1 Introduction
2.1 Materials
Weight of
sodium dihydrogen
phosphate salt [g]
Weight of
sodium hydrogen
phosphate salt [g]
Combined
weight [g]
0.5:1
1.0:1
1.5:1
2.0:1
2.5:1
3.0:1
3.5:1
30.40
60.81
91.22
121.63
152.05
182.46
212.87
16.21
32.43
48.66
64.87
81.08
97.30
113.52
46.62
93.25
139.88
186.51
233.14
279.77
326.40
0038-9056/2000/0404-0095$17.50+.50/0
95
Phosphorus was colorimetrically determined by the reaction with ammonium molybdate according to the method described by Murphy and Riley [16] in native and phosphorylated starch products and the DS was calculated using the
equation of Paschall [4] as follows:
DS of monosodium esters =
162P
3100102P
The data recorded in Tab. 2 show the degree of phosphorylation of corn starch during 4 h reaction time at 150 C under vacuum (800 mbar), pH 6 and a molar ratio 1:1 (mole
phosphate:mole anhydrous glucose).
Tab. 2. Effect of reaction time on the degree of phosphorylation extent
of corn starch using 1:1 molar ratio (mole phosphate: mole anhydrous
glucose) and pH 6 at 150 C.
Reaction time [h]
1.51
1.37
1.78
1.63
2.43
2.35
2.71
2.58
96
Fig. 1. Influence of the reaction temperature on the extent of corn phosphorylation. A.D.: After dialysis. B.D.: Before dialysis.
Starch/Strke 52 (2000) Nr. 4, S. 95100
Fig. 2. Effect of the reaction medium pH on the extent of phosphorylation of corn starch. A.D.: After dialysis. B.D.: Before dialysis.
3.1.3 Reaction pH
The data in Fig. 2 show the effect of pH on the phosphorylation of corn starch at 150 C, 2 h reaction time and a molar ratio 1:1 (mole phosphate : mole anhydrous glucose).
The obtained results revealed that the extent of phosphorylation was highest in the pH range 56 but diminished in
acidic (pH 4) and alkaline (pH 8,9) media. The best binding
of phosphate to starch occurred at pH 6. Low pH may result
in a certain degree of starch hydrolysis [4], while alkaline
pHs might affect the stability of the ester bonds formed
between the phosphate groups and the starch molecules
[19].
Calculating the percentage of phosphorus removed by
dialysis gave the values 11.0, 5.3, 5.2, 8.7, 11.5 and 52.6%
through the pH range 49, respectively. This implies that the
efficiency of the washing step was increased in the highly
modified starch (pH 5 and 6) as compared with the low-modified ones (pH 4.8 and 9).
3.1.4 Molar ratio
Tab. 3. Total phosphorus content and degree of substitution of unmodified and phosphorylated starches.
Molar ratio
Corn starch
Rice starch
Potato starch
Corn amylose
Corn amylopectin
Phosphorus [%]
0.0:1
0.5:1
1.0:1
1.5:1
2.0:1
2.5:1
3.0:1
3.5:1
B.D.
A.D.
B.D.
A.D.
B.D.
A.D.
B.D.
A.D.
B.D.
A.D.
0.02
1.67
3.06
3.34
3.56
3.79
4.24
4.59
0.02
1.55
2.99
3.16
3.29
3.43
4.05
4.18
0.04
1.41
3.10
3.61
4.00
4.44
4.97
5.51
0.04
1.30
2.89
3.42
3.73
4.27
4.70
5.26
0.06
1.23
3.49
4.38
0.06
1.20
3.36
4.23
0.00
2.07
3.77
4.68
0.00
1.97
3.68
4.50
0.01
1.69
2.99
3.97
0.01
1.46
2.91
3.80
Degree of substitution
0.0:1
0.5:1
1.0:1
1.5:1
2.0:1
2.5:1
3.0:1
3.5:1
0.00
0.09
0.17
0.18
0.19
0.2
0.24
0.25
0.00
0.07
0.17
0.2
0.22
0.26
0.29
0.33
0.00
0.07
0.2
0.26
0.00
0.11
0.22
0.28
0.00
0.08
0.17
0.23
The determination of mineral matter may give some indication of the starch grade. Ashing at too high a temperature
Tab. 4. Ash content of unmodified and phosphorylated starches, calculated as % of dry matter.
Molar ratio
Corn starch
Rice starch
Potato starch
Corn amylose
Corn amylopectin
0.0:1
0.23
0.32
0.37
0.07
0.08
0.5:1
1.32
1.26
1.23
1.48
1.29
1.0:1
1.69
1.50
1.5:1
2.07
2.55
2.34
2.0:1
2.68
2.89
2.5:1
3.13
3.56
3.32
3.0:1
3.90
4.17
3.5:1
4.44
5.01
98
Corn starch
Rice starch
Potato starch
Corn amylose
Corn amylopectin
0.0:1
0.5:1
1.0:1
1.5:1
2.0:1
2.5:1
3.0:1
3.5:1
0.02
0.21
0.43
0.45
0.46
0.51
0.60
0.74
0.00
0.20
0.31
0.46
0.54
0.75
0.81
0.94
0.01
0.15
0.45
0.63
0.00
0.11
0.22
0.28
0.00
0.08
0.17
0.23
ed starches may be due to the buffering action of the monoand disodium hydrogen orthophosphates used in the preparation of the phosphorylated polysaccharides.
The mono- and disodium hydrogen orthophosphates
added to the reaction medium at a ratio to maintain the pH at
6 (for all the molar ratios) during the reaction course seem to
maintain their buffering influence on the product pH, keeping it very close to the original pH value of 6. In addition the
conditions used in the reaction will allow producing modified starches having a pH close to the starting one, irrespective of the used molar ratio of the reagent.
3.2.3 Starch acidity
References
[1] J. Kerb (1919), cited in: Starch Production Technology. Ed. J. A.
Radley. Applied Science Publishers LTD., London 1976, p. 543.
[2] H. Pringsheim and K. Goldstein (1923): Production and
uses of starch phosphates, cited in: Starch Chemistry and
Starch/Strke 52 (2000) Nr. 4, S. 95100
99
100
Saadany and Mr. M. F. Ramadan, Biochemistry Dept., Faculty of Agriculture, Zagazig Univ., Zagazig, Egypt.
* Corresponding author.