ACTA BIOLOGICA CRACOVIENSIA

CHEMISTRY, ANALYSIS, CHEMICAL SYNTHESIS, AND INDUSTRIAL PRODUCTION OF CAROTENOIDS
Objective: To compare several commercial columns and
mobile phase combinations to determine the separation efficiency
and selectivity using UHPLC.
Results: A good HPLC separation with a 3 μm column produces
about 20,000 plates. Multiple UHPLC columns were used
in series to achieve unique selectivity and nearly 50,000 plates.
The data from carotenoid standards was used to predict elution
of other carotenoids and choose conditions for high resolution
separations. Selected conditions were used to separate serum
and food carotenoids.
Conclusions: UHPLC was successfully used in high-resolution
mode to achieve separations previously unobtainable with conventional
HPLC. Mapping the retention of known standards permitted
the prediction of unidentified components.
3.6.
Total synthesis of an oxidation product of
γ-carotene, a pro-vitamin A food carotenoid
Kristine Crawford, Frederick Khachik, Eugene Mazzola
Department of Chemistry and Biochemistry, 0107 Chemistry
Building, University of Maryland, College Park, Maryland, USA
20742, kskc@umd.edu, khachik@umd.edu
Human serum carotenoids and their metabolites are known to
function as antioxidants and inflammation mediators. In 1992,
an oxidative metabolite of lycopene was isolated from human
serum and tomato-based food products which was later prepared
by partial synthesis from lycopene and characterized as 2',6'cyclolycopene-1',5'-diol
{1} (Khachik et al., 1998). Results of in
vitro studies demonstrated that {1} was more effective at inhibiting
the growth of solid human tumor cells than lycopene (Monks
et al., 1991). While the metabolism of prominent hydrocarbon
carotenoids such as lycopene and β-carotene have been extensively
studied, the functional role of γ-carotene remains unexplored.
Because the chemical structure of γ-carotene is a hybrid
of lycopene and β-carotene, the total synthesis of 2',6'-cyclo-γcarotene-1',5'-diol
{2} which is a structural analog of {1} was targeted.
This was accomplished in six steps from commercially
available citral using a C 15 +C 10 +C 15 Wittig coupling strategy in
an overall yield of 15%. In another semi-synthetic approach, 12'apo-Ψ-caroten-12'-al
was transformed into {2} in a modest yield
by epoxidation at the 5,6-position followed by rearrangement and
elongation. The present methodology provides novel access to an
oxidation product of γ-carotene that could be potentially formed
in humans or biological systems. Further, supplementation studies
with γ-carotene from food sources or with dietary supplements
would be expected to provide an insight into possible metabolic
oxidation of this carotenoid to 2. In view of the well-established
health benefits of lycopene and β-carotene in the prevention
of chronic diseases, investigation of the metabolism of
γ-carotene that has structural features of both of these
carotenoids is essential.
REFERENCES
KHACHIK F, STECK A, NIGGLI U, PFANDER H. 1998. Partial synthesis and
structural elucidaiton of the oxidative metabolites of lycopene
identifed in tomato paste, tomato juice and human serum.
Journal of Agricultural and Food Chemistry 46: 4874-4884.
MONKS A, SCUDIERO D, SKEHAN P, SHOEMAKER R, PAUL K, VISTICA D, HOSE
C, LANGLEY J, CRONISE P. 1991. Feasibility of a high flux anticancer
drug screen using a diverse panel of cultured human
tumor cell lines. Journal of the National Cancer Institute 83:
757-766.
Vol. 53, suppl. 1, 2011
17–22 July 2011, Krakow, Poland
3.7.
Carotenoid composition of mamey fruit
(Pouteria sapota)
József Deli1 , Erika Turcsi1 , Ildikó Szabó1 ,
Yesuri Mosquera2 , Enrique Murillo2 1University of Pécs, Medical School, Department of Biochemistry
and Medicinal Chemistry Szigeti út. 12. Pécs H-7624 Hungary,
jozsef.deli@aok.pte.hu, erika.turcsi@aok.pte.hu,
ildiko.szabo@aok.pte.hu
2University of Panama, Biochemistry and Nutrition Laboratory,
Panama City, Panama, emurillo29@hotmail.com
A survey of local plants in Panama has revealed the presence of
ketocarotenoids in a range of species. Examples with high concentrations
of ketocarotenoids were found among fruits, e.g.
'Mamey' (Pouteria sapota), 'Maracuya Chino' (Cioniciscyos
macrunthus) and 'Jipijapa' (Carludovica palmata), and in young
brown leaves and red seeds of Zamia dressleri.
This paper focuses on the HPLC investigation of the
carotenoid composition of Mamey fruit.
Three 'Mamey rojo' and one 'Mamey naranja' varieties were
investigated. By using HPLC-DAD and HPLC-MS systems 50
compounds were detected. The parallel use of HPLC and classic
column chromatography (CC) allowed the identification of
numerous minor carotenoids. Based on their UV-VIS and mass
spectrum as well as co-chromatography with authentic samples,
the following carotenoids were identified: neoxanthin, violaxanthin,
luteoxanthin, capsanthin 5,6-epoxide, β-cryptoxanthin-
5,6,5',6'-diepoxide, (9Z)-violaxanthin, β-cryptoxanthin-5,6,5',8'diepoxide,
β-cryptoxanthin-5,8,5'8'-diepoxide, cryptocapsin 5,6epoxide,
cryptocapsin, 3'-dehidroxy-capsanthin, 3-dehydroxycapsorubin,
β-carotene, β-carotene-5,6-epoxide, β-carotene-5,8epoxide
and β-carotene-5,8,5',8'-diepoxide. Some carotenoids
with κ-end group but with no oxygen substituents on the
cyclopentane ring were tentatively identified by their UV-VIS and
MS spectra and their adsorption properties. The isolation and
structure elucidation of these compounds are in progress.
This study was supported by the grant OTKA K 83898 (Hungarian
National Research Foundation) and SENACYT (Secretaria Nacional de
Ciencia Tecnologia de Panamà).
3.8.
Novel microalgae as potential source of lutein:
optimization of solvent extraction conditions
Aysegül Erdogan1 , Ahmet E. Eroglu1 , Ali Cagir1 ,
Sevde Hatipoglu Uslu2 , Meltem Conk Dalay2 ,
Hayriye Soykan1 1Department of Chemistry, Izmir Institute of Technology, Urla,
35430, Izmir, aysegulseker@iyte.edu.tr, ahmeteroglu@iyte.edu.tr,
alicagir@iyte.edu.tr, hayriyesoykan@std.iyte.edu.tr
2Department of Bioengineering, Ege Universtity, Bornova, 35100,
Izmir, meltemconkdalay@gmail.com, sevdenat@yahoo.com
Microalgae have been one of the most important natural source of
products. Among these, carotenoids play a protective role for
many diseases. Within this group, lutein has received increasing
attention due to its potential health benefits, particularly in the
prevention of age-related macular degenaration. It has also been
claimed that lutein displays cancer-preventing properties.
Nowadays, microalgae have been proposed as potantial source of
lutein. For this reason, new studies must be directed towards its
accurate identification and quantification. This study aims to find
out the optimum solvent extraction conditions for lutein in order
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