Documente Academic
Documente Profesional
Documente Cultură
Chemical and rheological properties of a starch-rich fraction from the pulp of the fruit
cupuassu (Theobroma grandiorum)
Lcia C. Vriesmann, Joana L.M. Silveira, Carmen L. de O. Petkowicz
Universidade Federal do Paran, Departamento de Bioqumica e Biologia Molecular, CP 19046, CEP 81531-990, Curitiba-PR, Brazil
a r t i c l e
i n f o
Article history:
Received 8 May 2008
Received in revised form 28 November 2008
Accepted 9 December 2008
Available online 16 December 2008
Keywords:
Theobroma grandiorum
Cupuassu
Starch
Amylose
Gel
Rheology
a b s t r a c t
The pulp obtained from the fruit of cupuassu (Theobroma grandiorum) was extracted with hot aqueous 0.1%
citric acid to give fraction 0.1CA-2 in 15% yield. This was the predominant component polysaccharide, 91% of
which was composed of starch, by an iodine test and monosaccharide composition, and its 13C NMR
spectrum was consistent with that of a high amylose starch. The content of amylose found in fraction 0.1CA-2
was 71%. This value is higher than those of common starches of cereal grains, tubers, roots, and other fruits.
The fraction was submitted to rheological examination, gels being prepared on heating with concentrations
of 4 to 7% (w/w). A non-Newtonian behavior was observed, and gel viscosity and strength depended on the
concentration. The presence of starch, as well as the presence of previously investigated pectin, conferred the
high viscosity and gelling capability of the pulp.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Starch is the main reserve polysaccharide of many plants. It is an
important renewable and a low-cost polymer, occurring as granules,
which determine its physical properties. Due its thickening and
gelling properties, it is used in the food, pharmaceutical, and chemical
industry [13].
Cereal grains, legume seeds, tubers, and certain fruits contain from
30 to 85% starch on a dry-weight basis [3]. Commercial starches are
obtained mainly from yellow corn, although potato, wheat, tapioca,
rice and sorghum also are signicant sources [2,3].
Many reports have described the characterization of starch from
cereals, roots and tubers [47]. The fruit starches have also been
investigated, mainly those from banana [8,9], mango [8,10], apple [11],
squash [12], cherimoya [13] and Kamo Kamo [14].
Starch consists of a mixture of two polymers, amylose and
amylopectin. Whereas amylose is an essentially linear molecule,
consisting of (14)-linked -D-glucopyranosyl units, amylopectin is a
highly branched molecule with substitution of these at O-6 by -Dglucopyranosyl branches. These are composed of (14)-linked -Dglucopyranosyl units with various lengths [13].
It has been demonstrated that the pulp of the fruit of Theobroma
grandiorum, Schumann (family Sterculiaceae), growing in the
Brazilian Amazon, known locally as cupuassu, contains a considerable
amount of starch as well as pectin polysaccharides [15,16]. The pulp is
Corresponding author. Tel.: +55 41 3361 1661; fax: +55 41 3266 2042.
E-mail address: clop@ufpr.br (C.L.O. Petkowicz).
0928-4931/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2008.12.011
greatly appreciated for its pleasant acidic taste, being consumed fresh
or processed, mainly as juice, ice cream, candy and jellies [17]. It has an
intense fragrance [17], whose volatile compounds have been extensively analyzed [18], as well as its content of vitamin C [19].
As chemical and rheological characterization of native starch can
lead to improvements for predicting desirable functional properties of
starchy products, we now study some chemical and rheological
features of the native starch-rich fraction obtained from the pulp of
cupuassu fruit [15].
2. Experimental
2.1. Extraction of fraction 0.1CA-2
After enzyme-inactivation with methanolH2O (4:1, v/v) under
reux for 20 min, the grounded pulp fruit was defatted with ptoluene-ethanol (2:1, v/v) in a Soxhlet and dried. The residue was
submitted to sequential extractions with water (25 C and 60 C), citric
acid (0.1%, 0.5%, 1%, 2.5% and 5%, using temperatures of 50 C and
100 C at each concentration) and NaOH (2 mol L 1 and 4 mol L 1
NaOH; 25 C) [15,16]. Fraction 0.1CA-2 was obtained with 0.1% citric
acid at 100 C for 60 min. The extract was concentrated and treated
with ethanol (2:1 v/v) in order to obtain precipitated polysaccharide,
which was then washed three times with ethanol and dried under
vacuum.
The fraction was identied according to the conditions applied on
extraction: 0.1 displays the concentration of citric acid (CA) and 2
was used for the second hot extraction (100 C).
652
Table 1
Monosaccharidea composition of fraction 0.1CA-2 obtained from the pulp of cupuassu
Fraction
Rha
Ara
Xyl
Man
Gal
Glc
Uronic acidb
1.0
90.8
6.6
mol%
0.1CA-2
a
b
0.6
0.4
0.4
0.2
653
Fig. 1. 13C NMR spectra of fraction 0.1CA-2 in D2O at 70 C (A) and DEPT-135 (B).
654
Fig. 4. G as a function of concentration for 0.1CA-2 gels at different frequencies (25 C).
Fig. 6. Variation of G and G (1 Hz, 4 Pa) during initial heating from 5 to 95 C and
subsequent cooling from 95 to 5 C for a 5% (w/w) 0.1 CA-2 gel.
655
Fig. 7. Inuence of shear rate on the absolute viscosity of gels of fraction 0.1CA-2 at
25 C.
656
Table 2
Comparison of different models for the ow behavior of fraction 0.1CA-2 samples
obtained from the pulp of cupuassu
Concentration
(%, w/w)
Model
K (Pa sn)
0 (Pa)
p (Pa s)
R2
HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham
HerschelBulkley
Power-law
Bingham
1.52
5.22
10.22
21.94
11.52
23.66
12.16
24.72
10.34
15.08
38.40
107.1
40.43
117.8
44.45
120.1
0.70
0.51
0.55
0.45
0.55
0.45
0.55
0.44
0.2630
0.5416
0.5992
0.5998
0.980
0.946
0.951
0.989
0.985
0.960
0.996
0.993
0.964
0.997
0.992
0.960
observations were reported for cassava starch [53], sago starch pastes
[55] and corn starch [59].
4. Conclusions
For the rst time, a starch-rich fraction from the pulp of cupuassu
fruit (T. grandiorum) is described with a yield of 15% related to
defatted-dried material. The fraction was composed predominantly by
a high amylose (71%) starch, characterized by a blue coloration with
iodine solution, monosaccharide composition and 13C NMR spectroscopy. This fraction contained a minor proportion of pectin that may
contribute to its gel-like behavior. Analysis of the rheological properties of the fraction showed a non-Newtonian behavior at concentrations from 4 to 7% (w/w). Considering the R2 values, HerschelBuckley
was found to be the most adequate model to describe the rheological
comportment of the samples.
Dynamic oscillatory experiments indicated a highly elastic behavior with G signicantly larger than G, being independent of the
range of examined frequencies (0.110 Hz), conrming gel characters
for all concentrations. A gel-like behavior was demonstrated for
fraction 0.1CA-2, a native high amylose starch, suggesting a potential as
a gelling additive in pharmaceutical, cosmetic and food applications.
Acknowledgements
The authors thank the Brazilian agencies, CNPq and Fundao
Araucria-PRONEX for nancial support, and Dr. Philip A. J. Gorin for
help with the English language.
References
[1] P. Van Hung, T. Maeda, N. Morita, Trends in Food Science & Technology 17 (2006)
448456.
[2] H.F. Zobel, A.M. Stephen, in: A.M. Stephen (Ed.), Food Polysaccharides and Their
Applications, Marcel Dekker, 1995, pp. 1966.
[3] J.N. BeMiller, in: R.L. Whistler, J.N. BeMiller (Eds.), Industrial Gums: Polysaccharides and Their Derivatives, 3rd, Academic Press, san Diego, 1993, pp. 579600.
[4] G.E. Vandeputte, V. Derycke, J. Geeroms, J.A. Delcour, Journal of Cereal Science 38
(2003) 5359.
[5] N. Singh, N. Isono, S. Srichuwong, T. Noda, K. Nishinari, Food Hydrocolloids 22
(2008) 979988.
[6] R. Hoover, Carbohydrate Polymers 45 (2001) 253267.
[7] R.A. Freitas, R.C. Paula, J.P.A. Feitosa, S. Rocha, M.-R. Sierakowski, Carbohydrate
Polymers 55 (2004) 38.
[8] C.E. Milln-Testa, M.G. Mndez-Montealvo, M.A. Ottenhof, I.A. Farhat, L.A. BelloPrez, Journal of Agricultural and Food Chemistry 53 (2005) 495501.
[9] L.A. Bello-Prez, E. Agama-Acevedo, L. Snchez-Hernndez, O. Paredes-Lpez,
Journal of Agricultural and Food Chemistry 47 (1999) 854857.
[10] F. Iagher, F. Reicher, J.L.M. Ganter, International Journal of Biological Macromolecules 31 (2002) 917.
[11] D.G. Stevenson, P.A. Domoto, J. Jane, Carbohydrate Polymers 63 (2006) 432441.
[12] D.G. Stevenson, S. Yoo, P.L. Hurst, J. Jane, Carbohydrate Polymers 59 (2005)
153163.
[13] O. Goi, M.I. Escribano, C. Merodio, LWT Food Science and Technology 41 (2008)
303310.
[14] J. Singh, O.J. McCarthy, H. Singh, P.J. Moughan, L. Kaur, Carbohydrate Polymers 67
(2007) 233244.
[15] L.C. Vriesmann, Extrao, caracterizao e aspectos reolgicos de polissacardeos
da polpa dos frutos de Theobroma grandiorum (cupuau) (2008). MSc. Thesis.
Universidade Federal do Paran, Curitiba, Brasil. Available on-line on http://hdl.
handle.net/1884/13859.
[16] L.C. Vriesmann, C.L.O. Petkowicz, Carbohydrate Polymers (in press). doi:10.1016/j.
carbpol.2008.12.007.
[17] P.B. Cavalcante, Frutas Comestveis da Amaznia, 5th ed., CEJUP: CNPq: Museu
Paraense Emlio Goeldi, Belm, 1991, pp. 9091.
[18] C.E. Quijano, J.A. Pino, Food Chemistry 104 (2007) 11231126.
[19] M.C. Vieira, A.A. Teixeira, C.L.M. Silva, Journal of Food Engineering 43 (2000) 17.
[20] M. Dubois, K.A. Gilles, J.K. Hamilton, P.A. Rebers, F. Smith, Analytical Biochemistry
28 (1956) 350356.
[21] T.M.C.C. Filisetti-Cozzi, N.C. Carpita, Analytical Biochemistry 197 (1991) 157162.
[22] E.F. Hartree, Analytical Biochemistry 48 (1972) 422427.
[23] J. Chrastil, Carbohydrate Research 159 (1987) 154158.
[24] J. Techawipharat, M. Suphantharika, J.N. BeMiller, Carbohydrate Polymers 73
(2008) 417426.
[25] J. Jane, Y.Y. Chen, L.F. Lee, A.E. McPherson, K.S. Wong, M. Radosavljevic, T.
Kasemsuwan, Cereal Chemistry 76 (1999) 629637.
[26] N. Singh, J. Singh, L. Kaur, N.S. Sodhi, B.S. Gill, Food Chemistry 81 (2003) 219231.
[27] N.W. Polaske, A.L. Wood, M.R. Campbell, M.C. Nagan, L.M. Pollak, Starch/Strke 57
(2005) 118123.
[28] K. Behall, J. Hallfrisch, European Journal of Clinical Nutrition 56 (2002) 913920.
[29] P.A.J. Gorin, Advances in Carbohydrate Chemistry and Biochemistry 38 (1981)
13104.
[30] R.A. Freitas, Estrutura e interaes entre galactoxiloglucanas e amidos (2003). Ph
D. Thesis, UFPR, Curitiba, Brasil.
[31] J.-L. Doublier, L. Choplin, Carbohydrate Research, 193 (1989) 215226.
[32] M.J. Milles, V.J. Morris, S.G. Ring, Carbohydrate Research 135 (1985) 257269.
[33] P. Roger, V. Tran, J. Lesec, P. Collona, Journal of Cereal Science 24 (1996) 247262.
[34] J.-H. Chung, J.-A. Han, B. Yoo, P.A. Seib, S.-T. Lim, Carbohydrate Polymers 71 (2008)
365371.
[35] P. Roger, B. Baud, P. Colonna, Journal of Chromatography A 917 (2001) 179185.
[36] J.A. Patindol, B.C. Gonzalez, Y.-J. Wang, A.M. McClung, Journal of Cereal Science 45
(2007) 209218.
[37] N.W.H. Cheetam, L. Tao, Carbohydrate Polymers 33 (1997) 251261.
[38] S. Jobling, Current Opinion in Plant Biology 7 (2004) 210218.
[39] D.J. Prokopowich, C.G. Biliaderis, Food Chemistry 52 (1995) 255262.
[40] I. Rosalina, M. Bhattacharya, Carbohydrate Polymers 48 (2002) 191202.
[41] D. Khondkar, R.F. Tester, N. Hudson, J. Karkalas, J. Morrow, Food Hydrocolloids 21
(2007) 12961301.
[42] A.H. Clark, S.B. Ross-Murphy, Advanced Polymer Science 83 (1987) 57192.
[43] E.R. Morris, in: A.M. Stephen (Ed.), Food Polysaccharides and Their Applications,
Marcel Dekker, New York, 1995, pp. 517546.
[44] L.B. Iturriaga, B.L. Mishima, M.C. Aon, Food Research International 39 (2006)
660666.
[45] C.G. Biliaderis, B.O. Juliano, Food Chemistry 48 (1993) 243250.
[46] V.M.F. Lai, M.-C. Shen, A.-I. Yeh, B.O. Juliano, C.-y. Lii, Cereal Chemistry 78 (2001)
596602.
[47] M.J. Miles, V.J. Morris, P.D. Orford, S.G. Ring, Carbohydrate Research 135 (1985)
271281.
[48] F.E. Ortega-Ojeda, H. Larsson, A.-C. Eliasson, Carbohydrate Polymers 57 (2004)
5566.
[49] F.E. Ortega-Ojeda, H. Larsson, A.-C. Eliasson, Carbohydrate Polymers 56 (2004)
505514.
[50] M. Tako, S. Hizukuri, Journal of Carbohydrate Chemistry 18 (1999) 573584.
[51] L. Yu, G. Christie, Carbohydrate Polymers 46 (2001) 179184.
[52] X.-Z. Han, O.H. Campanella, H. Guan, P.L. Keeling, B.R. Hamaker, Carbohydrate
Polymers 49 (2002) 315321.
[53] L.-m. Che, D. Li, L.-j. Wang, N. zkan, X.D. Chen, Z.-H. Maoa, Carbohydrate
Polymers 74 (2008) 385389.
[54] M.A. Rao, P.E. Okechukwu, P.M.S. da Silva, J.C. Oliveira, Carbohydrate Polymers 33
(1997) 273283.
[55] I.M. Nurul, B.M.N.M. Azemi, D.M.A. Manan, Food Chemistry 64 (1999) 501505.
[56] C. Chaudemanche, T. Budtova, Carbohydrate Polymers 72 (2008) 579589.
[57] X.-Z. Han, O.H. Campanella, H. Guan, P.L. Keeling, B.R. Hamaker, Carbohydrate
Polymers 49 (2002) 315321.
[58] S. Lagarrigue, G. Alvarez, Journal of Food Engineering 50 (2001) 189202.
[59] P.N. Bhandari, R.S. Singhal, D.D. Kale, Carbohydrate Polymers 47 (2002) 365371.