Vol 3 | Issue 2| 2013 | 50-55.

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International Journal e-ISSN: 2248 – 9207
Print ISSN: 2248 – 9193
of
Pharmacy Review & Research
www.ijprr.com
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DEGRADATION STUDIES OF CURCUMIN
Suresh D.Kumavat*, Yogesh S.Chaudhari, Priyanka Borole, Preetesh Mishra,
Khusbu Shenghani, Pallavi Duvvuri
DR.L.H.Hiranandani College of Pharmacy, C.H.M College Campus,
Opp.Ulhasnagar Railway Station, Ulhasnagar-421003, India.

ABSTRACT
Curcumin, a yellow phytochemical constituent obtained from Curcuma longa shows profound biological activities.
Literature reveals that curcumin is insoluble in water and susceptible to higher pH conditions. This work is focused firstly to
study the susceptibility of curcumin in water, various pH conditions in presence and absence of light by a simple UV
absorption method. A series of buffer solutions of pH conditions such as 1, 1.2, 6.8, 7, and 7.4 were selected and the result
showed that decomposition was pH dependent and occurs faster at neutral-basic conditions. The stability was more in acidic
pH and decrease as the pH increases. It was more stable at pH of 1.2; less than 1% of curcumin decomposed within 6hrs of the
total curcumin in the absence of light while it was more than 40% in the presence of light. Solution at pH of 1, 1.2, 6.8, 7.4
were studied for Thin layer chromatography (TLC) and compared with the standard curcumin. Fourier transform infrared
spectroscopy (FTIR) study was also conducted.

Key words: Curcumin, Stability, pH dependent, Buffers.

INTRODUCTION
Curcumin is a polyphenolic phytochemical with decreasing the pH values, the dissociation
constituent derived from the herbal remedy and dietary equilibrium shifts towards the neutral form with very low
spice turmeric Curcuma longa and it has been used from aqueous solubility [13].
the time immemorial as a dietary supplement, coloring It is a bis-α, β-unsaturated β-diketone. It is
agent, spice and also for curing the diseases. A vast reported that curcumin exhibits keto-enol tautomeric
research revealed that curcumin has a wide spectrum of forms. The keto form predominates in acidic and neutral
therapeutic effects such as anti-inflammatory [1], aqueous solutions and it was also reported that the same is
antibacterial [2], antifungal [3], anticancer [4], stable in the cell membrane as compare to stability in
antispasmodic [5], antioxidant [6], antiamoebic [8], anti blood [14]. It show heptadienone linkage between the two
HIV [9], antidiabetic[10], antifertility [11] etc. It is also methoxy phenyl rings which contains a highly activated
reported that the curcumin is safe up to 8g/day [12-14]. carbon atom, and the C–H bonds on this carbon are very
Curcumin(1,7-Bis-(4-hydroxy-3- weak due to delocalization of the unpaired electron on the
methoxyphenyl)-hepta-1,6-diene-3,5-dione) is an oil- adjacent oxygens hence it acts as an extraordinarily potent
soluble pigment, practically insoluble in water at acidic H-atom donor at pH 3–7[15](Fig. 1). In contrast, the
and neutral pH, soluble in alkali and highly susceptible for enolate form of the heptadienone chain predominates as an
pH change having molecular weight 368.38g/mole and a electron donor and the mechanism involved is more
melting point of 1830C [12].However, in aqueous systems typical as that of the scavenging activity of phenolic
like water, it is understood that at alkaline pH, the acidic antioxidants above pH 8[16].
phenol group in curcumin donates its hydrogen, forming Curcumin is relatively insoluble in water, but
the phenolate ion that enables curcumin into dissolution in dissolves in acetone, dichloromethane, methanol and
water. It is not stable at neutral and alkaline pH for longer ethanol. Curcumin as such is unstable at basic and neutral
period of time and gets easily degraded into compounds pH, and degrades within 30 min to Trans-6-(40-hydroxy-
like vanillin, ferulic acid, etc. It is stable below pH 7.0 but 30-methoxyphenyl)-2, 4- dioxo-5- hexanal, ferulic acid,

*
Corresponding Author Suresh D.Kumavat E mail: [email protected]

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feruloylmethane and vanillin. The initial degradation Evaluation of curcumin solutions

products are formed after 5 minutes and the Thin layer chromatography (TLC) and Fourier
chromatographic pattern obtained after 28 h at pH 8.5 is transform infrared spectroscopy (FTIR) was performed to
representative for alkaline degradation. Ferulic acid and evaluate the formation of degraded products in the buffer
feruloylmethane are formed initially. Feruloylmethane solutions of curcumin. The buffer solutions of the
rapidly forms coloured (mostly yellow to brownish- curcumin were transferred to the petri dishes and kept in
yellow) condensation products. Degradation products the oven for 72 hrs at 700C. The solidified residue was
formed by hydrolysis of feruloylmethane are vanillin and then checked for FTIR.
acetone and their amount increase with incubation time.
The presence of foetal calf serum, human blood, or RESULTS AND DISCUSSION
addition of antioxidants such as ascorbic acid, N- A plot of logarithmic concentration versus time
acetylcysteine or glutathione completely blocks this was made and from this degradation constant (K), half-life
degradation in culture media or phosphate buffer above (T1/2) was calculated [20]. The absorbance at time 0 hrs
pH7 [17]. Under acidic conditions, the degradation of was considered to be 100%.
curcumin is much slower, with less than 20% of total The results revealed that curcumin is unstable at
curcumin decomposed at 1 h. higher pH conditions. In this study we found that more
The kinetics of hydrolytic degradative reactions than 90% of curcumin decomposed rapidly in buffer
of compound 1 (diferuloylmethane) over the pH range 1- system at neutral basic condition. The increased stability
11 was studied. At pH<1, aqueous solutions of of curcumin at acidic pH may be contributed by the
diferuloylmethane have a red colour which indicates the conjugated diene structure. However when the pH is
protonated form (H4A+). In the pH range 1-7, the majority adjusted to neutral basic condition, proton removed from
of diferuloylmethane species are in the neutral form the phenolic group leads to the destruction of this
(H3A). Water solubility is very low in this pH range and structure. The amount of curcumin remained after 60 min
solutions are yellow. At pH>7.5, the colour changes to red. in various pH conditions as follows pH 1.2 >pH 1 >
The pKa values for the dissociation of the three acidic Distilled water >pH 6.8 >pH 7 >pH 7.4 as shown in table
protons in compound 1 (forms H2A-, HA2- and A3-) have 4.However when the experiment was conducted in the
been determined to be 7.8, 8.5 and 9.0 respectively [18]. absence of light or in dark the degradation of the curcumin
was much lower in the pH range if 1, 1.2, 6.8 as compared
MATERIALS AND METHODS to the buffers in the presence of light. The curcumin
Material degradation in the pH of 1.2 at the time of 6 hrs was less
Curcumin extract 95% was generously gifted by than 1% of the total curcumin. This results shows that the
Neelam phytoextract. All the other chemicals and reagents degradation of the curcumin was much higher in the
used were from LUBA chemicals and SD fine and are of presence of light as shown in table 5 and figure 5. Thus
analytical grade. curcumin should be stored in the amber coloured bottle to
prevent its photo oxidation.
Method TLC of standard solution of curcumin (4µg/ml)
Curcumin is reported to be highly susceptible to and buffer solutions at the time of 60 mins were performed
pH change and light [19]. In order to quantify the with the mobile phase consists of Toluene, Chloroform,
instability of curcumin in various pH conditions such as and methanol in the ratio of 4:4:2 v/v for pH 1, 1.2, 6.8
pH 1, 1.2, 6.8, 7 and 7.4 a simple spectroscopic method and 7.4 as shown as in Figure 4 [20].Plates of buffer
was adopted while to study the light effect it was exposed solution of pH1 and 1.2 shows three distinct spots of
to natural light. curcumin (Rf- 0.39), demethoxy curcumin (Rf- 0.35) and
bis demethoxy curcumin (Rf- 0.32).this shows that there is
The stability was also found out in aqueous little or no degradation at pH of 1 and 1.2.
solution by using distilled water.A stock solution of However at buffer solution of pH 6.8 there are
100μg/ml of curcumin was made by dissolving weighed two spots having Rf value of 0.31 and 0.34.thus it can be
amount (10 mg) of curcumin in 100 ml of methanol in a concluded that there is some amount of curcumin left
volumetric flask. Then, 1 ml of the stock solution was behind and the spot which is there is of degraded ones.
transferred to the 24 ml of distilled water to obtain a Also at buffer of pH 7.4 there is one spot having Rf value
concentration of 4μg/ml solution. The absorbance of the of 0.54 indicating the presence of other compounds.
resultant solution was immediately measured at 428 nm The Infra-red spectrographs of pure curcumin
using Shimadzu UV Visible Spectrophotometer (UV-1700 shows the functional groups of phenolic OH stretching,
pharmaspec) at different time interval against blank. The C=O and aromatic C=C which shows the peaks at 3500-
absorbance was read at zero time was considered to be as 3300 cm-1, 1625 –1640 cm-1 and 1520 – 1400 cm-1 in the
100 %. All the solutions are then transferred to the IR spectrum [21]. It has been observed that at pH 7.4 of
incubator to maintain the temperature of 37±0.5 0C and to the curcumin it showed the additional peak of aldehyde at
avoid the interference of light. This procedure was 2845 cm-1 due to the presence of vanillin or
repeated with the different buffer solutions of pH 1, 1.2, feruloylmethane. It also shows the less intense peak at
6.8, 7, and 7.4. The effect of light and in the absence of 3508 cm-1 of OH stretching and the peak has been shifted
light on buffer solutions ofpH 1, 1.2, 6.8 was studied. from 3510 to 3508 cm-1.

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Table 1. Data showing the logarithmic concentration and its absorbance of DW, 1, 1.2,.8 in the presence of light.
Time Distilled water (DW) pH 1 pH 1.2 pH 6.8
(hrs) Abs Log Conc Abs Log Conc Abs Log Conc Abs Log Conc
0 0.2516 0.602 0.2512 0.602 0.2514 0.602 0.2167 0.602
1 0.2412 0.583 0.2412 0.583 0.2426 0.586 0.1539 0.453
2 0.2238 0.569 0.2274 0.558 0.2197 0.579 0.1262 0.367
3 0.2016 0.551 0.2116 0.526 0.2043 0.547 0.1021 0.275
4 0.1733 0.505 0.1834 0.465 0.1872 0.509 0.0084 -0.809
5 0.1548 0.391 0.1662 0.422 60.1467 0.403 0.0067 -0.91
6 0.1207 0.282 0.1217 0.286 0.1214 0.321 0.0042 -1.113
7 0.1172 0.270 0.1148 0.261 0.1178 0.308 0.0038 -1.15
8 0.1108 0.245 0.1103 0.244 0.1121 0.287 0.0034 -1.2
9 0.0073 -0.935 0.0036 -0.057 0.0084 -0.838 0.0021 -1.42

Table 2. Data showing the logarithmic concentration and its absorbance of pH7 and 7.4.
Time pH 7 pH 7.4
(mins) Abs Log Conc Abs Log Conc
0 0.2126 0.602 0.2114 0.602
15 0.1937 0.561 0.1724 0.513
30 0.1476 0.443 0.1253 0.374
45 0.1123 0.324 0.1087 0.313
60 0.1018 0.282 0.0081 -0.814
75 0.0071 -0.874 0.0037 -1.15
The degradation constant (K) and Half-life of the reaction (T1/2) was then calculated by the following equation.
K= -2.303 X –Slope
T1/2 = 0.693 / K.

Table 3. Solution stability data of curcumin in different pH solutions in light.

Sample Degradation constant (k) hr-1 Half-life (t½) hrs or mins
Distilled water 0.1188 hr-1 5.83 hrs
pH 1 0.1107 hr-1 5.92 hrs
pH 1.2 0.1098 hr-1 6.55 hrs
pH 6.8 0.245 hr-1 2.82 hrs
pH 7 0.0145 min-1 or 0.87 hr-1 47.7 mins
pH 7.4 0.0154 min-1 or 0.924 hr-1 45 mins

Table 4. Cumulative amount of curcumin remaining after 60 mins.

pH % Amount of drug remained after 60 mins
1.2 96.47%
1 95.94%
Distilled water 95.85%
6.8 71%
7 47.87%
7.4 3.83%

Table 5. Data showing the logarithmic concentration and its absorbance of pH 1, 1.2, 6.8 in the absence of light.
Time pH 1 pH 1.2 pH 6.8
(hrs) abs Log conc abs Log conc abs Log conc
0 0.2512 0.602 0.2517 0.602 0.2468 0.602
1 0.2511 0.601 0.2514 0.6015 0.2466 0.6017
2 0.2504 0.600 0.2511 0.6010 0.2466 0.6017
3 0.2497 0.599 0.2507 0.6003 0.2461 0.6008
4 0.2496 0.599 0.2498 0.5987 0.2458 0.6002
5 0.2491 0.598 0.2496 0.5984 0.2457 0.6001
6 0.2489 0.598 0.2402 0.5977 0.2457 0.6001
7 0.2487 0.597 0.2492 0.5977 0.2452 0.5912
8 0.2486 0.597 0.249 0.5973 0.2447 0.5988
9 0.2456 0.592 0.2489 0.5972 0.2446 0.5981

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Fig 1. Curcumin in Acidic and Basic condition.

Fig 2. Degradation products of curcumin at basic condition.

Fig 3. Red coloured compound formed above pH 7.

Fig 4. Comparative degradation constant profile of Fig 5. Comparison between the buffers in the presence
curcumin in different buffers. and absence of light.

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Fig 6. IR spectra of standard curcumin (red) and curcumin at pH 7.4 (black)

Infrared spectroscopy of the Standard curcumin and curcumin at pH 7.4 was taken and compared the spectral bands and its
shifts.

CONCLUSION formation of its degraded products such as ferulic acid and

From the above experiment, curcumin is found to vanillin.
be unstable in solution form. Stability increases in acidic ACKNOWLEDGEMENT
and decreases as the pH increases. Also in the presence of First of all I would like to say thanks to my
light the degradation was much higher as compared to in College Dr.L.H.Hiranandani College of Pharmacy for
the absence of light. It has been found that that curcumin helping throughout my research and the principal Dr.
at pH 1.2 is highly stable in the absence of light as Parag S. Gide for his constant support and guidance.
compared to pH 1.2 in the presence of light. Stability Lastly I would thanks to the Neelam phytoextract for
decreases as the pH of the solution increases with the providing the standard curcumin for my research work.

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