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Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium (Chenopodium album) starch
Accepted Manuscript Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium (Chenopodium album) starch Romee Jan, D.C. Saxena, Sukhcharn Singh PII:
S0023-6438(15)30258-9
DOI:
10.1016/j.lwt.2015.10.040
Reference:
YFSTL 5035
To appear in:
LWT - Food Science and Technology
Received Date: 22 June 2015 Revised Date:
13 October 2015
Accepted Date: 17 October 2015
Please cite this article as: Jan, R., Saxena, D.C., Singh, S., Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium (Chenopodium album) starch, LWT - Food Science and Technology (2015), doi: 10.1016/j.lwt.2015.10.040. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium
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(Chenopodium album) starch.
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Romee Jan*, D. C. Saxena and Sukhcharn Singh
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* Corresponding author
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Academic Affiliation:
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Department of Food Engineering and Technology,
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Sant Longowal Institute of Engineering & Technology
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Longowal, Sangrur, Punjab, INDIA
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Email: [email protected]
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Phone: 91-01672-253705
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Fax: 91-01672-280057
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Pasting, thermal, morphological, rheological and structural characteristics of
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Chenopodium (Chenopodium album) starch.
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Romee Jan*, D. C. Saxena and Sukhcharn Singh
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Abstract
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Chenopodium album is an annual fast-growing underutilized pseudo cereal with high percentage
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of s t a r c h c o n t e n t . The aim of present study was to analyze the isolated starch for
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its physicochemical, morphological, pasting, thermal, rheological and FTIR spectrometric
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characteristics. Amylose content of C. album V1 a n d C. album V2 starches was f o u n d
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16.75g/100g and 19.11g/100g. The starch showed polygonal s h a p e a n d granule size w a s
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f o u n d t o v a r y from 1.021 to 1.033 µm, respectively. P e a k gelatinization temperature
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(Tp) for C. album V1 was found to be 63.20°C while for C. album V2 it was 61.05°C. Peak
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viscosity of the starch varied from 1812 cP for C. album V1 to 4012 cP for C. album V2,
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respectively. Thus C. album starch showed higher paste viscosity and unique viscoelastic
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behavior that might enhance their potential usage in different product formulations. FTIR
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spectrometric analysis revealed almost similar structural components within C. album V1 and C.
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album V2 starches. However, morsel variability was observed with Amaranthus starch.
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Key words: Chenopodium, Amaranth, Starch, Dynamic rheology, physicochemical properties.
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1. Introduction
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Chenopodium album belongs to the family chenopodiaceae with Chenopodium as the
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generic name and grows as an annual wild plant at an altitude of 4,700 meters above sea level.
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The plant is cultivated widely in Europe, North America, Iran and Asia with Western
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Rajasthan, Kulu and Shimla acting as the prominent cultivators of the crop within the India.
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The weedy plant is known as “pigweed” in English while as its popular Hindi name is
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“Bathua”. The plant is relatively inexpensive, commonly available in India during summer
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and winter seasons in the fields of wheat, barley, mustard and gram. The seeds generally go
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to waste due to non availability of processing techniques for the crop. The valuable
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underutilized pseudo-cereals like the Chenopodium are regarded like the true cereals, rich
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in mealy material enabling their elaborative utilization in different types of flour, bread,
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noodles and other starch related products. The starch from Chenopodium can be isolated in
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saponin-free form. The main constituent of grain is the small sized (< 1 µm) starch granule
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with an amylose content of about 11% that creates unique applications in food industries and
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being a major constituent of grains it can confer to structure, texture, consistency and appeal
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to many food systems (Lorenz, 1990).
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Studies on new natural starches are essential for their best use and also to increase the
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utilization of starchy flours. A growing demand for starch from the food industry has created
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the need for new sources of this polysaccharide. The research on separation and
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characterization of starch from Chenopodium album grain is scanty and these grains c a n
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b e e x p l o r e d a s a new source of starch for various food formulations. However keeping
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in view of above, the present study aims to explore the pasting, thermal, morphological,
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rheological and structural properties of the starch extracted from different cultivars of
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Chenopodium album and compared to the starch isolated from other pseudocereal.
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2. Materials and methods
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2.1. Raw Material
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The grains of C. album (V1) are not commonly available in market. Hence, the grains of
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C. album var. IC415477 (V1) were procured from National Bureau of Plant Genetic
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Resources (NBPGR), Shimla, Himachal Pradesh, India. The grains of C. album var. local
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Punjab (V2) and Amaranthus cholai var. local Punjab (V3) was locally procured. The samples
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were analyzed for carbohydrate and protein by standard methods of analysis AOAC (992-23,
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1995).
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2.2. Isolation of starch
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The starch was isolated from different cultivars using the pre-standardized process of
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starch extraction. Grains (100g) were steeped in 100 ml of NaOH (0.25g/100ml) at 4°C for
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24h. The supernatant was decanted, and fresh volume of sodium hydroxide was added to the
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solid part and stirred for another 1h at ambient temperature, double deionized water was used
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during steeping. The steeped grains were ground in a grinder (wet grinding) and the paste
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obtained was mixed with (1:5 ratio) water to form the slurry. The slurry was filtered through
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200, 300 and 400 mesh sieve, respectively. The filtrate was centrifuged at 3830 x g for 10
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min. The process of washing and centrifugation were repeated six times until the white
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starchy layer was obtained. The starch was dried for 6h at 40°C and passed through a mesh of
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100 BSS (149 µm).
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2.3. Physicochemical properties 2.3.1. Color determination 4
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The color values of starches from three varieties was measured using Hunter colorimeter (Model
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I5 Green Macbeth, USA) in terms of lightness (L*). Whiteness index (WI) was calculated
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according to Chin-Lin Hsu, Wenlung Chen, Yih-Ming Weng & Chin-Yin Tseng, (2003) as per the
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following equation:
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= 100 − (100 − )² + ² + ²
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where: L, a, and b were Hunter L, a, and b values.
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2.3.2. Amylose content
Amylose content of the samples was examined by the method of Morrison & Laignelet,
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(1983). Starch sample of 70mg was mixed with 10 ml of urea and DMSO (Dimethyl Sulfoxide)
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solution in 1:9 ratio and heated for 10 min at 100 °C with continuous stirring. The mixed
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sample was incubated at 100°C for 1 h and then cooled to room temperature. Addition of 0.5
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ml solution of above mixed incubated sample was taken with subsequent addition of 25 ml
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distilled water and 1 ml solution of iodine (I) and potassium iodide (KI). Blank sample was also
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prepared and absorbance was taken at 635nm.
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Where blue value (BV) is the absorbance at 635nm of starch and I2/KI solution. 2.3.3. Swelling power and solubility
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The procedure of Bello-Perez, Acevedo, Zamudio-Flores, Mendez-Montealvo, &
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Rodriguez- Ambriz, (2010) with few modifications was used for determination of
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swelling power and solubility of starches. These were determined over a temperature
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range of 55 to 95°C. Starch slurry (2g/100ml, starch dry basis) in centrifuge tubes was
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heated at 55, 65, 75, 85 and 95°C for 30 minutes. The tubes after cooling were centrifuged at
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112 x g for 20 min. (C24, BL; M/s. Remi Laboratory Industries, Mumbai, India). The
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supernatant was carefully decanted in petriplates, evaporated and dried at 105°C for 5 h
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till constant weight is achieved and were weighed to calculate the g/100g Solubility. The
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residue was weighed for swelling power estimation. The experiment was conducted in
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triplicates. Swelling power and solubility was calculated as: %&ℎ *+% , (&) %&ℎ * , (+( %, &)
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%&ℎ * !(&) × 100 %&ℎ * , (+( %)
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2.4. Pasting properties
The pasting properties of the starches were evaluated with the Rapid Visco Analyser
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(RVA, Starch Master TM; Model N17133; Newport Scientific Pvt. Ltd., Warriewood,
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Australia). A programmed heating and cooling cycle was used, where the samples were held
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at 50 °C for 1 min, heated to 95°C at 12°C /min, held at 95 °C for 2.5 min, before cooling
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from 95 to 50°C at 12°C /min and holding at 50°C for 2 min. Parameters recorded were
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pasting temperature, peak viscosity, final viscosity (viscosity at 50°C), breakdown
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viscosity (peak trough viscosity) and setback viscosity (final trough viscosity).
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2.5. Thermal properties
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The gelatinization characteristics of the starches were studied using a differential
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scanning calorimeter (DSC-7, PerkinElmer, and Norwalk, CT). Starch (2 mg, dry basis)
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was loaded into aluminum pan and distilled water was added to achieve a starch – water
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suspension containing 70g/100g water. Samples were hermetically sealed and allowed to
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equilibrate for 1 h at room temperature before analysis. The DSC analyzer was calibrated
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using indium and the sample pans were heated at a rate of 10°C/min from 20 to 6
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° 140 C. The t em p eratu re at t h e on s et o f gelatinization (To), at the peak (Tp), at
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conclusion the (Tc) and the enthalpy (∆H) were calculated automatically (Sandhu & Singh,
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2007).
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2.6. Rheological properties
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Dynamic rheology of starches was analyzed wherein temperature sweep oscillatory test
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was performed with Modular Compact Rheometer (MCR102, M/s. Anton Paar, Austria),
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equipped with parallel plate system (50 mm diameter) and PP50-SN32770 (dia.=0.5 mm)
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probe. The gap size was set at 0.5 mm; strain and frequency was set to 0.5% and 1 Hz,
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respectively. About 2 ml of starch suspension (20g/100g) was loaded on the ram of
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Rheometer and the edge of sample was covered with a thin layer of low density silicon
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oil to minimize evaporation losses. The starch sample was subjected to temperature sweep
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test with a temperature ramp from 50 to 90°C at a heating rate of 2°C/min. The dynamic
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rheological properties of starches in terms of storage modulus (G'), loss modulus (G")
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and loss factor (tan δ) were determined as a function of temperature.
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2.7. Morphological properties
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The granule shape as a major morphological characteristic of the sample was analyzed
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at a moisture content of 5-6 g/100g. Scanning electron micrographs (SEMs) were taken
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with a JEOL, Tokyo, Japan, Model No.JSM 6610LV. The Starch samples were mounted
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on aluminum stub using a double backed cellophane tape, coated in auto finer coater,
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JEOLJFC1600, with gold palladium (60:40, g:g). The starch samples were examined at
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magnifications of 5000 and 10000X.
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2.8. X-ray Diffraction Analysis
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The crystallinity of the powdered starch samples was determined using an X-ray
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diffractometer, PAN analytical, Phillips, Holland, Model No. X‟ Pert PRO with the
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following conditions: target
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0.5°/min. Origin Pro software package was used for determining the total area under the
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curve and the area under each prominent peak. The percentage crystallinity was calculated
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using formula below:
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Cu-anode X-ray, 30 kV, 40 mA and scanning speed of
2.9. FTIR spectroscopy
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Infrared spectra were recorded using an Agilent Technologies Cary 660 FTIR spectrometer.
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The samples were analyzed by preparing KBr pellets using anhydrous potassium
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bromide. The proportion of sample was taken as 1:15 g/g of KBr and the granular
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mixture were ground vigorously in a pestle mortar until pulverized into fine powder.
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Small quantity of this powder was carefully put into pellet-forming mould, pressed under
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hydraulic pressure and then used for obtaining I R s p e c t r u m . The IR region measured was
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between 4000 cm-1 and 400 cm-1 representing the average of 64 scans. All spectra’s were
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recorded at room temperature under ambient conditions
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2.10. Statistical evaluation
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All the analysis were determined in triplicates and Statistical analysis was performed using
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Statistica-log software package version 7 (M/s.
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significant differences were obtained by a one-way analysis of variance (ANOVA)
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followed by Duncan’s multiple range test (DMRT) at significance level of P<0.05.
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3. Results and discussion
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StatSoft Inc., OK, USA).
The
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The carbohydrate content of C. album V1 and C. album V2 was found 51.18 and 53.65
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g/100g, while protein content of C. album V1 and C. album V2 was 13.83 and 13.12
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g/100g, respectively.
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3.1. Starch yield, purity and color value
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The starch yield, purity and color values of C. album V1, C. album V2, and A. cholai V3
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starches are s h o w n i n T a b l e 1 .Significant variation (p<0.05) in yield of starches was
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observed among C. album V1, C. album V2 and A. cholai V3, respectively. This variation in
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observed yield may be due to the varietal difference among the sources used for
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extraction. Purity of starches was observed in the range of 99.12 to 99.65 g/100g. However,
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significant differences were not observed in the purity of C. album V1 and C. album V2
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starch. While significantly highest purity was noted in A. cholai V3 starch. This might be
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due to the compositional changes (protein, fat and fiber content) of the starches. The L*
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value of extracted starches varied significantly (p≤0.05) from 95.95 to 96.83. While as the
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whiteness of the starches ranged from 94.14 to 94.61, respectively. Lowest L*
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value was observed for C. album V1 starch and the highest value was observed for A.
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cholai V3. H o w e v e r higher w h i t e n e s s w a s o b s e r v e d for A. cholai V3 starch
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a n d l o w e r w h i t e n e s s w a s n o t i c e d f o r C. album V1 starch. The observed
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values of lightness were found greater than 90, which gives a satisfactory whiteness for
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starch purity as reported previously by Boudries et al., (2009).
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3.2. Physico-chemical properties of starch
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3.2.1. Amylose content
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Amylose content of C. album starches differ significantly (p ≤ 0.05) with higher mean value
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of 19.11 g/100g in C. album V2 followed by 16.75 g/100g in C. album V1 (Table 1).
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Amylose content affects the functional and physicochemical properties of starch, including
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its pasting, gelatinization, retrogradation and swelling characteristics ( Svegmark,
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Hel m ers s o n , Nilsson, Andersson, & Svensson, 2002). Also the factors such as botanical
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sources, climatic conditions, harvest time and different types of soil during cultivation
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affects the variability in amylose and amylopectin ratio within the same specie (Noda et al.,
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2004).
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3.2.2. Swelling power and solubility
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Swelling power of the C. album V2 starch ranged from 1.5 to 1.48 g/g, where as solubility
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varied from 6.66 to 60.0 g/100g within the temperature range of 55 to 95°C, as shown in
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Figure 1(a) and (b). While in case of C. album V1 and A. cholai V3, the swelling power was
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found to be 1.63 to 1.85 g/g and 2.85 to 8.41g/g, whereas the solubility values ranged from
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5.0 to 50 g/100g and 4 to 36 g/100g, respectively. The trend showed by the curves related to
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swelling power and solubility of starches was found similar upon increase in the
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temperature. C. album V1 and C. album V2 starches showed similar increasing trend in
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early hours of heating that changed towards the decreasing trend thereafter in late periods
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of the study. Starch aqueous suspension when heated above gelatinization temperature
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results in the distraction of starch crystalline structure and exposure of water molecules to
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hydroxyl groups of amylose and amylopectin through hydrogen bonding, resulting in
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swelling of starch molecules, and increased solubility due to leaching of some soluble
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starch into liquid. A strongly bonded micellar structure of the starch granule may render it
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relatively defiant to swelling, also Sasaki, Yasui, Matsuki, & Satake, (2003) suggested
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that amylose reinforced the internal network within the granule that restricts the swelling
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and the waxy starch swell to a greater extent than normal amylose starch. Contrarily to it A.
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cholai V3 showed a significantly different behavior whose starch granules continued to
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swell with further increase in temperature as shown in Figure 1(a) & (b). It might be due to
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the presence of low amylose content in A. cholai V3 starch, as reported by Tester &
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Morrison, (1990) that amylose dominates the solubility of starch whereas amylopectin
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mainly influences the starch swelling power. Thus the ratio of amylose and amylopectin in
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the starch granule and the way in which they are arranged inside the granule affect the
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swelling and solubility of the starch.
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3.2.3. Pasting properties
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Pasting properties provide imminent information about the cooking behavior of starches
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during heating and cooling cycles. Viscosity of starches was found to increase with an
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increase in temperature with the C. album V2 exhibiting significantly higher peak viscosity
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(PV) (4012cP) in comparison to C. album V1 and A. cholai V3 starches. Peak viscosity is
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regarded as the maximum viscosity attained by the sample and tendency of starch
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granules to swell freely before physical breakdown.
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increase in temperature may be accredited to the removal of water from the exuded
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amylose of granules as they swell (Ghiasi, Marston & Hoseney, 1982). Pasting temperature
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is the minimum temperature required to cook the starch. C. album V2 starch showed a lower
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pasting temperature of 76.65°C than C. album V1 and A. cholai V3 starches. The high
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pasting temperature of starch indicates the higher resistance of starch granules towards the
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swelling. The break down viscosity (BD) and set back viscosity values (SV) of starch
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paste varied significantly (p ≤ 0.05) with respective mean values of 331cP and 1190cP for
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C.album V2 starch which was found to be higher than A. cholai V3 and lower than C.
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album V1 starch.
The increase in viscosity with
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Breakdown viscosity, measure of resistance of starch paste to heat and shear, indicates the
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stability of the paste and Setback reflects the degree of retrogradation that is
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expected to correlate positively with the amylose content of starch (Abdel-Aal, Hucl,
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Chibbar, Han, & Demeke, 2002). Final viscosity indicates a gelling tendency that gives an
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insight of stability to cooled-cooked starch paste under low shear. C. album V2 showed a
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higher final viscosity (FV) of 4871 cP followed by C. album V1 and A. cholai V3 as shown
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in Table 2. The viscosity of C. album V2 and C. album V1 continued to ascend quite sharply
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on cooling as compared to A. cholai V3 which may be attributed to the higher amylose
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content and water binding capacity of these starches.
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3.2.4. Thermal properties
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Thermal transition temperatures (To, Tp, Tc) along with enthalpy of gelatinization (∆H gel)
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and gelatinization temperature range (TR = Tc-To) are presented in Table 2. C. album
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V2 starch showed significantly (p ≤ 0.05) lower To, Tc and ∆H gel values of 41.75, 63.87°
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C and 12.81 J/g, respectively, in contrary to the higher range observed in C. album V1
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and A. cholai V3 starch. The lower gelatinization temperatures of starch indicated lesser
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energy usage requirement to instigate starch gelatinization and vice versa. Fredriksson,
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Silverio, Anderson, Eliasson, & Aman, (1998) reported starch crystallinity increases with
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amylopectin content and for this reason; higher amylopectin content containing starches
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(i.e. lower amylose content) would be expected to have higher onset, peak, and
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conclusion temperatures. Furthermore starches from various botanical sources diverge in
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compositions that reveal different transition temperatures and gelatinization enthalpies
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(Singh, Singh, Kaur, Sodhi, & Gill, 2003). The values of thermal transitions are in close
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conformity with the annotations of thermal values observed by Steffolani, Leon, & Perez,
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(2013).
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3.2.5. Morphological characteristics
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The scanning electron micrograph of the starches has revealed that the starch granules
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are polygonal and angular in shape. Morphological examination of the starches showed the
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varying size of starch granules with average granule size of 1.021 µm and 1.033 µm found
274
in C. album V2 and C. album V1, respectively. Microscopic observations (Figure. 2, A-
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C) of the starch samples reveal the established organization of starch granules in form of
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clusters, which may be due to the aggregation of starch granules natively in the starchy
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perisperm. The size and shapes of the observed granules are in close agreement with
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Villarreal, Ribotta, & Iturriaga, (2013).
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3.2.6. X-ray diffraction analysis
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The X-ray diffraction pattern of starches is shown in Figure 3. C. album V2 starch displayed
281
“A”type diffraction pattern with peak intensities observed at 15.23, 17.13, 18.19 and 23.32°
282
that are comparable with the findings of Manek et al., (2005) on cereal starches. C. album
283
V1 and A. cholai V3 starches showed similar diffractograms as that of C . album V2
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starch. X-ray diffractometry has been used to reveal the presence and characteristics of the
285
crystalline structure of the starch granules. The percentage starch crystallinity of C. album V2
286
was found to be 29.58%, while as C. album V1 and A. cholai V3 starches showed an average
287
value of 37.47 and 33.88 %, respectively. The starch crystallinity varies with crystal size
288
and amount of crystalline region, whereas the amylose chain is responsible for the
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amorphous region and orientation of double helices within the crystalline domain with
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degree of interaction involving double helices (Singh, McCarthy, & Singh, 2006).
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3.2.7. FTIR Spectroscopy
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Interpretation of the infrared (IR) absorption bands is achieved in the light of earlier
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investigation (Yadav, Mahadevamma, Tharanathan, & Ramteke, 2007). The IR spectra
294
of starch samples exhibited bands that originate mainly from the vibrational modes of
295
amylose and amylopectin. Infra red spectral patterns of C. album V1 and C. album V2
296
starches were found consistent to each other although spectra of A. cholai V3 starch
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powder was found to be up shifted in comparison to C. album V1 and C. album V2
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starches shown in Figure 4. The stretching frequency at about 3200 cm-1 to 3400 cm-
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the hydroxyl peak for A. cholai V3 was found up shifted at 3552.166 cm-1due to the less
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significant hydrogen bonding.
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Similarly the peaks at 2931.329 cm-1 and 2886.590 are due to the symmetric stretching of
303
C-H group and bands appearing at 2 3 6 1 . 1 6 3 c m - 1 are ascribed to the bending vibrational
304
modes of glycosidic linkage. The absorption band at 1637.913 cm-1 in C .album V1 and C.
305
album V2 is attributed to the O-H related vibration that indicate the inter and intra-
306
molecular hydrogen bonding between the amorphous region of starch and water
307
molecules. The above mentioned band appeared sharply at about 1652.052 cm -1 in case
308
of A. cholai V3 which again confirms the absence of hydrogen bonding (O-H) in its starch.
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Besides this the A. cholai V3 starch showed a broad band of C=N and C=C asymmetric
310
stretching due to presence of glycosidic linkage skeleton in the region of 1200-900 cm-1.
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The broad bands in the region of 800 cm -1 to 400 cm-1are bending vibrational modes of the
312
glucose pyranose ring.
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3.2.8. Rheological properties
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The rheological properties of starches during heating are shown in Table 3. Storage modulus
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(G') and loss modulus (G") of C. album V1 and C. album V2 starch suspensions increased
316
steeply to maxima and still tend to increase further with incessant heating indicating
317
their granule resistance to deformation, whereas the parameters for A. cholai V3
318
increased initially upon heating reaching a maximum and thereafter decreasing upon
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continuous heating. This reduction in G' and G'' values of A. cholai V3 may be due to the
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disintegration of starch granules leading to the melting of remaining crystallites and
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increasing the molecular mobility. The temperature (TG'max) of C. album V2 starch at
322
which the storage modulus (G') loss modulus (G") reached the highest value was found to
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be 87.3°C which was found to be higher than A. cholai V3 but lower than the C. album V1
324
starch (Table 3). This increase in both storage and loss moduli before T G'max is due to
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swelling of starch granules and leaching of amylose chains, contributing to the formation of a
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composite network of solvated materials supporting partially disintegrated starch granules
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(Arocas, Sanz & Fiszman, 2009; Hsu, Lu, & Huang, 2000). The G' value of 41,500 Pa, G''
328
value of 7590 Pa was observed with a damping factor (Tan δ Peak) of 0.182 in C. album V2
329
starch suspension. The variation in G', G'' and tan δ during heating cycle may be due to the
330
difference in starch granule structure and its amylose content (Svegmark & Hermansson,
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1993). The results are in close proximity with the study of Kong, Kasapis, Bao, & Corke,
332
(2012) on amaranth
333
4. Conclusion
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The carbohydrate content of C. album varieties V1 and V2 was found to be 51.18 and
335
53.65g/100g, respectively. The starch obtained was found 47.30 and 37.59g/100g being
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higher than A. cholai V3 with higher purity values of 99.12 and 99.20 g/100g,
starch
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respectively. Chenopodium starches showed lower swelling
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diameter, pasting temperature and gelatinization temperature, whereas higher values were
339
noticed for amylose content, pasting viscosity and solubility when compared to A. cholai
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V3 starch. A typical A-type X-ray diffraction pattern with crystallinity of 29.58%, 37.47 %
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was found for C. album V1 and V2 starches. The C. album starches showed higher Peak
342
G' and G" than A. cholai V3. The analysis of various properties of C. album starches will
343
provide valuable information associated with the functional properties of starch, as desirable
344
functional properties can be used in various food industries due to its impending
345
applications for the development of various products viz., in high viscous foods, as a good
346
gelling agent, in dessert and other food formulations and could replace chemically modified
347
starches that are currently being used in a number of products. Moreover due to small
348
granule size, starches may find wide applications in edible biodegradable films, as fat
349
substitutes (due to smooth creamy structure), as a binder with orally active ingredients. The
350
above all interesting and unique rheological
351
beneficially exploited in the formulation of specialty food products.
352
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Morrison, W. R., & Laignelet, B. (1983). An improved colorimetric procedure for
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Noda, T., Tsuda, S., Mori, M., Takigawa, S., Matsuura- Endo, C., & Saito, K. (2004). The
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Steffolani, M. E., Leon, A. E., & Perez, G. T. (2013). Study of the physicochemical
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observed and predicted structure. Food Structure, 12, 181-193.
Svegmark, K., Helmersson, K., Nilsson, G., Nilsson, P.O., Andersson, R., &
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Svensson, E, (2002). Comparison of potato amylopectin starches and potato starches.
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Influence of year and variety. Carbohydrate Polymer, 47, 331-340.
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Tester, R. F., & Morrison, W. R. (1990). Swelling and gelatinization of cereal starches.
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Effect of amylopectin, amylose and lipid. Cereal Chemistry, 67, 551-557.
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Villarreal, M. E., Ribotta, P. D., & Iturriaga, B. L. (2013). Comparing methods for
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extracting amaranthus starch and the properties of the isolated starches. LWT-Food
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Science and Technology, 51(2), 441-447.
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Yadav, R. A., Mahadevamma, S., Tharanathan, R. N., & Ramteke R. S. (2007).
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Characteristics of acetylated and enzyme-modified potato and sweet potato flours.
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FoodChemistry, 103, 1119-1126. .
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TABLE 1. PROXIMATE COMPOSITION AND FUNCTIONAL PROPERTIES OF CHENOPODIUM ALBUM RAW AND GERMINATED FLOUR Raw C.album flour 9.43b ±0.15 3.25a ±0.03 13.12b ±0.07 6.50a ±0.30 13.09b ±0.04 54.61a ±0.09 14.10b ±0.07
Germinated C.album flour 10.39a ±0.10 2.50b ±0.04 15.45a ±0.05 4.13b ±0.04 16.87a ±0.10 50.66b ±0.06 18.20a ±0.11
241b ±3.51 35.50b ±0.13 41.44a ±0.29
565a ±8.00 38.61a ±0.14 31.75b ±0.20
BD (g/ml) True density(g/ml) Porosity (g/100g) WAI (g/g) WSI (g/100 g) OAC (g/100 g)
0.59a ±0.06 1.30a ±0.10 54.70b ± 4.12 2.29b ±0.15
0.52a ± 0.06 1.36a ±0.10 61.80a ±2.68 3.55a ±0.18 9.60a ±0.70 2.81a ±0.11
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Parameter Moisture (g/100 g) Ash (g/100 g) Protein (g/100 g) Fat (g/100 g) Crude Fibre (g/100 g) Carbohydrate (g/100 g) DPPH radical scavenging activity (g/100 g) Total phenolics (mg/100g) Total dietary fibre (g/100 g) Total starch Functional properties
4.80b ±0.20
2.35b ±0.2
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TABLE 2. PASTING PROPERTIES OF CHENOPODIUM ALBUM FLOUR.
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Parameter Raw C.album flour Germinated C.album flour a Peak viscosity (cP) 925 ±15.01 863b ±25.50 Trough viscosity (cP) 887a ±12.05 645b ±7.54 a Breakdown (cP) 32 ±1.04 21b ±1.82 a Final viscosity (cP) 1412 ±21.50 1351b ±16.00 Setback (cP) 510a ±18.00 451b ±17.52 ° a Pasting temperature ( C) 86.45 ±2.41 84.83a ±0.58 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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TABLE 3. PHYSICAL, TEXTURAL PROPERTIES AND LIGHTNESS VALUES OF COOKIES Parameter *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies b b Weight (g) 12.80 ±0.05 13.04 ±0.36 14.43a ±0.49 b b Thickness (mm) 7.03 ±0.07 7.49 ±0.50 8.21a ±0.33 Diameter (mm) 50.72b ±0.06 54.37a ±0.52 54.76a ±0.89 a a Spread ratio 7.21 ±0.03 7.25 ±0.65 6.66a ±0.84 Hardness (N) 92.25a ±5.98 49.30b ±6.55 44.43b ±13.07 a c L* value 65.20 ±2.22 42.00 ±1.10 36.60b±1.04 *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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TABLE 4. ANTIOXIDANT ACTIVITY, TOTAL PHENOLICS AND TOTAL DIETARY FIBRE OF COOKIES. Parameter *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies c b DPPH radical 16.42 ±0.17 19.44 ±0.52 23.97a ±0.35 scavenging activity (g/100 g)/(TAC) Total phenolic NA 323b±3.44 671a± 5.60 Content(TPC) (mg/100g) Total dietary fibre 10.70c ±0.11 35.85b ±0.87 38.77a ±1.39 (g/100 g) *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n = 3).
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TABLE 5. SENSORY ANALYSIS OF COOKIES. *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies a a Color & appearance 7.25 ±0.50 6.50 ±0.75 6.75a ±0.22 a a Aroma 7.00 ±0.60 7.25 ±0.50 7.75a ±0.36 Taste 7.00a ±0.40 7.00a ±0.25 7.75a ±0.11 a b Mouth feel 7.50 ±0.77 6.75 ±0.25 7.25ab ±0.22 Texture 6.50b ±0.75 7.00ab ±0.38 7.50a ±0.12 ab b Overall acceptability 6.75 ±0.50 6.50 ±0.75 7.75a ±0.20 *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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Quality parameter
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(a)
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A2
B1
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A1
Figure 2. SEM micrographs of starches: (A1, A2) top two images representing C. album (V2) at magnification level of 5000 x and 10000 x. the middle two micrographs (B1, B2) belong to C. album (V1) at 5000 x and 10000 x, while the last two micrographs (C1, C2) are from A. cholai (V3) at 5000 x and 10000 x.
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Figure 4. FTIR spectrometric analysis of starch acquired from C .album (V1), C .album (V2) and A. cholai (V3).
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Highlights
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Smaller starch granule with higher paste viscosity and solubility was observed. Lower gelatinization temperature of starch with high degree of crystallinity. Unique viscoelastic behaviour and FTIR analysis of the starch were observed. The obtained starch can be a used as a replacement for chemically modified starches May find application in development of newer product formulations.
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• • • • •
S0023-6438(15)30258-9
DOI:
10.1016/j.lwt.2015.10.040
Reference:
YFSTL 5035
To appear in:
LWT - Food Science and Technology
Received Date: 22 June 2015 Revised Date:
13 October 2015
Accepted Date: 17 October 2015
Please cite this article as: Jan, R., Saxena, D.C., Singh, S., Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium (Chenopodium album) starch, LWT - Food Science and Technology (2015), doi: 10.1016/j.lwt.2015.10.040. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Pasting, thermal, morphological, rheological and structural characteristics of Chenopodium
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(Chenopodium album) starch.
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Romee Jan*, D. C. Saxena and Sukhcharn Singh
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* Corresponding author
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Academic Affiliation:
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Department of Food Engineering and Technology,
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Sant Longowal Institute of Engineering & Technology
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Longowal, Sangrur, Punjab, INDIA
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Email: [email protected]
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Phone: 91-01672-253705
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Fax: 91-01672-280057
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Pasting, thermal, morphological, rheological and structural characteristics of
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Chenopodium (Chenopodium album) starch.
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Romee Jan*, D. C. Saxena and Sukhcharn Singh
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Abstract
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Chenopodium album is an annual fast-growing underutilized pseudo cereal with high percentage
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of s t a r c h c o n t e n t . The aim of present study was to analyze the isolated starch for
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its physicochemical, morphological, pasting, thermal, rheological and FTIR spectrometric
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characteristics. Amylose content of C. album V1 a n d C. album V2 starches was f o u n d
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16.75g/100g and 19.11g/100g. The starch showed polygonal s h a p e a n d granule size w a s
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f o u n d t o v a r y from 1.021 to 1.033 µm, respectively. P e a k gelatinization temperature
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(Tp) for C. album V1 was found to be 63.20°C while for C. album V2 it was 61.05°C. Peak
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viscosity of the starch varied from 1812 cP for C. album V1 to 4012 cP for C. album V2,
37
respectively. Thus C. album starch showed higher paste viscosity and unique viscoelastic
38
behavior that might enhance their potential usage in different product formulations. FTIR
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spectrometric analysis revealed almost similar structural components within C. album V1 and C.
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album V2 starches. However, morsel variability was observed with Amaranthus starch.
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Key words: Chenopodium, Amaranth, Starch, Dynamic rheology, physicochemical properties.
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1. Introduction
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Chenopodium album belongs to the family chenopodiaceae with Chenopodium as the
50
generic name and grows as an annual wild plant at an altitude of 4,700 meters above sea level.
51
The plant is cultivated widely in Europe, North America, Iran and Asia with Western
52
Rajasthan, Kulu and Shimla acting as the prominent cultivators of the crop within the India.
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The weedy plant is known as “pigweed” in English while as its popular Hindi name is
54
“Bathua”. The plant is relatively inexpensive, commonly available in India during summer
55
and winter seasons in the fields of wheat, barley, mustard and gram. The seeds generally go
56
to waste due to non availability of processing techniques for the crop. The valuable
57
underutilized pseudo-cereals like the Chenopodium are regarded like the true cereals, rich
58
in mealy material enabling their elaborative utilization in different types of flour, bread,
59
noodles and other starch related products. The starch from Chenopodium can be isolated in
60
saponin-free form. The main constituent of grain is the small sized (< 1 µm) starch granule
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with an amylose content of about 11% that creates unique applications in food industries and
62
being a major constituent of grains it can confer to structure, texture, consistency and appeal
63
to many food systems (Lorenz, 1990).
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Studies on new natural starches are essential for their best use and also to increase the
65
utilization of starchy flours. A growing demand for starch from the food industry has created
66
the need for new sources of this polysaccharide. The research on separation and
67
characterization of starch from Chenopodium album grain is scanty and these grains c a n
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b e e x p l o r e d a s a new source of starch for various food formulations. However keeping
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in view of above, the present study aims to explore the pasting, thermal, morphological,
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rheological and structural properties of the starch extracted from different cultivars of
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Chenopodium album and compared to the starch isolated from other pseudocereal.
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2. Materials and methods
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2.1. Raw Material
74
The grains of C. album (V1) are not commonly available in market. Hence, the grains of
75
C. album var. IC415477 (V1) were procured from National Bureau of Plant Genetic
76
Resources (NBPGR), Shimla, Himachal Pradesh, India. The grains of C. album var. local
77
Punjab (V2) and Amaranthus cholai var. local Punjab (V3) was locally procured. The samples
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were analyzed for carbohydrate and protein by standard methods of analysis AOAC (992-23,
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1995).
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2.2. Isolation of starch
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The starch was isolated from different cultivars using the pre-standardized process of
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starch extraction. Grains (100g) were steeped in 100 ml of NaOH (0.25g/100ml) at 4°C for
83
24h. The supernatant was decanted, and fresh volume of sodium hydroxide was added to the
84
solid part and stirred for another 1h at ambient temperature, double deionized water was used
85
during steeping. The steeped grains were ground in a grinder (wet grinding) and the paste
86
obtained was mixed with (1:5 ratio) water to form the slurry. The slurry was filtered through
87
200, 300 and 400 mesh sieve, respectively. The filtrate was centrifuged at 3830 x g for 10
88
min. The process of washing and centrifugation were repeated six times until the white
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starchy layer was obtained. The starch was dried for 6h at 40°C and passed through a mesh of
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100 BSS (149 µm).
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2.3. Physicochemical properties 2.3.1. Color determination 4
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The color values of starches from three varieties was measured using Hunter colorimeter (Model
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I5 Green Macbeth, USA) in terms of lightness (L*). Whiteness index (WI) was calculated
95
according to Chin-Lin Hsu, Wenlung Chen, Yih-Ming Weng & Chin-Yin Tseng, (2003) as per the
96
following equation:
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= 100 − (100 − )² + ² + ²
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where: L, a, and b were Hunter L, a, and b values.
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2.3.2. Amylose content
Amylose content of the samples was examined by the method of Morrison & Laignelet,
100
(1983). Starch sample of 70mg was mixed with 10 ml of urea and DMSO (Dimethyl Sulfoxide)
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solution in 1:9 ratio and heated for 10 min at 100 °C with continuous stirring. The mixed
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sample was incubated at 100°C for 1 h and then cooled to room temperature. Addition of 0.5
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ml solution of above mixed incubated sample was taken with subsequent addition of 25 ml
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distilled water and 1 ml solution of iodine (I) and potassium iodide (KI). Blank sample was also
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prepared and absorbance was taken at 635nm.
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Where blue value (BV) is the absorbance at 635nm of starch and I2/KI solution. 2.3.3. Swelling power and solubility
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The procedure of Bello-Perez, Acevedo, Zamudio-Flores, Mendez-Montealvo, &
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Rodriguez- Ambriz, (2010) with few modifications was used for determination of
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swelling power and solubility of starches. These were determined over a temperature
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range of 55 to 95°C. Starch slurry (2g/100ml, starch dry basis) in centrifuge tubes was
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heated at 55, 65, 75, 85 and 95°C for 30 minutes. The tubes after cooling were centrifuged at
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112 x g for 20 min. (C24, BL; M/s. Remi Laboratory Industries, Mumbai, India). The
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supernatant was carefully decanted in petriplates, evaporated and dried at 105°C for 5 h
116
till constant weight is achieved and were weighed to calculate the g/100g Solubility. The
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residue was weighed for swelling power estimation. The experiment was conducted in
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triplicates. Swelling power and solubility was calculated as: %&ℎ *+% , (&) %&ℎ * , (+( %, &)
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%&ℎ * !(&) × 100 %&ℎ * , (+( %)
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2.4. Pasting properties
The pasting properties of the starches were evaluated with the Rapid Visco Analyser
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(RVA, Starch Master TM; Model N17133; Newport Scientific Pvt. Ltd., Warriewood,
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Australia). A programmed heating and cooling cycle was used, where the samples were held
123
at 50 °C for 1 min, heated to 95°C at 12°C /min, held at 95 °C for 2.5 min, before cooling
124
from 95 to 50°C at 12°C /min and holding at 50°C for 2 min. Parameters recorded were
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pasting temperature, peak viscosity, final viscosity (viscosity at 50°C), breakdown
126
viscosity (peak trough viscosity) and setback viscosity (final trough viscosity).
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The gelatinization characteristics of the starches were studied using a differential
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scanning calorimeter (DSC-7, PerkinElmer, and Norwalk, CT). Starch (2 mg, dry basis)
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was loaded into aluminum pan and distilled water was added to achieve a starch – water
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suspension containing 70g/100g water. Samples were hermetically sealed and allowed to
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equilibrate for 1 h at room temperature before analysis. The DSC analyzer was calibrated
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using indium and the sample pans were heated at a rate of 10°C/min from 20 to 6
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° 140 C. The t em p eratu re at t h e on s et o f gelatinization (To), at the peak (Tp), at
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conclusion the (Tc) and the enthalpy (∆H) were calculated automatically (Sandhu & Singh,
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2007).
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2.6. Rheological properties
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Dynamic rheology of starches was analyzed wherein temperature sweep oscillatory test
139
was performed with Modular Compact Rheometer (MCR102, M/s. Anton Paar, Austria),
140
equipped with parallel plate system (50 mm diameter) and PP50-SN32770 (dia.=0.5 mm)
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probe. The gap size was set at 0.5 mm; strain and frequency was set to 0.5% and 1 Hz,
142
respectively. About 2 ml of starch suspension (20g/100g) was loaded on the ram of
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Rheometer and the edge of sample was covered with a thin layer of low density silicon
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oil to minimize evaporation losses. The starch sample was subjected to temperature sweep
145
test with a temperature ramp from 50 to 90°C at a heating rate of 2°C/min. The dynamic
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rheological properties of starches in terms of storage modulus (G'), loss modulus (G")
147
and loss factor (tan δ) were determined as a function of temperature.
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2.7. Morphological properties
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The granule shape as a major morphological characteristic of the sample was analyzed
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at a moisture content of 5-6 g/100g. Scanning electron micrographs (SEMs) were taken
151
with a JEOL, Tokyo, Japan, Model No.JSM 6610LV. The Starch samples were mounted
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on aluminum stub using a double backed cellophane tape, coated in auto finer coater,
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JEOLJFC1600, with gold palladium (60:40, g:g). The starch samples were examined at
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magnifications of 5000 and 10000X.
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2.8. X-ray Diffraction Analysis
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The crystallinity of the powdered starch samples was determined using an X-ray
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diffractometer, PAN analytical, Phillips, Holland, Model No. X‟ Pert PRO with the
158
following conditions: target
159
0.5°/min. Origin Pro software package was used for determining the total area under the
160
curve and the area under each prominent peak. The percentage crystallinity was calculated
161
using formula below:
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Cu-anode X-ray, 30 kV, 40 mA and scanning speed of
2.9. FTIR spectroscopy
163
Infrared spectra were recorded using an Agilent Technologies Cary 660 FTIR spectrometer.
164
The samples were analyzed by preparing KBr pellets using anhydrous potassium
165
bromide. The proportion of sample was taken as 1:15 g/g of KBr and the granular
166
mixture were ground vigorously in a pestle mortar until pulverized into fine powder.
167
Small quantity of this powder was carefully put into pellet-forming mould, pressed under
168
hydraulic pressure and then used for obtaining I R s p e c t r u m . The IR region measured was
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between 4000 cm-1 and 400 cm-1 representing the average of 64 scans. All spectra’s were
170
recorded at room temperature under ambient conditions
171
2.10. Statistical evaluation
172
All the analysis were determined in triplicates and Statistical analysis was performed using
173
Statistica-log software package version 7 (M/s.
174
significant differences were obtained by a one-way analysis of variance (ANOVA)
175
followed by Duncan’s multiple range test (DMRT) at significance level of P<0.05.
176
3. Results and discussion
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StatSoft Inc., OK, USA).
The
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The carbohydrate content of C. album V1 and C. album V2 was found 51.18 and 53.65
178
g/100g, while protein content of C. album V1 and C. album V2 was 13.83 and 13.12
179
g/100g, respectively.
180
3.1. Starch yield, purity and color value
181
The starch yield, purity and color values of C. album V1, C. album V2, and A. cholai V3
182
starches are s h o w n i n T a b l e 1 .Significant variation (p<0.05) in yield of starches was
183
observed among C. album V1, C. album V2 and A. cholai V3, respectively. This variation in
184
observed yield may be due to the varietal difference among the sources used for
185
extraction. Purity of starches was observed in the range of 99.12 to 99.65 g/100g. However,
186
significant differences were not observed in the purity of C. album V1 and C. album V2
187
starch. While significantly highest purity was noted in A. cholai V3 starch. This might be
188
due to the compositional changes (protein, fat and fiber content) of the starches. The L*
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value of extracted starches varied significantly (p≤0.05) from 95.95 to 96.83. While as the
190
whiteness of the starches ranged from 94.14 to 94.61, respectively. Lowest L*
191
value was observed for C. album V1 starch and the highest value was observed for A.
192
cholai V3. H o w e v e r higher w h i t e n e s s w a s o b s e r v e d for A. cholai V3 starch
193
a n d l o w e r w h i t e n e s s w a s n o t i c e d f o r C. album V1 starch. The observed
194
values of lightness were found greater than 90, which gives a satisfactory whiteness for
195
starch purity as reported previously by Boudries et al., (2009).
196
3.2. Physico-chemical properties of starch
197
3.2.1. Amylose content
198
Amylose content of C. album starches differ significantly (p ≤ 0.05) with higher mean value
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of 19.11 g/100g in C. album V2 followed by 16.75 g/100g in C. album V1 (Table 1).
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Amylose content affects the functional and physicochemical properties of starch, including
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its pasting, gelatinization, retrogradation and swelling characteristics ( Svegmark,
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Hel m ers s o n , Nilsson, Andersson, & Svensson, 2002). Also the factors such as botanical
203
sources, climatic conditions, harvest time and different types of soil during cultivation
204
affects the variability in amylose and amylopectin ratio within the same specie (Noda et al.,
205
2004).
206
3.2.2. Swelling power and solubility
207
Swelling power of the C. album V2 starch ranged from 1.5 to 1.48 g/g, where as solubility
208
varied from 6.66 to 60.0 g/100g within the temperature range of 55 to 95°C, as shown in
209
Figure 1(a) and (b). While in case of C. album V1 and A. cholai V3, the swelling power was
210
found to be 1.63 to 1.85 g/g and 2.85 to 8.41g/g, whereas the solubility values ranged from
211
5.0 to 50 g/100g and 4 to 36 g/100g, respectively. The trend showed by the curves related to
212
swelling power and solubility of starches was found similar upon increase in the
213
temperature. C. album V1 and C. album V2 starches showed similar increasing trend in
214
early hours of heating that changed towards the decreasing trend thereafter in late periods
215
of the study. Starch aqueous suspension when heated above gelatinization temperature
216
results in the distraction of starch crystalline structure and exposure of water molecules to
217
hydroxyl groups of amylose and amylopectin through hydrogen bonding, resulting in
218
swelling of starch molecules, and increased solubility due to leaching of some soluble
219
starch into liquid. A strongly bonded micellar structure of the starch granule may render it
220
relatively defiant to swelling, also Sasaki, Yasui, Matsuki, & Satake, (2003) suggested
221
that amylose reinforced the internal network within the granule that restricts the swelling
222
and the waxy starch swell to a greater extent than normal amylose starch. Contrarily to it A.
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cholai V3 showed a significantly different behavior whose starch granules continued to
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swell with further increase in temperature as shown in Figure 1(a) & (b). It might be due to
225
the presence of low amylose content in A. cholai V3 starch, as reported by Tester &
226
Morrison, (1990) that amylose dominates the solubility of starch whereas amylopectin
227
mainly influences the starch swelling power. Thus the ratio of amylose and amylopectin in
228
the starch granule and the way in which they are arranged inside the granule affect the
229
swelling and solubility of the starch.
230
3.2.3. Pasting properties
231
Pasting properties provide imminent information about the cooking behavior of starches
232
during heating and cooling cycles. Viscosity of starches was found to increase with an
233
increase in temperature with the C. album V2 exhibiting significantly higher peak viscosity
234
(PV) (4012cP) in comparison to C. album V1 and A. cholai V3 starches. Peak viscosity is
235
regarded as the maximum viscosity attained by the sample and tendency of starch
236
granules to swell freely before physical breakdown.
237
increase in temperature may be accredited to the removal of water from the exuded
238
amylose of granules as they swell (Ghiasi, Marston & Hoseney, 1982). Pasting temperature
239
is the minimum temperature required to cook the starch. C. album V2 starch showed a lower
240
pasting temperature of 76.65°C than C. album V1 and A. cholai V3 starches. The high
241
pasting temperature of starch indicates the higher resistance of starch granules towards the
242
swelling. The break down viscosity (BD) and set back viscosity values (SV) of starch
243
paste varied significantly (p ≤ 0.05) with respective mean values of 331cP and 1190cP for
244
C.album V2 starch which was found to be higher than A. cholai V3 and lower than C.
245
album V1 starch.
The increase in viscosity with
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Breakdown viscosity, measure of resistance of starch paste to heat and shear, indicates the
247
stability of the paste and Setback reflects the degree of retrogradation that is
248
expected to correlate positively with the amylose content of starch (Abdel-Aal, Hucl,
249
Chibbar, Han, & Demeke, 2002). Final viscosity indicates a gelling tendency that gives an
250
insight of stability to cooled-cooked starch paste under low shear. C. album V2 showed a
251
higher final viscosity (FV) of 4871 cP followed by C. album V1 and A. cholai V3 as shown
252
in Table 2. The viscosity of C. album V2 and C. album V1 continued to ascend quite sharply
253
on cooling as compared to A. cholai V3 which may be attributed to the higher amylose
254
content and water binding capacity of these starches.
255
3.2.4. Thermal properties
256
Thermal transition temperatures (To, Tp, Tc) along with enthalpy of gelatinization (∆H gel)
257
and gelatinization temperature range (TR = Tc-To) are presented in Table 2. C. album
258
V2 starch showed significantly (p ≤ 0.05) lower To, Tc and ∆H gel values of 41.75, 63.87°
259
C and 12.81 J/g, respectively, in contrary to the higher range observed in C. album V1
260
and A. cholai V3 starch. The lower gelatinization temperatures of starch indicated lesser
261
energy usage requirement to instigate starch gelatinization and vice versa. Fredriksson,
262
Silverio, Anderson, Eliasson, & Aman, (1998) reported starch crystallinity increases with
263
amylopectin content and for this reason; higher amylopectin content containing starches
264
(i.e. lower amylose content) would be expected to have higher onset, peak, and
265
conclusion temperatures. Furthermore starches from various botanical sources diverge in
266
compositions that reveal different transition temperatures and gelatinization enthalpies
267
(Singh, Singh, Kaur, Sodhi, & Gill, 2003). The values of thermal transitions are in close
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conformity with the annotations of thermal values observed by Steffolani, Leon, & Perez,
269
(2013).
270
3.2.5. Morphological characteristics
271
The scanning electron micrograph of the starches has revealed that the starch granules
272
are polygonal and angular in shape. Morphological examination of the starches showed the
273
varying size of starch granules with average granule size of 1.021 µm and 1.033 µm found
274
in C. album V2 and C. album V1, respectively. Microscopic observations (Figure. 2, A-
275
C) of the starch samples reveal the established organization of starch granules in form of
276
clusters, which may be due to the aggregation of starch granules natively in the starchy
277
perisperm. The size and shapes of the observed granules are in close agreement with
278
Villarreal, Ribotta, & Iturriaga, (2013).
279
3.2.6. X-ray diffraction analysis
280
The X-ray diffraction pattern of starches is shown in Figure 3. C. album V2 starch displayed
281
“A”type diffraction pattern with peak intensities observed at 15.23, 17.13, 18.19 and 23.32°
282
that are comparable with the findings of Manek et al., (2005) on cereal starches. C. album
283
V1 and A. cholai V3 starches showed similar diffractograms as that of C . album V2
284
starch. X-ray diffractometry has been used to reveal the presence and characteristics of the
285
crystalline structure of the starch granules. The percentage starch crystallinity of C. album V2
286
was found to be 29.58%, while as C. album V1 and A. cholai V3 starches showed an average
287
value of 37.47 and 33.88 %, respectively. The starch crystallinity varies with crystal size
288
and amount of crystalline region, whereas the amylose chain is responsible for the
289
amorphous region and orientation of double helices within the crystalline domain with
290
degree of interaction involving double helices (Singh, McCarthy, & Singh, 2006).
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3.2.7. FTIR Spectroscopy
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Interpretation of the infrared (IR) absorption bands is achieved in the light of earlier
293
investigation (Yadav, Mahadevamma, Tharanathan, & Ramteke, 2007). The IR spectra
294
of starch samples exhibited bands that originate mainly from the vibrational modes of
295
amylose and amylopectin. Infra red spectral patterns of C. album V1 and C. album V2
296
starches were found consistent to each other although spectra of A. cholai V3 starch
297
powder was found to be up shifted in comparison to C. album V1 and C. album V2
298
starches shown in Figure 4. The stretching frequency at about 3200 cm-1 to 3400 cm-
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were assigned to the O-H group for both C. album V1 and C. album V2 starches, while as
the hydroxyl peak for A. cholai V3 was found up shifted at 3552.166 cm-1due to the less
301
significant hydrogen bonding.
302
Similarly the peaks at 2931.329 cm-1 and 2886.590 are due to the symmetric stretching of
303
C-H group and bands appearing at 2 3 6 1 . 1 6 3 c m - 1 are ascribed to the bending vibrational
304
modes of glycosidic linkage. The absorption band at 1637.913 cm-1 in C .album V1 and C.
305
album V2 is attributed to the O-H related vibration that indicate the inter and intra-
306
molecular hydrogen bonding between the amorphous region of starch and water
307
molecules. The above mentioned band appeared sharply at about 1652.052 cm -1 in case
308
of A. cholai V3 which again confirms the absence of hydrogen bonding (O-H) in its starch.
309
Besides this the A. cholai V3 starch showed a broad band of C=N and C=C asymmetric
310
stretching due to presence of glycosidic linkage skeleton in the region of 1200-900 cm-1.
311
The broad bands in the region of 800 cm -1 to 400 cm-1are bending vibrational modes of the
312
glucose pyranose ring.
313
3.2.8. Rheological properties
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The rheological properties of starches during heating are shown in Table 3. Storage modulus
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(G') and loss modulus (G") of C. album V1 and C. album V2 starch suspensions increased
316
steeply to maxima and still tend to increase further with incessant heating indicating
317
their granule resistance to deformation, whereas the parameters for A. cholai V3
318
increased initially upon heating reaching a maximum and thereafter decreasing upon
319
continuous heating. This reduction in G' and G'' values of A. cholai V3 may be due to the
320
disintegration of starch granules leading to the melting of remaining crystallites and
321
increasing the molecular mobility. The temperature (TG'max) of C. album V2 starch at
322
which the storage modulus (G') loss modulus (G") reached the highest value was found to
323
be 87.3°C which was found to be higher than A. cholai V3 but lower than the C. album V1
324
starch (Table 3). This increase in both storage and loss moduli before T G'max is due to
325
swelling of starch granules and leaching of amylose chains, contributing to the formation of a
326
composite network of solvated materials supporting partially disintegrated starch granules
327
(Arocas, Sanz & Fiszman, 2009; Hsu, Lu, & Huang, 2000). The G' value of 41,500 Pa, G''
328
value of 7590 Pa was observed with a damping factor (Tan δ Peak) of 0.182 in C. album V2
329
starch suspension. The variation in G', G'' and tan δ during heating cycle may be due to the
330
difference in starch granule structure and its amylose content (Svegmark & Hermansson,
331
1993). The results are in close proximity with the study of Kong, Kasapis, Bao, & Corke,
332
(2012) on amaranth
333
4. Conclusion
334
The carbohydrate content of C. album varieties V1 and V2 was found to be 51.18 and
335
53.65g/100g, respectively. The starch obtained was found 47.30 and 37.59g/100g being
336
higher than A. cholai V3 with higher purity values of 99.12 and 99.20 g/100g,
starch
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respectively. Chenopodium starches showed lower swelling
338
diameter, pasting temperature and gelatinization temperature, whereas higher values were
339
noticed for amylose content, pasting viscosity and solubility when compared to A. cholai
340
V3 starch. A typical A-type X-ray diffraction pattern with crystallinity of 29.58%, 37.47 %
341
was found for C. album V1 and V2 starches. The C. album starches showed higher Peak
342
G' and G" than A. cholai V3. The analysis of various properties of C. album starches will
343
provide valuable information associated with the functional properties of starch, as desirable
344
functional properties can be used in various food industries due to its impending
345
applications for the development of various products viz., in high viscous foods, as a good
346
gelling agent, in dessert and other food formulations and could replace chemically modified
347
starches that are currently being used in a number of products. Moreover due to small
348
granule size, starches may find wide applications in edible biodegradable films, as fat
349
substitutes (due to smooth creamy structure), as a binder with orally active ingredients. The
350
above all interesting and unique rheological
351
beneficially exploited in the formulation of specialty food products.
352
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TABLE 1. PROXIMATE COMPOSITION AND FUNCTIONAL PROPERTIES OF CHENOPODIUM ALBUM RAW AND GERMINATED FLOUR Raw C.album flour 9.43b ±0.15 3.25a ±0.03 13.12b ±0.07 6.50a ±0.30 13.09b ±0.04 54.61a ±0.09 14.10b ±0.07
Germinated C.album flour 10.39a ±0.10 2.50b ±0.04 15.45a ±0.05 4.13b ±0.04 16.87a ±0.10 50.66b ±0.06 18.20a ±0.11
241b ±3.51 35.50b ±0.13 41.44a ±0.29
565a ±8.00 38.61a ±0.14 31.75b ±0.20
BD (g/ml) True density(g/ml) Porosity (g/100g) WAI (g/g) WSI (g/100 g) OAC (g/100 g)
0.59a ±0.06 1.30a ±0.10 54.70b ± 4.12 2.29b ±0.15
0.52a ± 0.06 1.36a ±0.10 61.80a ±2.68 3.55a ±0.18 9.60a ±0.70 2.81a ±0.11
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Parameter Moisture (g/100 g) Ash (g/100 g) Protein (g/100 g) Fat (g/100 g) Crude Fibre (g/100 g) Carbohydrate (g/100 g) DPPH radical scavenging activity (g/100 g) Total phenolics (mg/100g) Total dietary fibre (g/100 g) Total starch Functional properties
4.80b ±0.20
2.35b ±0.2
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TABLE 2. PASTING PROPERTIES OF CHENOPODIUM ALBUM FLOUR.
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Parameter Raw C.album flour Germinated C.album flour a Peak viscosity (cP) 925 ±15.01 863b ±25.50 Trough viscosity (cP) 887a ±12.05 645b ±7.54 a Breakdown (cP) 32 ±1.04 21b ±1.82 a Final viscosity (cP) 1412 ±21.50 1351b ±16.00 Setback (cP) 510a ±18.00 451b ±17.52 ° a Pasting temperature ( C) 86.45 ±2.41 84.83a ±0.58 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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TABLE 3. PHYSICAL, TEXTURAL PROPERTIES AND LIGHTNESS VALUES OF COOKIES Parameter *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies b b Weight (g) 12.80 ±0.05 13.04 ±0.36 14.43a ±0.49 b b Thickness (mm) 7.03 ±0.07 7.49 ±0.50 8.21a ±0.33 Diameter (mm) 50.72b ±0.06 54.37a ±0.52 54.76a ±0.89 a a Spread ratio 7.21 ±0.03 7.25 ±0.65 6.66a ±0.84 Hardness (N) 92.25a ±5.98 49.30b ±6.55 44.43b ±13.07 a c L* value 65.20 ±2.22 42.00 ±1.10 36.60b±1.04 *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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TABLE 4. ANTIOXIDANT ACTIVITY, TOTAL PHENOLICS AND TOTAL DIETARY FIBRE OF COOKIES. Parameter *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies c b DPPH radical 16.42 ±0.17 19.44 ±0.52 23.97a ±0.35 scavenging activity (g/100 g)/(TAC) Total phenolic NA 323b±3.44 671a± 5.60 Content(TPC) (mg/100g) Total dietary fibre 10.70c ±0.11 35.85b ±0.87 38.77a ±1.39 (g/100 g) *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n = 3).
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TABLE 5. SENSORY ANALYSIS OF COOKIES. *Wheat flour cookies Raw C. album flour Germinated C. (control) cookies album flour cookies a a Color & appearance 7.25 ±0.50 6.50 ±0.75 6.75a ±0.22 a a Aroma 7.00 ±0.60 7.25 ±0.50 7.75a ±0.36 Taste 7.00a ±0.40 7.00a ±0.25 7.75a ±0.11 a b Mouth feel 7.50 ±0.77 6.75 ±0.25 7.25ab ±0.22 Texture 6.50b ±0.75 7.00ab ±0.38 7.50a ±0.12 ab b Overall acceptability 6.75 ±0.50 6.50 ±0.75 7.75a ±0.20 *Chauhan et al., 2015 Mean values in the same row which is not followed by the same letter are significantly different (p < 0.05). Mean ± standard deviation (n=3).
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Quality parameter
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Figure 2. SEM micrographs of starches: (A1, A2) top two images representing C. album (V2) at magnification level of 5000 x and 10000 x. the middle two micrographs (B1, B2) belong to C. album (V1) at 5000 x and 10000 x, while the last two micrographs (C1, C2) are from A. cholai (V3) at 5000 x and 10000 x.
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Figure 4. FTIR spectrometric analysis of starch acquired from C .album (V1), C .album (V2) and A. cholai (V3).
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Highlights
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Smaller starch granule with higher paste viscosity and solubility was observed. Lower gelatinization temperature of starch with high degree of crystallinity. Unique viscoelastic behaviour and FTIR analysis of the starch were observed. The obtained starch can be a used as a replacement for chemically modified starches May find application in development of newer product formulations.
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