Degradation Kinetics of Red Beet (Beta vulgaris) Powder during Thermal Processing and Changes of pH - Unika Repository

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DEGRADATION KI

DEGRADATION KINETICS OF RED BE

NETICS OF RED BEET (

ET (

Beta vulgariss

Beta vulgari

)

POWDER DURING

POWDER DURING THERMAL PROCE

THERMAL PROCESSING AND CHANG

SSING AND CHANGES OF pH

ES OF pH

Monica Ariyani Santoso

Monica Ariyani Santoso , Ellena Widuriati Dewi1)1), Ellena Widuriati Dewi , Victoria Kristina 1)1), Victoria Kristina Ananingsih

Ananingsih2)2), Alberta Rika Pratiwi, Alberta Rika Pratiwi2) 2)

1)_{Students of Food Technology Department, Faculty of Agricultural Technology,}

Soegijapranata Catholic University

2)

Lecturer of Food Technology Department, Faculty of Agricultural Technology, Soegijapranata Catholic University

ABSTRACT ABSTRACT

Red beet (Beta vulgaris) is a source of antioxidants and often used as a natural colorant in the food processing. Antioxidant content in beets is called betalain, which are classified into betacyanin which is purplish red pigment and betaxhantin which is the yellow orange pigment. Antioxidants are compounds that can delay or prevent the oxidation of free radicals such as rancidity and discoloration but are very susceptible to degradation. Free radicals are highly reactive molecules because it has unpaired electrons in the outer orbital of the molecule so that it can react with the cells of the body that can cause disease. Antioxidant activity degradation is determined by calculating the activation energy. The activation energy is the minimum energy required to perform a reaction. The purpose of this study was to determine the effect of pH, temperature and heating duration on antioxidant degradation of red beet powder and to determine the degradation kinetics by calculating the value of the activation energy based on the decrease in antioxidant activity with Arrhenius model. Preparation of red beet powder is conducted by drying red beet using cabinet dryer. Methods of research conducted with three levels, i.e. pH 6, 7 and 8; with four different temperatures, i.e. 40 C, 60 C, 80 C and 90 C; and at five heating rate, i.e. 0, 5, 10, 15 and, 20 o o o o minutes. The analysis performed in this study is the analysis of antioxidant activity in red beet powder using DPPH method. The results were calculated using the Arrhenius equation. The results showed that lowest decreasing antioxidant activity is at pH 6, temperature 40 C and 0 minute; is o equal to 25.40% and the highest decreasing antioxidant activity is at pH 8, temperature 80 C and o 20 minutes is equal to 49.76%. The highest activation energy (Ea) is pH 6, at 0 minute that equal to 7303.85 J/mol. While the lowest Ea is pH 8 at 20 minutes that equal to 4230.16 J/mol.

Keywords:

Keywords: red beet powder, antioxidants, activation energy, degradation kinetics

1.INTRODUCT

1.INTRODUCTION ION cause carcinogenic effects. To reduce the use

Red beet (Beta vulgaris) is purplish red tuber of synthetic food colorant, we can use natural

and often used as natural food colorant so the food colorant, i. e. red beet. The benefits of

product can improve consumer attraction. this colorant are safe use and also contain

Nowadays, synthetic food colorant already high of antioxidants. Antioxidants found in

widely circulated in the community. red beet called betalain. Betalain classified

However, it becomes dangerous if we into two pigment, betaxhantin which has

consumed it for a long period because it will orange and yellow color and betacyanin

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which has purplish red color (Pitalua et al.,

2010).

Besides betalain, antioxidants contained in

red beet namely polyphenols, vitamins,

flavonoids and folic acid. Antioxidants work

to prevent the oxidation reactions of free

beverage processing using heat treatment,

antioxidants found in red beets will be

degraded. Stability of betalain influenced by

light, oxygen, water activity, pH and

temperature (Gaztonyi et al., 2001).

Temperature affects the rate of reaction as a

factor affecting the decline of the food

product quality. Higher temperature will

caused reaction rate become faster so the

antioxidant activity became decrease.

Betalain stable at temperatures below 40oC and in acidic conditions with a pH range of

4-6 (Fennema, 1997)

This research use three different pH

condition; pH 6 (acidic), 7 (neutral), and 8

(alkaline). Selection of the pH to determine

antioxidant degradation of red beet, because

not all products are produced under

conditions of acidic beverages. Based on that

statement, the research is conducted to

determine the degradation kinetics of the

antioxidant activity in red beet powder with a

combination of pH, temperature and heating

duration. Besides that, the Arrhenius

approach is used to calculate the changes of

activation energy.

2.MATERIALS A

2.MATERIALS AND METHODSND METHODS

2.1.Chemicals and To 2.1.Chemicals and Tools. ols.

The materials used in this study are red beet

powder, methanol, distilled water, DPPH

solution, 10% HCl solution and 10% NaOH

solution. The tools used in this study are the

cabinet dryer, blender, slicer, pH meter, a

closed reaction tube, water bath,

thermocouple and spectrophotometer. The

data analyses are conducted with Microsoft

Excel 2010 and MatLab 2010a.

2.2.Sample Prepar 2.2.Sample Preparation. ation.

Red beet is dried with dryer cabinet to form a

powder blend. The powder is dissolved, and

then treated with 3 levels of pH (pH 6, pH 7,

and pH 8). NaOH solution is added to make

alkaline condition; meanwhile HCl solution is

added to make acidic condition of sample.

Next, the sample are placed in a reaction tube

and heated in a water bath. Each pH level is

heated with four level of temperature (40 C, o 60oC, 80 C, and 90 C) for 0, 5, 10, 15 and, o o 20 minutes. Heating temperature of 40oC betalain pigments to represent optimum

degree of stabilization of pigment; and the

temperature of 60 C, 80 C and 90 C are o o o

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represent pasteurization temperature.

Combination treatment performed three

replications. Determination of antioxidant

activity is conducted with DPPH (2,

2-diphenyl-1-picrylhydrazyl) method.

2.3.Antioxidant Act

2.3.Antioxidant Activity oivity of the Red Beet f the Red Beet

Powder (DPP

Powder (DPPH method). H method).

A (t) = 1+ − C= −1

Description:

A: antioxidant activity degradation A0: antioxidant activity degradation at t=0 Af: antioxidant activity degradation at t time r : constant

t: heating duration (min)

0.5 gram sample was weighed and extracted

with 5 ml of methanol for 2 hours in the dark

control, use 0, 1 ml of methanol were reacted

with 3.9 DPPH solution and methanol used

as a blank solution.

Antioxidant activity is expressed as %

inhibition with the following equation:

%inhibition_{= {(A}_B-A )/A_A _B_{} x 100%}

Description:

AA = sample absorbance at 30 minutes

AB= control absorbance (methanol+DPPH)

(Williams et al., 1995)

2.3.Logistic Equat 2.3.Logistic Equation. ion.

The mathematics equation model(logistic

equation) is used to determine degreeof

antioxidantactivity degradationwith

equation:

(Wolf & Venus, 1992 in Garnier et al., 1999;

modification).

2.4.Antioxidant Degr

2.4.Antioxidant Degradation Kinadation Kinetics of etics of

Red Beet Powd Red Beet Powder. er.

The determination of the Ea value using

Arrhenius equation, the data obtained by

analysis of linear equations where Ea is the

activation energy, whose value is assumed to

be constant at a certain temperature range, R

is the gas constant (8.314 J/mol K), T is the

temperature expressed in Kelvin (K).

Arrhenius equation can be seen as follows:

ln k = ln k 0–Ea/RT

Where the rate constant k showed a decrease

in quality, k is a constant (independent of 0

temperature), Ea is the activation energy, T is

absolute temperature (K), R is the gas

constant (8.314 J/mol.K) (Arpah, 2003).

3.RESULT

3.RESULTS AND DISCS AND DISCUSSION USSION

3.1.Antioxidant

3.1.Antioxidant Activity Activity DegradationDegradation of of

Red Beet Powd Red Beet Powder er

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Table 1

Table 1 .Antioxidant Activity Degradation in Red Beet Powder with Variation of pH, Temperature,

and the Heating Duration

Temperature Antioxidant Activity Degradation (%)

pH Heating Duration

(oC)

0 minute 5 minutes 10 minutes 15 minutes 20 minutes

6 40 25.40±0.64 28.32±1,55 32.53±1.00 35.53±0.96 36.11±0,59

60 27.77±0.29 29.53±0.99 34.30±2.72 35.85±2.62 36.79±2.35

80 34.28±0.90 36.02±0.35 39.32±1.50 39.40±1.13 41.42±2.54

90 37.76±0.21 42.11±0.75 43.98±1.70 45.02±1.82 45.52±0,47

7 40 29.05±0.20 32.86±0.76 32.95±1.18 36.03±1.20 37.58±3.38

60 30.30±0.47 33.04±0.45 35.63±1.61 37.64±1.62 40.19±2.38

80 34.20±0.88 37.45±0.36 39.21±1.94 41.77±1,49 42.72±1.03

90 39.86±0.61 43.90±1.52 44.46±0.76 45.13±0.79 46.51±0.94

8 40 29.71±0.98 32.59±1.56 35.38±2.06 37.89±3.29 39.71±2.61

60 31.13±0.41 35.09±1.96 39.11±2.84 41.20±0.46 42.50±1.43

80 36.44±0.59 36.53±0.66 43.00±1.21 45.79±0.15 47.59±0.38

90 41.05±0.89 44.98±1.79 46.01±0.15 47.33± 0.99 49.76±2.77

Description:

All values are mean ± SD (Standard Deviation)

From Table 1. there was gradual increase

antioxidant activity degradation from red beet

powder at pH 6 in temperatures ranging from

40oC to 90 C also in the heating duration is o started from minute 0 to minute 20. At pH 7

and pH 8 also showed similar results,

Antioxidant activity degradation will increase

with higher heating temperature and longer

heating duration. The higher degradation is at

pH 8 with a temperature of 90 C in the 20 o minutes. Fennema (1997) said that red beet

has a pH optimum between pH 4 and pH 6.

Therefore the antioxidant activity

degradation of red beet at pH 6 is lower than

at pH 7 and 8 because in pH 6 the sample is

at stable pH conditions. Acidic conditions

can increase antioxidant activity stability

because it can prevent oxidation so as to

minimize the damage of betalain pigments

(Ravichandran et al., 2013). Temperature of

40oC is the optimal temperature for the pigment stability so the damage or the

degradation is still relatively lower than the

higher temperature (Roy et al., 2004).

Heating causes degradation in the form of

betalain pigment degradation. This pigment

is converted into betalamic acid and

cycloDOPA 5-O-glycoside. The longer the

heating process, the pigment betalain

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breakdown process will be greater

(Delgado-Vargas et al., 2000).

(a)

(b)

(c)

Figure

Figure 11. Decrease in antioxidant activity of

red beet powder on (a) pH 6, (b) pH 7, (c) pH

8.

In Figure 1. shows that the higher pH will

caused higher degradation of antioxidant

activity of red beet powder. On the research

from Stintzing and Carle (2004), it said that

pH is a factor determines the stability of

antioxidant activity. In addition to pH,

temperature and heating duration can also

cause antioxidant activity of red beet become

unstable. Temperature affects the stability of

the antioxidants in red beets. In theory of

Stintzing and Carle (2004), betalain stability

is affected by temperature, pH, moisture,

light and oxygen. At high temperature,

antioxidants in red beet powder will be

damaged.

Logistic model Logistic model

(a)

(b)

(c)

Figure 2.

Figure 2. Decrease antioxidant activity of red

beet powder to the logistic equation on (a)

pH 6, (b) pH 7, (c) pH 8

In Figure 2. we can be see that the antioxidant

activity degradation will increased with the longer heating duration. Highest antioxidant

activity degradation is on 90 C at 20 minutes o and the lowest antioxidant activity

degradation is on 40oC at

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5 minutes.

Table 2

Table 2 .Correlation Coefficient of Linear

Equations in Red Beet Powder

Temperature

Table 3 .Correlation Coefficient of

Logistic Equations in Red Beet Powder.

Temperature

Temperature pH 6pH 6pH 7pH 7 pH 8 pH 8

According to D'Amico et al. (2006), the

temperature and time of pasteurization for red

beet powder is 60 C for 18 minutes; while o according Klewicka & Czyzowska (2011)

using temperature 80 C for 10 minutes and o

90oC for 5 min. When the pasteurization temperature and time applied in the logistic

equation for each pH, the value of %

antioxidant activity degradation of red beet

powder can be seen in Table 4. From Table 4 it can be seen that the pasteurization time and

temperature are inversely related. The higher

the heating temperature, the shorter the time

the higher correlation coefficient, the

relationship between x and y will be higher

too (Labuza, 1978). Based on these results it

can be concluded that the antioxidant activity

degradation of red beet powder tends to use

the principle of logistic equation, where the

initial heating of antioxidant degradation

begins to rise higher and then increases the

longer the increase be fixed at some point.

Timuneno (2008) states that the logistic

equation is showed that at a certain point

decrease in antioxidant activity reaches

equilibrium, so that the graph will be a

Temperature/duration % degradation

of pasteurization pH 6 pH 7 pH 8

3.2.Antioxidant Degradation Degradation Kinetics Kinetics of of

Red Beet Powd Red Beet Powder er

Degradation kinetics of the antioxidant of red

beet powder was analyzed using the

Arrhenius equation. The trick is plotting ln k

(%antioxidants degradation) with 1/T

(temperature heating) for each heating time

and pH conditions in order to obtain a linear

equation. From this linear equation obtained

value gradient/slope equal to the activation

energy that divided with the gas constant

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values (Table 5).

Table 5.

Table 5. Activation Energy Values at Each

pH

T = heating duration (menit)

Slope = gradient (K)

Ea = activation energy (J/mol)

R = gas constant (J/mol.K)

From the Table 5 it can be seen that the

activation energy of each sample is

proportional to the value of degradation

quality constant. The highest activation

energy is red beet powder at pH 6 were

heated for 0 minutes; while the lowest

activation energy is red beet extract at pH 8

were heated for 20 minutes. According

Azeredo (2009), degradation of the pigment

betalain will caused the value of the

activation energy decreases. This means that

the greater the degree of degradation of

betalain pigments, the value of the activation

energy decreases.

The activation energy the minimum amount

of energy supplied to a reaction (Hariyadi,

2004). From the theory of Robertson (1993),

states that the smaller the activation energy,

the faster the product will be severely

degrades. To calculate the activation energy,

make a graph of ln k with 1/T, can be seen in

Figure 3. it can be seen that the obtained

linear equation y=mx+b. The slope of the

equation above represents the value (-Ea/R)

with constant gas of 8,314 J/mol.K. In the

linear equation y=-878,5x+1.433 (R =0.995) 2 obtained Ea value of 7303.85 J/mol.

CONCLUSION CONCLUSION

•Decrease in the antioxidant activity of

extracts of red beet will increase when

the temperature and heating time

increased. Decrease in antioxidant

activity in red beet powder will increase

when conditioned in neutral and alkaline

pH.฀ ฀

•The best temperature of pasteurization is

at a temperature of 60 C while the o pasteurization temperature which causes a decrease in antioxidant activity was

highest in the temperature of 90oC.฀ •The higher the temperature of฀

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pasteurization, the heating duration will

be lower, stable antioxidant activity

carried out at a temperature of 60 C at o 18 minutes pasteurization, pasteurization

is done at a temperature of 80 C at 10 o minutes and at a temperature of 90 C at o 5 minutes.

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