ACTA BIOLOGICA CRACOVIENSIA

CHEMISTRY, ANALYSIS, CHEMICAL SYNTHESIS, AND INDUSTRIAL PRODUCTION OF CAROTENOIDS
3.17.
Carotenoid composition from unexploited
Amazonian fruits
Eliseu Rodrigues, Renan Campos Chisté, Lilian Mariutti,
Adriana Zerlotti Mercadante
Department of Food Chemistry, University of Campinas (UNI-
CAMP). Postal code: 13083-862, Campinas, São Paulo, Brazil,
eliqca@fea.unicamp.br, renanchiste@gmail.com,
lilianmariutti@uol.com.br, azm@fea.unicamp.br
Brazil has a wide variety of native, wild and not well-known fruits,
such as the Amazonian fruits, and few information about their constituents
are available. Maná-cubiu (Solanum sessiflorum) has 5-6
cm in diameter and the comestible fraction represents approximately
91% of total fresh weight (9% of peel). Piquiá (Caryocar villosum
(Aubl.) Pers) presents 7-9 cm in diameter and the pulp represents
approximately 12% of the total fresh weight (24% of seed
and 64% of shell). Both fruits are irregularly oblong-globose with a
yellowish pulp. Since the carotenoid profiles of maná-cubiu and
piquiá were not reported yet in the literature, the main purpose of
this work was to identify and quantify by HPLC-DAD-MS/MS (APCI
– positive ion mode) the carotenoids from these Amazonian fruits.
The carotenoids were separated on a C30 column and identified
according to the UV/Vis and MS spectra features as compared to
standards (lutein, zeaxanthin, antheraxanthin, violaxanthin, neoxanthin
and β-carotene) and carotenoid extracts from other sources
(kale and mango with or without HCl acidification), all analyzed in
the same conditions. The contents of total carotenoids in the freezedried
pulp of maná-cubiu was 12.43 μg/g and the main carotenoids
found were all-trans-lutein (2.74 μg/g), all-trans-β-carotene (2.66
μg/g), all-trans-violaxanthin (2.59 μg/g), 9-cis-luteoxanthin (2.01
μg/g), 9-cis-violaxanthin (1.29 μg/g) and all-trans-neoxanthin (1.13
μg/g). The total carotenoid level in the freeze-dried pulp of piquiá
was 16.96 μg/g and the main carotenoids found were all-transantheraxanthin
(3.44 μg/g), all-trans-zeaxanthin (2.88 μg/g), alltrans-neoxanthin
(2.26 μg/g), all-trans-violaxanthin (1.10 μg/g) and
all-trans-β-carotene (0.73 μg/g). A non-identified carotenoid was
also found in piquiá (2.84 μg/g), presenting λmax at 445 nm in
methanol/MTBE (%III/II = 55 and no cis peak) and an in-source
fragment at 583 m/z ([M+H-18] + ). Since the major carotenoids
identified in both fruits presented epoxide groups, all analysis were
performed in both fresh and freeze-dried pulps, with and without
addition of NaHCO3 during extraction step, and the carotenoid profiles
did not show any difference. Considering that the essential role
of biodiversity for its sustainable use in food security and nutrition
is world-wide recognized, these natural resources from Amazonia
should be commercially exploited.
Acknowledgements: CNPq and FAPESP.
3.18.
Chemical and colour changes associated to the
epoxidation and oxidative cleavage of β-carotene
Poliana D. Gurak 1 , Adriana Z. Mercadante 1 ,
ML González-Miret 2 , Francisco J. Heredia 2 ,
Antonio J. Meléndez-Martínez 2
1Department of Food Science, Faculty of Food Engineering,
University of Campinas, Postal code 13083-862, Campinas, SP,
Brazil. poligurak@hotmail.com, azm@fea.unicamp.br
2Laboratory of Food Colour and Quality, Department of Nutrition
and Food Science, Faculty of Pharmacy, Universidad de Sevilla,
41012, Sevilla, Spain, heredia@us.es, miret@us.es,
ajmelendez@us.es
Vol. 53, suppl. 1, 2011
The oxidation of carotenoids leads to important changes in their
colour, biological and other properties. The objective measurement
of colour could therefore be harnessed to monitor the oxidation
of these compounds and for the rapid estimation of oxidation
products, some of which are attracting much interest as they
seem to be involved in the modulation of intracellular signalling
pathways. In this sense, the objectives of this study were two:
(1) to identify by HPLC-DAD-MS/MS the oxidation products
derived from β-carotene after epoxidation with meta-chloroperbenzoic
acid (MCPBA) and oxidative cleavage with KMnO 4 ; and
(2) to assess the related colour changes. In the epoxidation reaction,
the major carotenoids identified were 5,6-epoxy-β-carotene,
5,6,5',6'-diepoxy-β-carotene, 5,6,5',8'-diepoxy-β-carotene and 5,8epoxy-β-carotene,
while β-apo-8'-carotenal, semi-β-carotenone,
10'-apo-β-carotenal, 12'-apo-β-carotenal, 14'-apo-β-carotenal and
15-apo-β-carotenal were the major products identified in the
oxidative cleavage reaction. The (13Z)- and (9Z)- isomers of βcarotene
were also detected in both reactions. More than 95% of
(all-Z)-β-carotene oxidized after 60 minutes; however, the
amounts of (all-Z)-β-carotene lost were not compensated by those
of the new compounds formed. As a result of both reactions, most
of the compounds formed had shorter chromophore and therefore
shorter maxima wavelengths as compared to those of βcarotene
(450 nm). This led to important changes in the values of
colour parameter b* and colour differences (ΔE*). Thus, the values
of ΔE* relative to the original β-carotene solution after 1 hour
of reaction were 16.2 (epoxidation) and 48.1 (oxidative cleavage),
indicating that colour changes could be visually noticed. The values
of b* (r>0.99) and C* ab (r>0.99) highly correlated with the
absorbance at 450 nm, thus these parameters seem promising
for the rapid assessment of the formation of oxidative derivatives.
Since C* ab is the quantitative attribute of colourfulness, visual
changes in colour vividness can be used to monitor de oxidation
of β-carotene.
Acknowledgements: FAPESP for the financial support.
3.19.
The influence of the spreading solvent on the
Langmuir monolayer characteristics of
β-carotene
Justyna Mildner, Patrycja Dynarowicz-Łątka
17–22 July 2011, Krakow, Poland
Jagiellonian University, Faculty of Chemistry, Ingardena 3,
30-060 Kraków, Poland, mildner@chemia.uj.edu.pl
Our work was aimed at finding appropriate solvent for spreading
β-carotene onto the air/water interface for Langmuir monolayer
formation. We have thus chosen a number of organic solvents and
their mixtures that dissolve β-carotene, namely: benzene, cyclohexane,
chloroform, isooctane, petroleum ether, benzene/
dichloromethane, chloroform/hexane/methanol. In each of the
tested solvent we observed the increase of surface pressure upon
film compression, which was monotonous, without typical collapse
at the end of compression. However, a surface pressure
increase alone is an insufficient criterion to evidence a true monolayer
formation. Therefore, in addition to the surface pressure
monitoring, we engaged an optical method – Brewster angle
microscope (BAM), for a direct visualization of a film structure.
We observed that β-carotene deposited from all the tested solvents
onto the water surface, form crystalline domains instead of
a homogenous film. Therefore, an increase in surface pressure
observed for β-carotene can thus be accounted for the decrease of
available total surface area upon compression that gives rise to
the domains compacting, and not monomolecular layer formation.
Therefore so called "isotherm" recorded for β-carotene is
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