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HYDROCOLLOIDS
Food Hydrocolloids 22 (2008) 298304 www.elsevier.com/locate/foodhyd

FOOD

Studies on functional properties of borassus starch from fresh germinating nuts of giginya (Borassus aethiopum) palm
J.T. Barminasa,b,, A.I. Onenb, E.T. Williamsb, M.Z. Zaruwab, S.A. Mamurub, D. Haggaic
a

Department of Chemistry, Federal University of Technology, P.M.B. 2076, Yola, Adamawa State, Nigeria b Department of Chemistry, Adamawa State University, P.M.B. 25, Mubi, Adamawa State, Nigeria c Department of Basic Sciences, College of Agriculture, P.M.B. 1010, Mubi, Adamawa State, Nigeria Received 22 August 2006; accepted 30 November 2006

Abstract Starch, an agricultural biodegradable biopolymer is increasingly being demanded recently for use in versatile industrial products. This has equally increased the search for new sources of this plant product. The young fresh germinating nuts of giginya (Borassus aethiopum) palm, locally called muruchi in some rural communities of Northern Nigeria, contain starch which is eaten when cooked. A new starch was isolated from these germinating nuts which yielded 24.73% of starch on dry weight basis. The chemical composition, swelling power, solubility, water-binding capacity, gelation, effect of storage on gel strength, thermal and pasting characteristics were studied. The chemical composition data were 0.08% ash, 0.18% crude protein, 0.26% crude ber, 0.09% total lipids, and 26.18% amylose contents. The starch exhibited low water-binding capacity, and limited swelling power and solubility behaviors which were dependent on temperature. DSC measurement showed that the starch has low enthalpy of gelatinization (8.12 J/g) and transition temperatures (T0, Tp, and Tc), and high gelatinization temperature range (13.1 1C). The gelatinization temperature was 64.5 1C and a low breakdown (BD) viscosity value of 192 Brabender units (BU) is suggestive of high paste stability of borassus starch during heating. Based on the high viscosity, BD viscosity, setback viscosity, nal viscosity, and ability of the starch to be easily cooked and form gels, the starch may be a potential hydrocolloid for application in sauces, baby food, and a variety of new food products. r 2006 Elsevier Ltd. All rights reserved.
Keywords: Borassus aethiopum Starch; Gelatinization; Swelling power; Setback viscosity; Enthalpy of gelatinization; Pasting properties

1. Introduction Giginya (Borassus aethiopum) palm is a tall tree with leathery, gray green, and fan-shaped leaves. The plant is found in the wild in Northern Nigeria and commonly cultivated in other tropical countries (Bokhari & Ahmed, 1978). It is an important source of food for the rural people of Northern Nigeria. The female tree bears a number of coconut-like fruits having a juicy brous orange or yellow pulp surrounding a hard nut. The mature nut contains a solid white kernel producing a sap which is used as a refreshing drink and good source of vitamin B complex
Corresponding author. Current address: Chemistry Department, Adamawa State University, P.M.B. 25, Mubi Adamawa State, Nigeria. Tel.: +234 805 347 3665. E-mail address: bjtsware@yahoo.com (J.T. Barminas).

(Bokhari & Ahmed, 1978; Morton, 1988). The sap is usually boiled immediately after extraction to make sugar or fermented to produce an alcoholic beverage. Also, the mature hard nuts are ground and used in porridge (Bokhari & Ahmed, 1978). The genus Borassus, with Borassus aethiopum and Borassus abellifer as the major species, has many traditional medicinal uses. They have been used in treating gonorrhea, dysentery, and respiratory diseases. The young plants are valued as diuretic and anthelmintic agents. Sap from the ower stalk is prized as a tonic, diuretic, stimulant, laxative, anti-phlegmatic, and amebicide. Sugar from the sap is a typical agent used to counteract poisoning and prescribed in treating liver disorders, and the pulp of the mature fruit is known to relieve dermatitis (Morton, 1988). The soft kernel of the young fruit is edible and the germinating nuts of B. aethiopum have an enlarged starchy

0268-005X/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodhyd.2006.11.018

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eshy radical locally called muruchi in Hausa in Nigeria. These germinating nuts are brous underground tubers which serve as storage organs for the seedlings and for the development of the growing palm. The tubers are regarded as common foodstuffs which provide a good source of starch for the local community where the plant grows. These tubers are eaten when boiled and could be a substitute for many starch sources. No scientic information is currently available on the starch. A closely related species which equally contains starch is palmyra palm (B. abellifer) (Morton, 1988). The carbohydrates of the tender kernel of palmyra palm were studied and found to be composed of polysaccharides characterized as a galactomannan (Subrahmanyan, Bains, Natarajan, & Bhatia, 1956). The induction of sister-chromatid exchange in human blood lymphocytes and mutagenicity of palmyra palm our has been investigated by Anderson and Poulsen (1985) and Kangwanpong, Maratana, and Temcharoen (1989). The objective of this work was to study the chemical characteristics, swelling, and water-binding behaviors, thermal and pasting properties of borassus starch from fresh geminating nuts of giginya (B. aethiopum) palm which will form the basis of its use, and modication for specic industrial applications. 2. Experiment 2.1. Starch isolation Giginya (B. aethiopum) palm is the genotype available in the area of study (Bokhari & Ahmed, 1978) and only tubers from such trees are studied. Fresh tubers from germinating nuts of giginya palm were purchased from local farmers in Hong, Adamawa state Nigeria. The tubers (weighing 400 g) were washed thoroughly with tap water and grated into a pulp. The pulp was suspended in excess distilled water (1:25 w/v) and homogenized in a blender (Waring blender, Model 38BL40, Christison Particles Technology) at medium speed for 5 min at room temperature (30 1C). The homogenized slurry was strained and ltered through a muslin bag. The waste residue in the bag was washed four times with 20 ml of distilled water until clear. The resulting milky ltrate was centrifuged at 1500g for 10 min and the clear supernatant decanted. The whole starch sediment was washed with 10 ml of distilled water to remove adhering protein layer. The starch was dried at 40 1C in a convection oven for 48 h. Finally the isolated starch was ground in a mortar, sieved through a 100-mesh sieve, and stored at room temperature in plastic bags. 2.2. Chemical composition Quantitative evaluations of moisture, ash crude ber, and lipid were performed by standard methods of AOAC (2000). The nitrogen content was determined by the microKjeldahl equipped with Kjeltec digester and distilling

system. The protein of the starch was estimated by multiplying the nitrogen content by 6.25. The lipid was extracted with petroleum ether (b.p. 4060 1C) for 12 h in a soxhlet extractor. The pH of a suspension containing starch slurry in distilled water (1:5 w/v) was determined using a Jenway model 3015 digital pH meter. Amylose content of the starch was determined by the colometric procedure of Chrastil (1987) at 620 nm. For determination of phosphorus, the sample treatment method outlined by Chaisawang and Suphantharika (2006) was followed, and the phosphorus content was then determined by the molybdenum blue method using spectrophotometer (Smith & Caruso, 1964). All determinations were in triplicates. 2.3. Swelling power, solubility, water-binding capacity, and leached amylose (LAM) Swelling behavior, solubility, and water-binding capacity at 50, 60, 70, 80, and 90 1C were determined in triplicate by the method of Waliszewski, Aparicio, Bello, and Monroy (2003). LAM in the dissolved material (Srichuwong, Sunarti, Isono, Mishima, & Hisamatsu, 2005) was determined by the colometric method reported by Chrastil (1987) in triplicate. 2.4. Differential scanning calorimetry Differential scanning calorimetry was carried out in a Perkin-Elmer DSC-7 (Norwalk, CT, USA) at a heating rate of 10 1C/min to evaluate the thermal transition of starch gelatinization. Melting points of indium (m.p. 156.6 1C, DH 28.55 J/g) and n-dodecane (m.p. 96.5 1C, DH 218.73 J/g) were used for temperature and heat quality capacity calibration. Distilled water (6.0 ml) was added to 2.0 mg of starch in DSC pans. It was sealed, reweighed, and kept at 3072 1C for 24 h for equilibrium of the starch sample and water. An empty pan was used as a reference to balance the heat capacity of the sample pan. The analysis was started at 30 1C and continued to 130 1C. The characteristics onset (T0), peak maximum (Tp), and conclusion (Tc) temperatures were determined. The enthalpy of gelatinization (DH) was estimated by integrating the area between the thermogram and the baseline under the peak and expressed in J/g of dry starch. Native maize, potato, and cassava starches, kindly provided by Northern Scientic Co., Ltd. Nigeria were included for comparison. 2.5. Gelation properties Starch suspensions (214% w/v) were prepared in distilled water with constant stirring. These samples (200 ml) were taken in weighed beakers and immersed in a boiling water bath for 30 min and stirred with a glass stirring rod. The beakers were weighed again and the volume of suspension corrected for any evaporation loss on heating using hot distilled water. A volume of 30 ml of the viscous solution

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300 J.T. Barminas et al. / Food Hydrocolloids 22 (2008) 298304 Table 1 Chemical composition of borassus starch (on dry weight basis) Characteristics Starch yield (%) Moisture (%) Ash (%) Crude protein (%) Crude ber (%) Total lipids (%) Phosphorus (ppm) Amylose (%) Aqueous pH Composition 24.7370.01 9.1570.02 0.0870.01 0.1870.02 0.2670.01 0.0970.01 86.1271.23 26.1870.22 5.1070.21

was transferred to a storage jar, cooled at 30 1C and stored at that temperature in a circulating water bath before the gel strength was determined (Ahmad, Williams, Doublier, Durand, & Buleon, 1999). Gel strengths were determined at intervals of 6 h, 1, 2, 4, and 7 days using a texture analyzer (TA-XT2; Stable Micro Systems, Surrey, England). For this measurement a conical probe, 4.0 cm in height and 3.0 cm in base diameter, was used to penetrate a cylindrical acrylic cup (55 70 mm2) containing samples to a depth of 10 mm at a rate of 2 mm/s. The maximum force (g) required to penetrate the gel was recorded as a measure of the gel strength. 2.6. Pasting characteristics A Brabender Visco-amylograph (Model 800221) was used to study pasting properties of 8% (w/w) starch water suspension (i.e., a total of 36 g of starch on dry weight basis was dispersed in 450 ml of distilled water). The mixture was heated from 50 to 95 at 6 1C/min (after an equilibrium time of 1 min at 50 1C), a holding period at 95 1C for 30 min, cooling from 95 to 50 1C at 6 1C/min and a holding phase at 50 1C for 30 min. The speed of the rotor was xed at 160 rpm. The viscosity was expressed in Brabender units (BU). The peak viscosity, the maximum viscosity during pasting, breakdown (BD) viscosity (difference between the peak viscosity and minimum viscosity during pasting), setback viscosity (difference between the maximum viscosity during cooling and the peak viscosity during pasting (PV)), nal viscosity, and pasting temperature (1C), i.e., the temperature indicating an initial increase in viscosity of the starch were determined. 2.7. Paste freezethaw stability This was obtained by heating 400 ml of 8% starch suspension in the Brabender visco-analyser machine to 95 1C at a rate of 6 1C/min, held at this temperature for 30 min, then cooled to 50 1C at the same rate, and nally held at 50 1C for another 30 min. Ten grams of this starch paste was taken into several test tubes and subjected to freezing in a refrigerator for 18 h. The gels were then thawed at 30 1C for 6 h. The exuded water was determined gravimetrically by vortexing the thawed gels for 30 s followed by centrifugation at 4000 rpm for 10 min (Waliszewski et al., 2003). Ten freezethaw cycles were performed and freezethaw stability was expressed as the percentage of water separated after each freezethaw cycle. 3. Results and discussion 3.1. Chemical composition Borassus starch was isolated from fresh germinating nuts of giginya palm. The composition of this starch and its yield (24.73%) were presented in Table 1. This yield might be an indication of appreciable accumulation of starch in

the young tubers for conversion to energy during the physiological development of the palm. Normally, during germination arrays of enzymes including amylases developed and remain in an active form. Since no preservatives were used during isolation, there could be a possibility of some amount of the starch getting hydrolyzed by the enzymes which might affect the starch yield. The inorganic materials in the starch might be low as shown by the low ash content. The crude protein of the starch was 0.18% which is low compared to banana (0.22%; Waliszewski et al., 2003), potato (0.63%), and corn (0.88%) starches (Ahmad et al., 1999). Hence borassus starch could be a feasible raw material in the food industry for production of glucose or fructose, where interference with Maillard reactions may be absent (Chavan, Shahidi, Hoover, & Perera, 1999). The total lipid content obtained at 0.09% is equally low compared to potato (0.12%), sago (0.25%), and corn (0.20%) starches (Ahmad et al., 1999). The low contents of both lipid and protein obtained might suggest good purity of the isolated starch. The phosphorus value is low compared to sago (110 ppm), cassava (113 ppm), corn (171 ppm), and potato (715 ppm) starches (Srichuwong et al., 2005). The amylose (26.18%) content falls within the apparent amylose range of 2431% for sago starch (Ahmad et al., 1999), but higher than 21.8% for maize (Spence & Jane, 1999). The high amylose content found for borassus starch may place it as an enzyme-resistant starch, and may also indicate the presence of fewer amylopectin branch linkages located in the crystalline region of the starch (Spence & Jane, 1999). The pH measurement showed that borassus starch is acidic and comparable with the previous pH values reported for tuber starches (Rasper & Coursey, 1967). 3.2. Swelling power, solubility, and water-binding behaviors The swelling power and solubility of starch over a range of temperature provide evidence of the associative bonding within the granules (Rincon, Padilla, Araujo, & Tillet, 1999). The swelling power of borassus starch as a function of heating temperatures ranging between 50 and 90 1C is shown in Fig. 1. A period of rapid swelling was observed at

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15 Swelling power (g/g)

301

25
10

Solubility (%) LAM (%)

Solubilty (%);LAM (%)

20 15 10 5 0 50 60 70 80 Temperature (C) 90

0 50 60 70 Temperature (C) 80 90

Fig. 1. Swelling power (g/g) of borassus starch at different temperatures. Error bars represent standard deviations.

temperatures between 60 and 70 1C and a slow rate recorded between 70 and 90 1C. This behavior has been attributed to two sets of bonding forces which relax at different temperatures (Leach, McCowen, & Schoch, 1959) and amyloselipid complexes (Galliard & Bowler, 1987). Phospholipids are known to form water-insoluble complexes with amylose during heating. These complexes severely restrict granular swelling, and maintain the integrity of swollen granules thereby limiting the swelling behavior of the starch (Galliard and Bowler). Hence, the decrease in the rate of swelling power suggests a loss of starch granule integrity after successive swelling (Srichuwong et al., 2005). In this study, the limited swelling value obtained over the temperature range may be attributed to the presence of strong bonding forces in the starch granules and amyloselipid complexes (Soni, Sharma, Dun, & Gharia, 1993). Fig. 2 shows the effect of temperature on the solubility and LAM of borassus starch. Solubility increased with increasing temperature between 60 and 80 1C. This might be due to the amylose that was preferentially solubilized and leached into solution as LAM during swelling. Solubility and LAM have been shown to be positively correlated with swelling, suggesting that solubilization occurred along with granular swelling (Srichuwong et al., 2005). Therefore at higher temperatures the swollen granules may be enriched with amylopectin, whereas most amylose molecules were preferentially leached out of the swollen granules at 90 1C. The ability of starch to absorb water is an indication of its moisture stability more especially in the food industry (Adebowale, Afolabi, & Olu-Owolabi, 2006). Water-binding capacity of starches also provides evidence of the degree of intermolecular association between starch polymers due to associative forces such as hydrogen and covalent bonding (Rincon et al., 1999). The water-binding capacity of borassus starch as a function of temperature is given in Fig. 3. The water-binding capacity increased with increasing temperature, and a higher rate of water absorption was found to be between 60 and 70 1C. Above 70 1C, there could be a higher proportion of swollen granules containing amylopectin which might occupy more volume and enhance viscosity due to close association of

Fig. 2. Solubility (%) and percentage of leached amylose (LAM) of borassus starch at different temperatures. Error bars represent standard deviations.

80 Water-binding capacity (%)

60

40

20

0 50 60 70 80 Temperatures (C) 90

Fig. 3. Water-binding capacity of borassus starch at different temperatures. Error bars represent standard deviations.

this polymer leading to a reduction in the rate of hydration at temperatures between 70 and 90 1C. 3.3. Thermal properties Table 2 compares the result of the gelatinization process of borassus starch with other starches using a differential scanning calorimetry. Gelatinization process of starch has been explained to involve the uncoiling and melting of the external chains of amylopectin that are packed together as double helices in clusters (Chavan et al., 1999). In Table 2, borassus starch showed the lowest T0 (61.1 1C), Tp (66.2 1C), Tc (74.2 1C) transition temperatures and gelatinization temperature range (13.1 1C) compared to maize potato and cassava starches. The low onset (T0) of gelatinization for the starch under study may be attributed to a higher proportion of short branch lengths of amylopectin and the probable presence of monophosphate derivatives (Spence & Jane, 1999). In Table 2, the gelatinization enthalpy of 8.12 J/g for borassus starch is lower than 11.02 J/g for maize but higher than 4.35 J/g potato, and 5.01 J/g for cassava. Both gelatinization temperature and enthalpy gelatinization of

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302 J.T. Barminas et al. / Food Hydrocolloids 22 (2008) 298304 Table 3 Effects of storage on the gel strength of borassus starch Concentration (%w/v) Gel strength (g) 6h 2 4 6 8 10 12 14 ND 68 96 108 122 164 190 1 day ND 68 95 107 123 163 188 2 days ND 67 97 107 123 164 188 4 days ND 67 96 106 122 163 187 7 days ND 67 95 106 122 162 187 Table 2 Thermal properties of borassus starch compared with other starches Type of starch Borassus Maize Potato Cassava T0 (1C) 61.1 63.5 62.1 63.9 Tp (1C) 66.2 67.5 68.5 70.8 Tc (1C) 74.2 73.4 79.8 83.6 TcT0 (1C) 13.1 9.9 17.7 19.7 DH (J/g) 8.12 11.02 4.35 5.01

starches are known to depend on the micro-structures, presence of crystalline regions of different strengths in the granule, granule size, and amylose-to-amylopectin ratio (Ahmad et al., 1999; Singh & Singh, 2001). 3.4. Gelation properties

ND: not determined; viscous solution.

60 Water separation (%) 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 Freeze-thaw cycles (no)

The gel strengths of borassus starch pastes are presented in Table 3 where the least gel concentration (LGC) was obtained at 4% (w/v). The gel obtained at LGC was observed to be a cloudy translucent soft gel. However, rm translucent gels were obtained at concentrations X10% (w/v). During gelation process, gelatinization and absorption of water to build a three-dimensional network takes place. The building of the structural networks involves intergranular binding forces among the starch molecules which largely involves hydrogen bonding (Lawal & Adebowale, 2005). Hence, substantial interaction between starch molecules may contribute to the ready formation of gels shown by the starch in this study. The re-association among gel components may occur during cooling, which might lead to the increase in gel strength as the concentration of the starch increases as shown in Table 3. Despite maintaining their gel strength for 7 days period (Table 3), the gels became cloudy, non-uniform, and showed decrease in paste clarity after 4 days. Fig. 4 gives the freezethaw stability of borassus starch paste. This presentation shows freezethaw stability suggestive of a low retrogradation tendency. This retrogradation could be reduced and other gelation properties enhanced by introduction of hydrocolloids such as xanthan, galactomannan, or other gum molecules. Such starchhydrocolloid systems may offer application in the food industries because hydrocolloids exhibit many functions to control rheological and textural properties of food, improve moisture retention, and maintain overall product quality (Funami et al., 2005). 3.5. Pasting properties The pasting characteristics of 8% (w/w) starch water suspension are presented in Table 4. The gelatinization temperature obtained was 64.5 1C which is lower than 67.4, 71.3, and 82.0 1C reported for cassava, rice, and corn starches, respectively (Srichuwong et al., 2005). A difference was observed between DSC gelatinization onset (T0) in Table 2 and the pasting temperature (Table 4) suggesting

Fig. 4. Freezethaw stability of 8% (w/w) paste of borassus starch. Error bars represent standard deviations.

Table 4 Pasting characteristics of borassus starch Parameter Apparent gelatinization temperature (1C) Peak viscosity during heating (PV) Viscosity at 95 1C after 30 min holding, HV30 Cold paste viscosity at 50 1C (CV) Setback viscosity, SB (CVPV) Breakdown viscosity (PVHV30) Percentage of breakdown, BD% [(BD/PV) 100]
a

Valuea 64.5 470 278 585 115 192 40.85

Values are reported in Brabender units (BU).

that the melting process preceded the initial increase in viscosity (Chaisawang & Suphantharika, 2006). Further, the lower gelatinization temperature implies a shorter cooking time for this starch. The highest peak viscosity recorded at 470 BU was actually obtained at 67 1C showing that the DSC peak temperature, Tp (66.2 1C) (Table 2) and the pasting temperature measured from Brabender equipment are comparable. This is attributed to the melting of starch crystallites which occurred cooperatively in excess water, and coincided with that of the rst rise in viscosity where the rate of development of viscosity was the greatest (Rao, 1999). The viscosity at 95 1C after 30 min holding (HV30) was found at 278 BU (Table 4). This is a thinning effect which

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might be due to the weakening of bonding forces within the granules and their physical BD (Rasper, 1980). In Table 4, a signicant increment in viscosity (585 BU) was observed on cooling the slurry paste at 50 1C for 30 min which may be due to the association of the starch molecules to form aggregates of low solubility leading to gel formation (Leelavathi & Sidhu, 1987) or retrogradation tendency (Rincon et al., 1999). The peak viscosity of the paste from borassus starch shows that it may form thick and rm gels rather than a viscous paste on cooling. It could also contribute to good textural quality in food products. Table 4 also shows a drop in viscosity of 192 BU which is the BD viscosity indicating the possible BD of the starch granules, and is a measure of the fragility of starch (Krishnakumari & Thayumanavan, 1998). The percentage BD (BD %) of 40.85 during cooking is lower than 62.671.2% reported for sago, cassava, and potato starches (Srichuwong et al., 2005). This result shows low BD viscosity during the continuous heating phase at 95 1C. This cooked paste stability may show the potential of the starch for use in porridges (Hadimani & Malleshi, 1993) with less susceptibility to enzyme attack (Krishnakumari & Thayumanavan, 1995). A setback viscosity of 115 BU is equally indicative of paste stability; a high setback viscosity is associated with cohesiveness of the pastes (Otegbayo, Aina, Asiedu, & Bokanga, 2006). 4. Conclusion Starch isolated from the germinating nuts of giginya palm showed low water-binding capacity and limited swelling and solubility values. The physicochemical and pasting characteristics, particularly, high peak viscosity, low DH, low retrogradation, cheapness, and considerable starch yield of borassus starch are indices for possible application in food and non-food industries. Acknowledgement We appreciate and thank the University Board of Research of Adamawa State University Mubi, Adamawa State, Nigeria for support and provision of fund for this research. References
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