygen quenching activity. Significant correlations
between insoluble bound ferulic acid contents and ABTS
radical scavenging activities point to their contribution to
antioxidant capacity. The antioxidant capacity was positively
correlated with the portion of pericarp per kernel weight
(Table 5). Kernels of small to medium size produce darker red
and blue flour coloration and a higher concentration of phenolic
compounds per g of d.m. because they possess a higher
proportion of aleurone and bran layer and are less diluted by the
Journal of Agricultural and Food Chemistry Article
dx.doi.org/10.1021/jf204367z | J. Agric.Food Chem. 2012, 60, 12241231 1228
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Journal of Agricultural and Food Chemistry Article
dx.doi.org/10.1021/jf204367z | J. Agric.Food Chem. 2012, 60, 12241231 1229
starchy endosperm.
5
In our study, the light blue maize (ZPP-2
selfed) with the highest portion of pericarp per kernel weight
(11.49%) (the results are not shown) had the highest content of
total plenolics, flavonoids, ferulic acid, and ABTS radical
scavenging activity (35.66 mmol Trolox/kg d.m.).
Our results provided the evidence of high levels of health
beneficial phytochemicals and antioxidant capacity of colored
maize. Significant differences were found in lutein and
-carotene contents for the 10 different colored maize
genotypes. It can be concluded that the orange (ZPL-4)
genotype has a superior potential for use as a source of
pro-vitamin A compounds. The results of total anthocyanin
contents indicate that some of the colored maize kernels such
as dark red, dark blue, and light blue maize may hold promise
for the development of functional foods and/or natural
colorants.
AUTHOR INFORMATION
Corresponding Author
*Tel: +312 297 71 08. Fax: +312 299 21 23. E-mail:
vgokmen@hacettepe.edu.tr.
Funding
This work was supported by the Ministry of Education and
Science of the Republic of Serbia (Grant no. TR-31069).
ABBERVATIONS USED
ABTS, 2,2-azino-bis/3-ethyl-benothiazoline-6-sulfonic acid;
ANOVA, analysis of variance; CE, catechin equivalents; CGE,
cyanidin 3-glucoside equivalents; DPPH, 2,2-diphenyl-1-
picrylhydrazyl; GAE, gallic acid equivalents; HPLC, high-
performance liquid chromatography; LSD, least significant
differences; RCB, randomized complete block design; TEAC,
Trolox equivalent antioxidant capacity
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Figure 1. Total antioxidant capacity of different colored maize
genotypes obtained by QUENCHER method with ABTS (
) and
DPPH (