Food Chemistry 121 (2010) 10291038

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Physicochemical properties of commercial semi-sweet biscuit

Hasmadi Mamat a, Madian O. Abu Hardan b, Sandra E. Hill a,*
a b

Food Sciences Division, School of Biosciences, Sutton Bonington Campus, University of Nottingham, Loughborough, Leicestershire, LE12 5RD, United Kingdom Nestle Product Technology Centre, Applied Science Department, Haxby Road, P.O. Box 204, York, YO91 1XY, United Kingdom

a r t i c l e

i n f o

a b s t r a c t
This study was performed to provide information about the physical and chemical characteristics of commercial semi-sweet biscuits and to ascertain the key characteristics of commercial semi-sweet biscuits (rich tea type), in terms of starch properties, such as gelatinisation, pasting, granule crystallinity and morphology, and to compare the magnitudes of changes of physical characteristics (diameter, thickness, weight and bulk density) for selected brands. A total of 10 rich tea biscuits from different brands were bought locally and were measured for physical and chemical characteristics. The three-point bend test showed that a biscuit with lower fat content was harder than a biscuit with normal fat content, except for sample B. Starch gelatinisation properties show that To, Tp and Tc were higher than for wheat our whereas DH was lower than for wheat our. X-ray results showed that commercial biscuits still retained their crystallinity but at lower intensities than native wheat our. Microscopy observations revealed that some of the granule birefringence of commercial biscuits can still be observed under polarised light. Different brands of biscuits showed different physical and chemical characteristics. 2010 Published by Elsevier Ltd.

Article history: Received 10 November 2008 Received in revised form 1 December 2009 Accepted 26 January 2010

Keywords: Semi-sweet biscuit Starch Three-point bend test Polarised microscopy Differential scanning calorimetry X-ray diffraction

1. Introduction Many studies dealing with biscuit have been reported in the scientic literature. In biscuit making, the principal ingredients are wheat our, sugar, fat, water and salt. These are mixed together with other minor ingredients (baking powder, skimmed milk, emulsier and sodium metabisulphite) to form dough containing a well-developed gluten network. The nature and quantity of ingredients used determine the quality of the biscuit. Several researchers have described the effect of major ingredients in biscuit dough systems and on the nal product (Chevallier, Colonna, Buleon, & Della Valle, 2000a; Chevallier, Colonna, Della Valle, & Lourdin, 2000b; Maache-Rezzoug, Bouvier, Karim, & Patras, 1998). Different types of wheat our produce dough and nal products with different rheological and baking characteristics (Pedersen, Kaack, Bergsoe, & Adler-Nissen, 2004). The fat (or shortening) contributes to the plasticity of the dough and acts as a lubricant. Sugar (sucrose) contribute to sweetness, volume, tenderness, texture and colour, and also acts as a preservative. A number of techniques have been used to study starch properties in biscuit affected by the baking process and the ingredients used. Differential scanning calorimetry (DSC) is the most commonly used technique in studies of starch gelatinisation, providing quantitative measurement of the enthalpy of the energy of transformation that occurs during the melting of crystallites in the
* Corresponding author. Tel.: +44 0 115 951 6143; fax: +44 0 115 951 6142. E-mail address: sandra.hill@nottingham.ac.uk (S.E. Hill). 0308-8146/$ - see front matter 2010 Published by Elsevier Ltd. doi:10.1016/j.foodchem.2010.01.043

starch granules. The Rapid Visco Analyser (RVA) is a useful tool for studying starch pasting properties and the effects of other food ingredients on starch performance. The RVA indicates starch viscosity (by measuring the resistance of our and water slurry to the stirring action of a paddle). The three-point bend test (also called three-beam snap technique) is a common technique, used to evaluate textural quality (hardness and fracturability) of cookies (Gaines, Kassuba, & Finney, 1992). In each test, the peak force (hardness) and distance to peak (i.e. distance to reach peak height) are measured. These two parameters were used to estimate the texture characteristics of biscuits. Wide-angle X-ray diffraction (WAXD) is an X-ray diffraction technique that is often used to determine the crystalline structure of polymers and widely used to determine starch crystallinity (Jagannath, Jayaraman, Arya, & Somashekar, 1998). Rich tea is a type of semi-sweet biscuit with a circular shape and the biscuits are very popular in the United Kingdom. At the moment, very limited information about physicochemical characteristics of commercial rich tea biscuit can be found in the scientic journals. The present study was performed to provide information about the physical and chemical characteristics of commercial semi-sweet biscuits, using several techniques. The aim of the work was to ascertain the key characteristics of commercial semi-sweet biscuits (rich tea type) in terms of starch properties, such as gelatinisation, pasting, granule crystallinity and morphology, and to compare the magnitudes of changes of physical characteristics (diameter, thickness, weight and bulk density) of selected brands, which may useful for bakers.

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2. Materials and methods 2.1. Sampling A total of 10 rich tea biscuits of different brands were bought locally. They were divided into two main groups based on fat content; normal rich tea biscuits and fat-reduced rich tea biscuits. Normal rich tea biscuit were A, C, D, F, G, I and J; while reduced-fat rich tea biscuits were B, E and H. Wheat our, sugar, vegetable oil, raising agent, malt extract and salt were the common ingredients used, as indicated on the packaging, while emulsier, sucrosefructose syrup, glucose syrup, cultured skimmed milk, preservatives and invert sugar were also used for certain brands. From each brand, several samples were bought, which were from different batches and they were randomly selected for the experiments performed. 2.2. Proximate analysis Crude protein content (N 5.7) of the biscuits was determined according to the Dumas method, using a protein nitrogen analyser (Leco FP-200). Total lipid content was determined by a fat extraction method, using isooctane. After extraction, the collection bottle was placed on a hotplate for 2 h at 120 C. To determine the quantity of total fat, the collection bottle was weighed before and after extraction. Starch content was determined, using a total starch Megazyme assay kit (amyloglucosidase/a-amylase method) (Megazyme International Ireland Limited, Wicklow, Ireland). Sugar content was determined, using sucrose/d-glucose/d-fructose Megazyme assay kit (Megazyme International Ireland Limited, Wicklow, Ireland). 2.3. Dimensions, density and moisture content The diameter and the thickness were measured with a Vernier Calliper. The diameter of a biscuit is given as the average value of two orthogonal diameters and in each measurement, the average of 10 biscuits, was recorded. The density was determined by the solid replacement technique using rapeseed. A container of known weight and volume was lled with rapeseed and excess rapeseeds were trimmed off slowly. The bottom of the container was covered with rapeseed and a biscuit of measured weight was placed in the container with the attest surface downwards. The container was lled with rapeseed and the total weight measured. For every biscuit, the mean of ve determinations was taken as the density. The moisture contents were measured gravimetrically by drying in a 105 C oven. For each measurement, 12 g of samples were placed in an aluminium tray and left in the oven for 24 h. Each measurement was performed in triplicate. All moisture contents are reported on a percentage wet weight basis, i.e. gram of water per 100 g of total sample (w/w w.w.b). 2.4. Colour The colour of the two surfaces of a biscuit (top and bottom), in terms of brightness (L*), redness (a*) and yellowness (b*), was measured using the Hunterlab (Labscan spectrophotometer V1A30, Hunter Associates Lab Inc., Reston, VA), calibrated with a black glass and a white tile (Illuminant D65, CIE 10 observer, Ls 13593). The scale for a* varies from green (negative) to red (positive) and the scale for b* corresponds to a yellow-blue scale on which yellow is positive. The colour data correspond to averages of ve measurements for each biscuit for a total of 10 biscuits.

2.5. Hardness The hardness of the biscuits was studied using a three-point bend test performed on a TAXT2 Texture Analyzer, equipped with the three-point bending rig (HDP/3 PB). The span between the supports was 40 mm. Texture Analyzer settings were pre-test speed at 1.0 mm/s, test speed at 3.0 mm/s, post-test speed at 10.0 mm/s, distance at 10 mm and data acquisition rate at 500 pps. The load cell used was 5 kg. The maximum force was recorded and is can be referred to as the hardness of the biscuit. An average value of 10 replicates is reported. The distance to break was also recorded. 2.6. Pasting properties Pasting properties of the biscuits were measured using the RVA4 (Newport Scientic, Australia) instrument. The samples were milled for 30 s, using a Tecator Knifetec 1095 sample mill (Foss tecator, Sweden) and the powders were sieved for 5 min to a particle size of 150250 lm, using a sieve shaker (Analysette SRL 5300, Fritch, Idar-Observation, Germany). The RVA measurements were then performed, using 4 g of biscuit sample, and 24 g of distilled water were added, followed by mixing in the canister and placing in the RVA. The suspension was kept at 25 C for 2 min, heated to 95 C for 6 min at 13.5 C/min, and kept at 95 C for 3 min; it was then cooled to 25 C at 14 C/min for 6 min and kept at 25 C for 2 min. The peak viscosity and the nal viscosity were determined from the RVA plots. Three repetition measurements were conducted to obtain the reported value. 2.7. Starch gelatinisation properties The starch gelatinisation properties and fat melting prole were measured using DSC as follows: samples (3.5 0.2 mg) with 10 mg of distilled water (i.e. in excess water) were hermetically sealed in DSC pans and kept at room temperature for 12 h. Next, samples were scanned against a blank (empty pan) using a Perkin Elmer Pyris 7 DSC (Perkin-Elmer Co., Norwalk, CT) by heating from 5 to 95 C at 10 C/min. An empty pan was used as a reference. Starch gelatinisation parameters, given by DSC thermogram, are the onset temperature (To), the conclusion temperature (Tc), the peak temperature or maximum temperature (Tp), and the enthalpy (DH). 2.8. X-ray diffraction Wide-angle X-ray diffraction (Bruker AXS 5005 GmbH, Karlsruhe, Germany) was used to analyse the crystallinity of the samples. The X-ray generator is equipped with a copper source operating at 40 kV and 30 mA, producing Cu Ka radiation with a wavelength of 1.54 . Data were recorded over an angular range of 430 with an angular interval of 0.05. The spectrum of the metal holder was rst recorded under the same experimental conditions and then subtracted from the spectra acquired for the sample. 2.9. Polarised light microscopy The morphology of the starch granules was visualised and recorded with a polarised light microscope (Wild Leitz GmbH, Wetzlar, Germany) tted with a digital camera. Dry samples powders (125250 lm) were placed on a standard glass microscope slide and a drop of water was carefully added. They were then covered with cover slip. Visual magnications were 200. 2.10. Statistical analysis Statistical differences were determined by an analysis of variance (ANOVA), with mean separations performed by the Tukey

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HSD test, using SPSS version 10. Mean and STDV were calculated for each measurement where applicable. 3. Results and discussion 3.1. Biscuit dimensions and moisture content During the baking process, many changes take place in the biscuit dough. The most important of these are changes in dimension, loss of moisture and development of colour and avour. The dimensions of the end-product are important in the quality control of baked products (Cronin & Preis, 2000). Results of thickness, diameter, weight, moisture content and density of commercial biscuits are presented in Table 1. Thickness, diameter and weight ranged from 5.41 to 6.23 mm, 63.50 to 70.64 mm and 7.73 to 9.80 g, respectively. Sample B had the highest thickness value and was signicantly different (p < 0.05) from the other samples while F and I had the highest values for diameter and weight, respectively. The thickness of hard dough biscuits results from the balance between the setting of the biscuit structure by thermal denaturation of the gluten network and the expansion of the dough by the action of the aerating agents and the steam. This balance will be affected by the rate of rise of temperature of the dough during the early stages of baking. Thus, the use of lower temperatures in the rst part of baking, which reduces the rate of temperature rise in the dough piece, would produce signicantly thicker nal products (Wade, 1988). For the three most important properties of biscuit, thickness, diameter and weight, it can be stated that the coefcients of variation (standard deviation divided by mean of commercial biscuits measured) were between 0.44% and 4.00% (Table 2). Samples with the lowest coefcient of variance (%) indicate that the manufacturer has a better process control over the production. The moisture content of commercial biscuits ranged from 2.24% to 3.23% (Table 1). Biscuits are very low moisture content products. The majority of the moisture lies in a thin lamella of material near the centre, while the surface and the outer periphery of the product are nearly dry. The typical initial moisture content of biscuit dough ranges from about 1130%, comprising both water added at the dough mixing stage and water naturally occurring in the ingredients. Thermal processing reduces the nal moisture content to 15% in the nal product. 3.2. Colour of biscuits Colour appears to be a very important element for the initial acceptability of baked products by consumers. Moreover, as colour
Table 1 Physical properties of commercial semi-sweet biscuit. Thickness (mm)1 A B C D E F G H I J 5.36 0.17 6.23 0.25a 5.62 0.15c,d,e 5.41 0.15b 5.85 0.15b 5.74 0.15b,c 5.54 0.07e,f,g 5.58 0.17d,e,f 5.47 0.14f,g,h 5.69 0.18c,d
h

Table 2 Coefcients of variance (%) of thickness, diameter and weight. Sample A B C D E F G H I J Thickness coefcient of variance (%) 3.2 4.0 2.7 2.8 2.6 2.6 1.2 3.0 3.1 2.6 Diameter coefcient of variance (%) 0.99 1.42 0.58 0.66 0.44 0.64 1.43 0.46 0.78 0.63 Weight coefcient of variance (%) 2.04 1.54 1.85 2.31 2.04 1.43 3.88 1.54 1.77 1.55

development occurs largely during the later stages of baking (Wade, 1988), it can be used to judge completion of the baking process. The Hunter parameters L*, a* and b* for the top and bottom surface of commercial biscuits are shown in Fig. 1. L* value is a measure of the lightnessdarkness fraction (L* = 0 yields black and L* = 100 indicates white). Sample D had the highest L* value for the top surface as well as the bottom surface and was signicantly different (p < 0.05) from the other samples. The L* value of the bottom surface samples was higher than the value for the top surface, except for samples J and H. The a* value gives an indication of the redness and high a* values were found for both surfaces of biscuits that were dark in colour (low L-value.). Top surface results showed that D had the lowest a* value while C had the highest, and they were signicantly different (p < 0.05) from the other samples. The b* value is a measure of the yellowness of the surface colour. Sample B and J top surfaces had the highest and lowest b* values, respectively and they were signicantly different (p < 0.05) from the other samples. Colour development of baked products is caused by Maillard reactions between sugars and proteins (Lingnert, 1990). The Maillard reaction is a non-enzymatic reaction which causes the formation of melanoidins. The melanoidins give an impression of brownness which increases with increasing concentration of melanoidins. Others factors that might contribute to the colour of nal products were ingredients composition, time of baking (Cronin & Preis, 2000) and humidity in the oven atmosphere in the early stages of baking (Wade, 1988). Malt extract, used as one of main ingredients, is a source of soluble sugars and protein contributing avour and colour to the nished baked products (Mahdi, Abdal, Behra, Verma, Sanone & Makhija, 2008). It is also reported that protein content has a negative correlation with L* value, indicating that increasing protein content in biscuit formulation reduces L* value (Gallagher,

Diameter (mm)2 65.20 0.65 63.94 0.91e 69.57 0.41b 65.18 0.43d 70.16 0.31a 70.11 0.45a,b 63.51 0.91e 68.69 0.32c 63.50 0.40e 70.64 0.55a
d

Weight (g)3 8.35 0.17 8.44 0.13b 9.74 0.18a 8.22 0.19b 9.78 0.20a 9.80 0.14a 7.73 0.30c 9.74 0.15a 7.74 0.12c 9.58 0.17a
b

Moisture content4 2.24 0.32 2.63 0.08 2.37 0.24 3.19 0.17 3.23 0.21 2.79 0.52 3.25 0.12 2.77 0.10 2.72 0.11 2.43 0.59

Density (g/l)5 396.1 20.3 399.7 17.8 349.9 22.3 398.2 27.7 402.4 21.9 342.7 14.6 344.6 23.8 354.2 24.8 328.7 11.5 374.1 20.5

Superscript (15) indicate numbers and type of measurement. Means with different letters (ah) in each column are signicantly different (p < 0.05). 1 n = 10 (average at three different points (angle of 120) of ten samples). 2 n = 10 (average at two orthogonal points of ten samples). 3 n = 10. 4 n = 3. 5 n = 5.

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Kenny, & Arendt, 2005; OBrien, Chapman, Neville, Keogh, & Arendt, 2003). 3.3. Biscuit texture evaluation Texture is a very important quality characteristic which makes a signicant contribution to the overall quality acceptance of food
76 74 72 70

products. It was one of the three main acceptability factors used by consumers to evaluate food, the other two being appearance and avour (Bourne, 1990). Biscuit hardness and distance to break the samples of 10 commercial rich tea biscuits are presented in Fig. 2(a) and (b), respectively. The results indicate that the breaking strengths of the samples were comparable. Generally, peak forces required to break the biscuits can be divided into three groups,

Top

Bottom

L* value

68 66 64 62 60 58 56 A B C D E F G H I J

Sample

(a)
10

Top

Bottom

a* value

0 A B C D E F G H I J

Sample

(b)
35

Top
30

Bottom

25

b* value

20

15

10

0 A B C D E F G H I J

Sample

(c)
Fig. 1. (a), (b) and (c) showing L*, a* and b* values of commercial semi-sweet biscuit.

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40 35 30
ab ab b bc bcb b ab a

Peak force (N)

25 20 15 10 5 0 A B C

Sample

(a)
1 0.9
abc ab abc c abc a

0.8

c c

bc

Peak distance (mm)

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 A B

Sample

(b)
Fig. 2. Textural properties of biscuits, as measured using three-point bend test, for peak force (a) and distance to break (b). The same small letter denotes values not signicantly different (p > 0.05) one from the other.

which: are peak force below 20 N (sample F), between 20 and 30 N (samples A, B, C, D, G, I, and J) and above 30 N (samples E and H). The gure shows that most biscuits had a peak force in the range 20 to 30 N. Sample F required the least force to break and this force was signicantly different (p < 0.05) from samples A, B, D, E, H, I and J. Reduced fat samples E and H required signicantly greater forces to break the biscuits compared to many samples (C, D, F, G and I). However, sample B, the other low fat sample, was not significantly different in hardness from all the other samples, except F. It would appear that ingredient information alone cannot explain the perceived hardness of these biscuits. The distance the biscuit will deform before breaking is given in Fig. 2(b). Samples H and I deformed to distances of 0.90 and 0.87 mm, respectively. These values were signicantly different (p < 0.05) from samples C, E, F, G and J. There was no correlation between the distance to break and the force required (Fig. 3). However, the dimension of the biscuit would also be expected to be relevant. Typically, for three-point bending, the value alters with the cube of thickness (Bourne, 2002). Therefore biscuit thickness might be expected to be relevant, but the correlation between hardness and thickness was only 0.017. The poor correlation may reect

the ingredients used. Two products of reduced fat gave products of higher break strength compared to their full fat equivalents (E vs. D and H vs. G). Removal of the fat typically increases the proportion of sugar in the recipe. However, for the samples studied, only sample E had signicantly more sugar than had the full fat equivalent (Table 3). This was in agreement with Sudha, Srivastava, Vetrimani, and Leelavathi (2007). They found that the force required for breaking biscuits containing 70% less fat was almost three times more than that required to break the control biscuit. Sugar crystallization and formation of a glassy solid after baking would inuence hardness of biscuit (Gaines et al., 1992; Slade & Levine, 1994; Slade, Levine, Ievolella, & Wang, 1993); although the sugar levels are not different their location and state may be inuenced by the fat level. Sugar may recrystallise during cooling or product storage as water is removed during baking, creating a supersaturated sucrose solution in the biscuit. Sugar syrups are used at relatively low levels in biscuits for their distinctive avours. They are also used as humectants (materials that prevent the loss of water from food) and, as such, prevent the baked textures from being too hard and brittle.

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60

50

40

Peak Force (N)

30

20

10

0 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3

Distance (mm)
Fig. 3. Correlation between distance to reach maximum peak and maximum peak force required to break the biscuits.

The coefcient of variance (ratio of standard deviation to the mean) of the measurement of mechanical parameters (peak force and distance to break) was between 12.5% and 30.9%. Kim and

Table 3 Proximate analysis of commercial semi-sweet biscuits. Sample A B C D E F G H I J Total fat content (%, wb) 15.8 0.3 9.7 0.1 15.4 0.2 14.7 0.2 9.3 0.8 14.9 0.2 14.7 0.9 9.5 0.0 14.1 0.2 14.5 0.3 Crude protein (%)* 6.4 7.0 6.3 6.4 6.6 6.5 6.2 6.7 6.2 6.2 Sugar (%) 18.5 0.7 18.0 0.5 17.2 0.0 18.2 0.0 18.8 0.4 17.7 0.7 18.4 0.8 18.5 0.3 19.4 0.4 19.3 0.4 Total starch (%, dw) 52.4 0.2 55.7 0.1 54.5 0.7 53.6 0.5 55.0 0.5 54.0 0.2 53.7 0.3 56.4 0.0 52.8 0.5 52.5 0.2

Okos (1999) investigated the mechanical properties of crackers, using a three-point bending technique, and found coefcients of variance of the samples between 12.8% and 47.8%. Brittle and crunchy foods are known to have very irregular and irreproducible forcedeformation relationships (Peleg & Normand, 1992). This seems to be due to the non-uniformity in internal structure and surface characteristics of this type of cellular material. Gormley (1987) also reported 2439% variation of the fracture force measured for ve brands of cream crackers. Therefore, an understanding of the inuence of ingredients on the texture may be difcult without a greater insight into the structure of the products. 3.4. Pasting properties The Rapid Visco Analyser has been used extensively to determine pasting properties of starch (Kim & Walker, 1992; Ravi, Sai Manohar, & Haridas Rao, 1999), mixtures of starch and other components (Zhou, Robards, Helliwell, & Blanchard, 2007) and baking properties (Keskin, Ozturk, Sahin, Koksel, & Sumnu, 2005). Fig. 4 shows typical RVA proles of four selected samples, while the peak

All values are means of duplicate samples except for protein (mean SD). * N 5.7

3000

A
2500

2000

Viscosity (cP)

1500

1000

500

0 0 200 400 600 800 1000 1200

Time (s)
Fig. 4. Rapid visco-analyser proles of four selected commercial rich tea biscuit samples.

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viscosity and nal viscosity values of all samples, based on equivalent starch levels, are shown in Fig. 5. The RVA proles reect the combined features of biscuit particle swelling and solubility with prole due to pasting of the starch still in semi-crystalline form. Below an onset temperature of gelatinisation (usually below 60 C), starch granules are insoluble in water and the viscosity of an aqueous dispersion remains low, and no cold viscosities were observed for the biscuits. Swelling, to the extent of recordable increases in viscosity for the samples, started when the temperatures were in excess of 80 C. Comparisons between biscuits showed signicant differences both in the peak viscosities, occurring after about 9 min, and the nal viscosity of the sample (Fig. 4). Direct comparison between the low fat and the normal sample showed high viscosities, both peak and nal, for the low fat sample. However, as indicated in Table 4, the level of starch in these samples was higher than in their controls. Fig. 5 shows the peak and nal viscosities for all the biscuits when the starch content was adjusted to the same amount (50% of product). Although there is again signicant difference between samples, the relationship between the low fat samples and their controls is not the same for different manufacturers of the biscuit. No clear reasons for the difference in RVA proles can be deduced if the starch levels are made equivalent. It is suggested that oil type and level can affect the pasting properties (Davis,

Grinder, & Gordon, 1986; Zhou et al., 2007) but, in these samples, all the fat levels are probably high enough to inuence the RVA and no discrimination between samples is possible. 3.5. Gelatinisation properties and fat melting prole The thermal properties of the biscuits were examined using DSC. Table 4 shows biscuit (starch) gelatinisation and fat melting properties (biscuits were added to excess water), whereas Fig. 6 depicts DSC prole for normal (A) and reduced-fat biscuit (B). Onset temperature (To), peak temperature (Tp), conclusion temperature (Tc) and energy enthalpy (DH) ranged from 56.6 to 60.5 C, 65.2 to 67.3 C, 67.2 to 73.0 C and 5.09 to 9.78 J/g, respectively. To, Tp and Tc were higher than for wheat our because of the presence of other ingredients in the system, especially sugar and salt. It is reported that sugar can interact with the amorphous region of the starch granules, and lead to an increase starch gelatinisation temperature. Sugar will affect the gelatinisation of starch by delaying or inhibiting gelatinisation of starch. Sugar molecules may form bridges between neighbouring polysaccharides located within the amorphous region of the granules and restrict movement of these areas so that gelatinisation is shifted to higher temperatures (Eliasson, 1992; Johnson, Davis, & Gordon, 1990). The original cooking, at the low starting levels of water could be assumed to anneal

3500

Peak viscosity
3000 ab cd 2500 e f 2000 de de a de

Final viscosity
bc

cd

Viscosity (cP)

1500 b 1000 ef g cd a f de ef bc bc

500

0 0 1 A 2 B 3 C 4 D 5 E 6 F 7 G 8 H 9 I 10 J 11

Sample
Fig. 5. Peak viscosity and nal viscosity value of all samples, based on equivalent starch levels. The same small letter denotes values not signicantly different (p > 0.05) one from the other.

Table 4 Starch gelatinisation and fat melting proles. Sample Starch To (C) A B C D E F G H I J Wheat our 60.1 59.8 59.7 59.4 59.7 60.2 60.5 60.2 60.1 60.2 56.6 Tp (C) 67.3 67.2 65.8 66.7 65.2 65.8 65.8 65.8 65.8 66.0 62.5 Tc (C) 71.9 71.8 71.2 72.0 71.7 71.3 71.8 71.4 73.0 71.8 67.2 Fat

DH (J/g) of dry starch

7.91 8.35 7.67 8.82 8.34 7.87 5.09 7.99 7.80 7.98 9.78

To (C) 25.0 27.4 23.9 25.1 23.7 25.8 23.8 25.4 23.7 23.7

Tp (C) 29.8 30.8 28.5 30.2 29.7 30.2 29.7 30.2 26.0 28.3

Tc (C) 32.4 33.9 32.6 33.4 34.7 32.8 32.9 33.4 36.3 35.8

DH (J/g) of biscuit
2.94 1.99 1.48 1.68 0.72 0.86 2.04 0.89 1.29 1.96

* To onset temperature, Tp peak temperature, Tc conclusion time, DH energy enthalpy.

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the starch, hence, reducing the amounts encountered at the lower end of the temperature range (Vanessa, 2002). Commercial biscuits showed lower DH than did native wheat our. However, a signicant amount (approximately 80%) of the starch was retained its native order. Sample G showed only 50% of the expected original crystallinity/helical order. DSC is important tool for studying melting characteristics of fats and oils (DSouza, de Man, & de Man, 1991; List, Adlof, Carrierre, & Dunn, 2004). Semi-sweet biscuit contains up to about 15% of fat (percentage of our weight). To, Tp, Tc and DH ranged from 23.7 to 27.4 C, 26.0 to 30.8 C, 32.4 to 36.3 C and 0.72 to 2.94 J/g, respectively (Table 4). Enthalphy (DH) measured the energy required to melt all the fats present. The composition (solid fat content and degree of saturation) inuence the energy required. The greater the solid fat content of the sample the greater was the energy needed to melt the sample. 3.6. Crystallinity measurement X-ray diffraction was used in this study to investigate changes in crystallinity of starch due to the baking process. It has been used to study various existing starch crystal types (Cheetham & Tao,

1998), the extent of starch melting and gelatinisation (Zobel, Young, & Rocca, 1988), and the extent of retrogradation (Karim, Norziah, & Seow, 2000; Pablo, Cufni, Len, & An, 2004). Fig. 7 shows the X-ray diffraction diagrams of native wheat our and commercial biscuit for different brands. Native wheat our shows an A-type with strong peak reection at about 15 and 23 and unresolved double at 17 and 18. It is noticeable that commercial biscuit samples have peak intensities, i.e. starch crystallinity, lower than those of the native wheat our. All the commercial biscuits obviously still retained the peaks at 15, 18, 17 and 23 but at lower intensities, indicating decreases in the relative crystallinity and increases the amorphous region. No amyloselipid complex was observed in the samples (no peak observed at 19). Gelatinisation causes starch granules to loose their crystallinity, and the peak intensities of the commercial biscuits showed that starch granules were not completely gelatinised and retained some crystallinity. 3.7. Microscopy observation Changes in the internal structure of the starch granule, as a function of the baking process, were observed with polarised light microscopy (PLM). Samples were defatted with isoacetone three

Heat flow endo up(mW)

10

20

30

40

50
o

60

70

80

Temperature ( C)
Fig. 6. DSC prole for normal (A) and reduced-fat biscuit (B).

14

12

Native E D H

10

Intensity

G J

B A

J
2

C F

0 3 6 9 12 15 18 21 24 27 30 33

2 Theta
Fig. 7. X-ray diffraction diffractogram illustrating peak intensity of commercial biscuits and native wheat our.

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times and were left to dry at 40 C for 8 h, to remove fat, which could interfere with starch granule observation because fat present causes wheat granules to clump together. Fig. 8 shows the starch

granule images of native wheat starch, wheat our and commercial biscuits. Native wheat starch and resolute wheat our (Fig. 8(I) and (II)) were observed using PLM, to allow comparisons to be made with baked starch observed using the same techniques. Under polarised light, all native wheat granules were strongly birefringent. By observation of Fig. 8(III)(XII), four different morphologies are present in the population of baked wheat starch granules: intact granules, granules with partially lost birefringence, granules with no birefringence but which maintain a spherical from and disrupted granules which have lost their granular integrity. All of these forms were observed for each biscuit sample. This supports the DSC measurements and the RVA proles. The level of gelatinisation after baking will depend on the temperature and the water available in the system. Starch granules are only partly gelatinised in biscuit, due to lack of sufcient water as well as the presence of excess sugar. 4. Conclusion Physical properties of commercial biscuits (size, thickness, weight and colour) were signicantly different for the different brands measured. The three-point bend test shows that biscuits with less fat content were harder than were biscuits with normal fat content, except for sample B. Starch gelatinisation properties show that To, Tp and Tc were higher than those for wheat our whereas DH was lower than that for wheat our. The degree of gelatinisation varies among the samples. X-ray results show that commercial biscuits still retained their crystallinity but at lower intensities than for native wheat starch. Microscopy observations revealed that some of the granule birefringence (maltese cross phenomenon) of commercial biscuits can still be observed under polarised light. Acknowledgments The authors wish to thank the Ministry of Higher Education, Malaysia and University of Malaysia, Sabah for nancial support provided. References
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