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Sugar Tech (Oct-Dec 2012) 14(4):428431 DOI 10.

1007/s12355-012-0159-8

SHORT COMMUNICATION

Effect of Reducing Sugars on Non-enzymic Browning During Thermo-Evaporation of Sugarcane Juice for Making Jaggery
R. Banerji Pushpa Singh S. I. Anwar S. Solomon

Received: 7 March 2012 / Accepted: 1 June 2012 / Published online: 18 July 2012 Society for Sugar Research & Promotion 2012

Abstract Jaggery samples were prepared from sugarcane juice having different concentrations of reducing sugars (by adding glucose/fructose) for studying the contribution of invert sugars towards colour development of jaggery by non-enzymic browning reactions during jaggery making process. Addition of 0.5 and 1.0 g glucose/100 ml cane juice did not alter the colour of juice after boiling for 30 min at 98 C, while addition of same quantities of fructose/100 ml in the cane juice enhanced the colour of boiling juice over control. Further, evaporation of cane juice till 118 C for preparation of jaggery indicated that the colour of jaggery samples prepared from juice having additional 0.5 and 1.0 g fructose/100 ml juice increased indicating more contribution of fructose towards darkening of colour development of jaggery during thermo-evaporation process. As the pH of juice remained below 6 through out the jaggery making process, fructose of cane juice seemed to be contributing more towards colour of jaggery in comparison to glucose in the non-enzymic browning. This was indicated by signicantly more colour development by caramelization of fructose at 118 C in comparison to glucose and sucrose since carbonylamine browning does not take on much signicance until the pH is greater than 6.
R. Banerji P. Singh (&) S. Solomon Division of Plant Physiology and Biochemistry, Indian Institute of Sugarcane Research, Raibareilly Road, Lucknow 226002, Uttar Pradesh, India e-mail: parampushpa@yahoo.com R. Banerji e-mail: ramanbanerji@rediffmail.com S. I. Anwar Division of Agricultural Engineering, IISR, Lucknow 226002, Uttar Pradesh, India

Keywords Sugarcane Thermo-evaporation Non-enzymic browning Jaggery Reducing sugars Glucose Fructose

Jaggery (Gur) is an eco-friendly traditional sweetener prepared from sugarcane juice by thermo-evaporation (Roy 1951). It contains 8085 % sucrose, 1015 % of reducing sugars inclusive of glucose and fructose, 0.25 % of proteins, 0.5 % of fat and 0.61 % minerals (Kumar 1999). It is nutritionally superior to white sugar and has various medicinal properties (Ghosh et al. 1998). About 19.1 % of sugarcane is utilized by the jaggery and khandsari industry in India, producing about 7 million tonnes of jaggery annually (Anon 2005). The major factor that governs the consumer preference and marketing of jaggery is its external appearance i.e. colour, texture and storability (Kapur and Kanwar 1983). The darkening and poor storability of jaggery has been accounted for by several workers to be due to the presence of reducing sugars. Ghosh and Agarwal (1983) reported that jaggery colour was positively correlated with total reducing sugars. The cane juice, which is processed for jaggery contains different chemical constituents that include reducing and nonreducing sugars, amino acids, phenols, inorganic anions and cations (Irwine 1977). Among these constituents, the reducing sugars present in the cane juice and formed during thermo-evaporation due to acid inversion of sucrose (Honig 1953) play a major role in imparting the colour to the jaggery. Sugars are known to be the principal browning reactants in several food products formed either during the processing or upon storage of the nished product (Babsky et al. 1986). Sucrose and its hydrolysis products (glucose

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and fructose) have been prime sources for the manufacture of caramel (Tomasik et al. 1989). The coloured compounds are formed both in absence of nitrogenous compounds (caramelization reactions) and in presence of nitrogenous compounds by Maillard reaction (Hodge 1953). In dilute solutions of reducing sugars, the initial stages of the caramelization reactions parallel the events described for enolisation, isomerisation, dehydration and fragmentation reactions (Shallenberger and Birch 1975). Subsequently, polymerisation reactions occur which lead to the formation of pigments similar to those formed in caramelization at either higher temperature or in more concentrate solution. Though information on effect of reducing sugars on colour development of jaggery are available, information on contribution of glucose and fructose separately towards non-enzymic browning during thermo-evaporation processing for jaggery making is lacking. Keeping these in view, the present work was undertaken to study the contribution of glucose and fructose separately on colour development in sugarcane juice and jaggery. Sugarcane varieties (mid late variety CoSe 92423 and early variety CoS 95255) were harvested from the farm at the Indian Institute of Sugarcane Research. Lucknow, India, located at 26560 N, 80520 E and 111 m above the sea level. Juice was extracted by a commercial vertical crusher installed in the unit. Fresh ltered cane juice (2 l) was taken in an aluminium pan and immediately heated. First scum was removed just before boiling of juice. After removal of scum, aqueous extracts of Deola (Hibiscus culneus, grown in the farm) was added during boiling for clarifying the juice. Scum formed on the surface was again removed by stainless steel strainer leaving a clear juice. When all the scum formed was removed, the juice became transparent and yellowish brown in colour. This was concentrated till the attainment of striking temperature 116118 C (Roy 1951; Agarwal et al. 1988) and transferred to mould for setting of jaggery. To determine the effect of glucose and fructose on darkening of sugarcane juice during thermo-evaporation process, 0.5 g fructose, 1.0 g fructose, 0.5 g glucose and 1.0 g glucose were separately added in different asks having 100 ml of freshly extracted juice, while no addition was made in control having 100 ml of freshly extracted juice. The asks containing juice were boiled (98 C) for 30 min. After cooling, volume of the concentrated juice was made up to 100 ml with distilled water and ltered. The optical density of coloured juices after ltration was recorded at 540 nm. The experiment was repeated ve times with juice sample. For determination of the effect of glucose and fructose on colour development of sugarcane jaggery, ve different jaggery samples were prepared from 2 l freshly extracted juice, each having additional quantity of reducing sugars

(T1: Control; T2: 0.5 g glucose/100 ml; T3: 1.0 g glucose/ 100 ml; T4: 0.5 g fructose/100 ml; T5: 1.0 g fructose/ 100 ml). The colour of the jaggery sample was measured by recording the optical density of 13 % jaggery solution at 540 nm. The experiment was repeated three times. To study the caramelization, 4 ml each of 50 % aqueous solutions of glucose, fructose and sucrose were taken in triplicate and were kept in an autoclave at 118 C for 70 min. These were then taken out and after cooling, the volume was made up to 4 ml with distilled water for recording of optical density of caramelized solutions at 540 nm against the respective unheated 50 % sugar solutions. The data of all the experiments have been presented as mean SE. Statistical signicance was determined with analysis of variance. The aim of the study was to evaluate the contribution of glucose and fructose towards colour formation in sugarcane jaggery. The experiments were conducted to study the effect of glucose and fructose on colour development of cane juice after boiling at 98 C for 30 min. It was observed that addition of 0.5 and 1.0 g glucose/100 ml in the cane juice did not alter the colour of juice at 98 C and was at par with the control, while addition of same quantities of fructose enhanced the colour of the boiling juice over control (Fig. 1). However, darkening in colour of juice with increasing concentration of glucose and fructose was not found. Further evaporation of cane juice till the attainment of striking point at 118 C for preparation of the nal product in the form of jaggery conrmed that the colour of jaggery prepared from juice having additional amount of fructose at both the concentrations was darker than the jaggery prepared from juice having same quantities of additional glucose. With 0.5 and 1.0 g/100 ml of additional fructose, an increase by 38.7 and 19.4 % in the colour of jaggery with respect to control was recorded, respectively (Fig. 2). The colour of fresh cane juice is due to the presence of reducing sugars, amino acids, carotenes, anthocyanins,

Fig. 1 Effect of exogenous addition of glucose and fructose (g/100 ml) to cane juice on darkening of juice during thermoevaporation

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Colour of jaggey ( OD at 540nm)
0.4

Sugar Tech (Oct-Dec 2012) 14(4):428431

0.45 0.4 0.35 0.3 0.25 0.2 0.15


control Glucose 0.5 Glucose 1.0 Fructose 0.5 Fructose 1

0.35 0.3

OD* at 540 nm

0.25 0.2 0.15 0.1 0.05 0 Fructose Glucose Sucrose

Additional reducing sugars in cane jiuce (g/100ml)

Fig. 2 Effect of exogenous addition of reducing sugars to cane juice on darkening of colour of jaggery

Sugars

xanthophylls and chlorophyll and anthrocyanin. This coloured juice when subjected to heating for making jaggery begins to darken. Initially when the temperatures are low (below 50 C), the darkening is due to enzymatic browning caused by polyphenol oxidase activity leading to the oxidation of phenolic constituents (Chisari et al. 2008). As the temperature is raised, the enzymatic activity stops but the darkening continues further till the attainment of striking temperature of jaggery (116118 C). This darkening is explained by the gradual formation of dark coloured compounds melanodins through caramelization and Maillard reactions (Tomasik et al. 1989; Hodge 1953). The results of our present studies revealed that relative to glucose, fructose contributed more towards darkening of sugarcane juice during thermo-evaporation and the ultimate nal product (i.e. jaggery). This may be explained by the relative reactivities of the aldose and ketoses in browning reactions (Burton and McWeeny 1963). Burton et al. (1963) reported that the intensity of the colour formed by fructose and amino acids was more than the intensity of colour formed by glucose and amino acids through Maillard reactions as indicated in the results of our experiment also. In sugarcane juice, both Maillard reactions and caramelization might be attributing to the darkening of juice and the jaggery product. It has been reported that carbonylamine browning due to Maillard reactions does not take on much signicance until the pH is greater than 6.0 and the browning of the sugars is primarily due to the caramelization reaction (Schroeder et al. 1955). As observed in our study, the pH of cane juice was throughout below 6.0 during the thermo-evaporation till 116118 C. This indicated that the caramelization of sugars might be attributing more to the colour development of the nal product. This nds support from the results of our ndings of relative assessment of the colour development through caramelization of sucrose, glucose and fructose (Fig. 3). The results indicated that fructose contributed signicantly (p \ 0.05) more towards darkening of colour in comparison to glucose and sucrose. Least colour was developed by

Fig. 3 Caramelization of sugars solutions (50 %) at 118 C

sucrose. Sucrose is generally inert at relatively low temperatures, but when conditions lead to its hydrolysis to glucose and fructose, these compounds readily enter into caramelization and carbonylamine reactions and lead to browning. It is concluded that amongst sucrose and invert sugars, fructose contributes more towards the non-enzymatic browning due to caramelization in comparison to glucose and sucrose during thermo-evaporation process for making jaggery from cane juice.
Acknowledgments Authors thank the Director, Indian Institute of Sugarcane Research, Lucknow, for providing facilities and constant encouragement.

References
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Sugar Tech (Oct-Dec 2012) 14(4):428431 Honig, P. 1953. Chemical reactions in the settling of limed cane juices. Proceedings of the ninth congress of the International Society of Sugarcane Technologists 9(2): 583594. Irwine, J.E. 1977. Composition of cane and juice. In Cane sugar handbook, 10th ed, ed. G.P. Meade, and J.C.P. Chen, 1529. New York: Wiley. Kapur, J., and R.S. Kanwar. 1983. Studies on storage of gur in Punjab. Maharashtra Sugar 8: 4549. Kumar K. 1999. Oscillations in Jaggery and Khandsari industry, Proceedings of the natural seminar on status, problems and prospects of jaggery and khandsari industry pp 87. Roy, S.C. 1951. Monograph on gur industry of India, 1843. Kanpur: I.I.S.T.

431 Schroeder, L.J., M. Iacobellis, and A.H. Smith. 1955. The inuence of water and pH on the reaction between amino compounds and carbohydrates. Journal of Biological Chemistry 212: 973983. Shallenberger, R.S., and G.G. Birch. 1975. Intrinsic chemical reactions of the sugars. In Sugar chemistry, ed. R.S. Shallenberger, and G.G. Birch, 89112. Westport, CT: Avi Publishing Company, Inc. Tomasik, P., M. Palasinski, and S. Wiejak. 1989. Thermal decomposition of carbohydrates: Part I-the decomposition of mono-, di and oligosaccharides. In Advances in carbohydrate chemistry and biochemistry, ed. R.S. Tipson, and D. Horton, 203255. San Diego, CA: Academic press, Inc.

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