Enantiomeric separation and validation of D-isomer in Pemetrexed disodium–An anti-cancer agent using Chiral HPLC

 

S. Hemchand*1, R. Ravi Chandra Babu1 , Mukthinuthalapati Mathrusri Annapurna2

1GITAM Institute of Science, GITAM (Deemed to be University), Visakhapatnam, India

2Department of Pharmaceutical Analysis & Quality Assurance, GITAM Institute of Pharmacy,

GITAM (Deemed to be University), Visakhapatnam, India

*Corresponding Author E-mail: hemchand.suryadevara@gmail.com

 

ABSTRACT:

Pemetrexed disodium is an anti-cancer agent. It is an anti-folate drug used for the treatment of malignant pleural mesothelioma and non-small cell lung cancer. In the present study the authors have proposed a chiral HPLC method for the separation and determination of Pemetrexed disodium and its D-isomer using Chiralpak AD-H (250 x 4.6 mm, 5 µm) column within a run time of 30 mins. A mixture of n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) was the final optimized mobile phase composition after many trials for the separation of D-isomer of Pemetrexed disodium (at 35°C) using Waters Alliance 2695 series HPLC system with 2998 photodiode array detector (UV detection at 240 nm). The method is very much useful for the pharmacokinetic studies as well as the metabolite study in vitro and in vivo for the determination of therapeutic activities of optical isomers.

 

KEYWORDS: Pemetrexed disodium, HPLC, D-isomer, Validation.

 

 

INTRODUCTION:

Pemetrexed disodium is a disodium salt of (2S)-2-[[4-[2-(2-amino-4-oxo-3,7-dihydropyrrolo[2,3-d] pyrimidin-5-yl)ethyl]benzoyl]amino]pentanedioate (Figure 1A) and is available as hepta hydrate or hemi penta hydrate whereas the (D-Isomer impurity) is chemically N-[4-[2-(2-Amino-4, 7-dihydro-4-oxo-1H-pyrrolo [2, 3-d] pyrimidin-5-yl) ethyl] benzoyl]-D-glutamic acid disodium hemi penta hydrate (Figure 1B). Pemetrexed disodium was approved for the treatment of cancer. It can be used alone or also in combination with other drugs for the treatment of malignant pleural mesothelioma for patients who cannot be treated using surgery and also certain types of non-small cell lung cancer for patients whose disease is advanced and metastasized1-5. Pemetrexed disodium was determined by using in human plasma, metabolites and urine by Ultrafast LC-MS/MS6-7, HPLC8, UPLC9, Chiral HPLC10, HPLC11-14, visible spectrophotometric methods15 and electrochemical method16 in the literature.

 

Waters Alliance 2695 series HPLC system with 2998 photodiode array detector (UV detection at 240 nm) along with Chiralpak AD-H (250 x 4.6 mm, 5 µm) column was used for the determination of D-isomer in Pemetrexed disodium in the present chiral-LC study and the method was validated (ICH guidelines) 14-16.

 

 

Figure 1A: Chemical structure of Pemetrexed disodium

 

Figure 1B: Chemical structure of D-Isomer of Pemetrexed disodium

 

MATERIALS AND METHODS:

Pemetrexed disodium and its related substances were procured and HPLC grade acetonitrile, n-Hexane, Ethanol, Isopropyl alcohol, methanol, TFA, DEA, Propanoic acid, sodium hydroxide, hydrochloric acid and hydrogen peroxide were purchased from Merck (India). Milli-Q water was used for the entire work. Stock solution containing Pemetrexed disodium and D- isomer was prepared in mobile phase and diluted using the diluent and stored. During the robustness study the above solution was spiked with four related substances available, stored and diluted as per the necessity.   

 

Chromatographic conditions

The D-isomer was separated from Pemetrexed disodium and quantified using Chiralpak AD-H (250 x 4.6 mm, 5 µm) column within a run time of 30 mins. A mixture of n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) was the optimized mobile phase composition after many trials for the separation of D-isomer of Pemetrexed disodium (at 35°C) using Waters Alliance 2695 series HPLC system with 2998 photodiode array detector (UV detection at 240 nm). The system was operated on isocratic mode with flow rate 0.5 ml/min with an injection volume 5µl.

 

Method validation17

A series of linearity solutions containing D-isomer (1.3523-11.3067 µg/mL) and Pemetrexed disodium standard (0.9437-9.9702 µg/mL) at different concentrations at LOQ level, 0.075%, 0.12%, 0.15%, 0.18% and 0.225% were prepared with respect to the working concentration. The peak area was noted and the linearity graph was drawn with concentration of the solutions on X-axis and the mean area on Y-axis. The slope, y-intercept and correlation coefficient of the calibration curve were calculated. Precision studies (n=6) were performed for the mixture of Pemetrexed disodium and its D-isomer and the % RSD of the mean peak area was determined. Accuracy study was performed for Pemetrexed disodium and its D-isomer (i.e. 50%, 100% and 150%). Robustness was also performed by varying flow rate (0.1 ml/min), mobile composition and column temperature (5°C).

 

Assay of Pemetrexed disodium injection

Pemetrexed disodium is available with brand names Alimta (Eli Lilly and Company, India) (Label claim: 100 mg and 500 mg); Pexate (Miracalus Pharma Pvt Ltd) (Label claim: 100 mg), Giopem (GLS Pharma Ltd) (Label claim: 100 mg and 500 mg) as solution for injection. Two different brands were chosen and extracted and diluted with mobile phase as per the requirement and the percentage purity of Pemetrexed disodium was determined.

 

RESULTS AND DISCUSSION

A specific and simple chiral RP-HPLC method was developed and validation for the separation and determination of Pemetrexed disodium and its D-isomer using Chiralpak AD-H (250 x 4.6 mm, 5 µm) column within a run time of 30 mins.

 

Method optimization

A Chiral RP-HPLC method has been developed for the separation and quantification of Pemetrexed disodium and its D-isomer. During optimization a mixture of solvents containing n-Hexane, Ethanol, TFA, DEA, Propionic acid, Isopropyl alcohol were used in different composition with different flow rates, concentration etc. and finally n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) / 35 / 240 was chosen for the present work. The observations recorded during the trials were shown in Table 1 and that of the optimized chromatographic conditions Table 2. Pemetrexed disodium and its D-isomer were eluted at 9.632 ± 0.001 min and 12.272 min respectively (Figure 2).

 

Table 1: Method optimization

Trial

Mobile phase (v/v) / Column temp (°C) /

λ (nm) / Flow rate (mL/min)

Observations and conclusions

1

n-Hexane : Ethanol : TFA :DEA: Propionic acid (350:654:1:1:10) / 27 / 240 / 1

Concentration (2 mg/mL) and injection volume (10 µL).

D-isomer impurity and one of the process related unknown impurities are closely eluting. Mobile phase was used as diluent.

2

n-Hexane: Ethanol: TFA

(400: 600: 1) / 27 / 220 and 240

Peak broadening and two wavelength maxima for Pemetrexed peak at 220 nm and 240 nm were observed and 240 nm was selected to monitor D-isomer.

3

n-Hexane: Ethanol: TFA (400 : 600 : 1) / 40 / 240

D-isomer and unknown impurity were merged together.

4

n-Hexane: Ethanol: TFA: Propanoic acid

(350 : 650 : 1:10) / 40 / 240

D-isomer is resolved but D-isomer was eluted at the tailing of Pemetrexed peak.

5

n-Hexane: Ethanol :TFA: DEA: Propanoic acid  (350: 650 : 1:1:10) / 40 / 240

All the peaks were resolved but the solution is un-stable in the diluent.

6

n-Hexane: Ethanol: TFA: DEA: Propanoic acid (350: 650: 1:1:10) / 40 / 240

Solution are stable for 24 hrs even at room temperature. New impurity, Alanine derivative was identified. Methanol was used as diluent.

7

n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) / 35 / 240 / 0.5

Alanine derivative impurity and D-isomer resolved with USP resolution of 1.4 and Pemetrexed disodium and D-isomer also well resolved with resolution 3.8.

8

n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) / 35 / 240

Concentration (5 mg/mL) and injection volume (5 µL) were changed. S/N ratio of D-isomer is 250.

9

n-Hexane: Ethanol: Isopropyl alcohol: TFA (250:650:100:1) / 35 / 240

S/N ratio of D-isomer peak is 220 and resolution between Pemetrexed and

D-isomer peak is 2.9. Method optimized.

 

 

Trial 1: Overlay Chromatograms of spike solution with samples

 

Trial 2: Chromatogram of sample solution

 

Trial 3: Chromatogram of sample solution

 

Trial 4: Chromatogram of sample solution

 

Trial 5: Chromatogram of sample solution

 

Trial 5: Chromatogram of   Pemetrexed API spiked with D-isomer at different time intervals

 

 

Trial 6: Chromatogram of Pemetrexed spiked solution (Initial)

 

Trial 6: Chromatogram of Pemetrexed spiked solution (24hrs)

 

Trial 6: Chromatogram of Blend solution of  D-isomer and Alanine derivative of Pemetrexed impurity at lower level

 

Trial 7: Chromatogram of Pemetrexed spiked with D-isomer and Alanine derivative of Pemetrexed impurity

 

 

Trial 8: Chromatogram of D-isomer impurity and Pemetrexed

 

Trial 9: Chromatogram of methanol as blank

 

Trial 9: Chromatogram of system suitability of Pemetrexed and D-isomer

 

 

Trial 9: Chromatogram of Pemetrexed disodium

Figure 2: Chromatograms observed during method optimization (Trials)

 

 

 

 

 

 

 

 

Table. 2. Optimized chromatographic conditions

Column

Chiral pak AD-H (250 x 4.6 mm, 5 µm)

Detector

PDA detector

Mobile phase (v/v)

n-Hexane : Ethanol : Isopropyl alcohol :TFA (250:650:100:1)

Mobile phase program

Isocratic

Flow rate

0.5 mL/min

Detection Wavelength

240 nm

Sample temperature

Ambient

Sample Temperature

15°C

Injection volume

5 µL

Diluent

Methanol

 

Method validation

Linearity

Pemetrexed disodium and its D-isomer have shown linearity over 0.9437-9.9702 and 1.3523-11.3067 µg/mL (Table 2) with linear regression equations y = 19600x - 765.3 (R2 = 0.9969) (Figure 3A) and y = 17033x - 2285.9 (R2 = 0.9986) (Figure 3B) respectively. The relative retention time (RRF) for Pemetrexed disodium and D-isomer was calculated basing on the slope ratio (API to D-isomer) method. The relative response factor was found to be 1.00 and 1.15 for Pemetrexed disodium and its D-isomer respectively. As the relative response factor for Pemetrexed disodium D-isomer is within the range 0.8-1.2 and therefore the relative response factor will be considered as 1.00 for D-isomer.

 

Table 3: Linearity of Pemetrexed disodium and D-isomer

 

Pemetrexed disodium

D-isomer

Conc.  (µg/mL)

Mean peak area

Conc. (µg/mL)

Mean peak area

0.9437

14210

1.3523

18592

3.3234

67291

3.7689

63868

5.3174

102605

6.0302

99124

6.6468

132496

7.5378

129360

7.9762

158809

9.0454

152370

9.9702

189891

11.3067

187967

Slope

19600

Slope

17033

y-intercept

-765.3

y-intercept

-2285.9

Correlation coefficient

0.9969

Correlation coefficient

0.9986

 

 

 

                                                 

                                                      

 

 

Figure 3A: Linearity of Pemetrexed disodium

 

 

Figure 3B:  Linearity of D-isomer

 

Accuracy

Pemetrexed disodium sample (5.0 mg/mL) was injected to estimate the content of D-isomer. D-isomer at three concentration levels i.e. 50%, 100% and 150% w.r.t. specification limit of test concentration was spiked with Pemetrexed disodium sample solution (5.0 mg/mL). Each level was prepared in triplicate and each of nine solutions was injected once and amount of D-isomer obtained in each solution was calculated (Table 4). The % recovery was 82.1-97.9 which is within the acceptance criteria (80.0%-120.0%) the % RSD is 6.3 for D-isomer with indicating that the acceptance criteria (<10) was satisfied.

 

Table 4: Accuracy

Spiking

level

Amount

Added (µg/mL)

Amount

obtained (µg/mL)

% Recovery

50%

3.2725

2.7172

83.0

3.2725

2.8349

86.6

3.2725

2.6867

82.1

100%

6.5450

6.4087

97.9

6.5450

6.2583

95.6

6.5450

5.8023

88.7

150%

9.8175

8.2429

84.0

9.8175

8.3537

85.1

9.8175

8.5936

87.5

RSD

6.3%

 

Precision

Six replicate sample solutions of Pemetrexed disodium (5.0 mg/mL) in diluent containing 0.15 % of D-isomer w.r.t. sample concentration were prepared and each spiked sample solution was injected and RSD was calculated D-isomer content. Intermediate precision of the method was determined by analyzing six samples spiked with D-isomer on different day, by different analyst, different columns and using different equipment. The % D-isomer was found to be 0.14 and the % RSD was zero in both method precision and intermediate precision studies (Acceptance criteria: RSD should not be more than 10.0%).

 

 

Solution of Pemetrexed disodium and its D-isomer at LOQ level was injected in six replicates and RSD for the peak areas of Pemetrexed disodium and D-isomer was calculated. The RSD of peak areas was found to be 8.2% for D-isomer and 11.1% (Table 5) for Pemetrexed disodium indicating that the method is precise (Acceptance criteria: RSD of peak areas should not be more than 15.0% for each analyte).

 

Table 5: Precision of Pemetrexed disodium and D-isomer

S. No.

D-isomer

Pemetrexed disodium

1

16459

13735

2

13928

11791

3

13274

10554

4

14084

11547

5

14113

14148

6

13322

12879

Mean

14197

12442

RSD

8.2%

11.1%

 

 

 

Robustness

The effect of column temperature, flow rate, mobile phase composition on system suitability were summarised in Table 6. As per the system suitability criteria, for the robustness study is the resolution between Pemetrexed disodium and D-isomer peak should not be less than 2.0 and that of S/N ratio for D-isomer peak should be more than 50. As small variations of the chromatographic conditions did not affect the system suitability and relative retention time (RRT) of D-isomer it indicates that the method is robust. Pemetrexed disodium solution was spiked with D-isomer and the related substances such as acid intermediate, alanine derivative of Pemetrexed, DMF derivative of Pemetrexed and Pemetrexed diethyl ester to prove the specificity of the method during robustness study (Figure 4). It was observed that the D-isomer was well separated from that of Pemetrexed disodium even in presence of the related substances.

 

 

Table 6: Robustness of Pemetrexed disodium and its D-isomer

Condition

System suitability solution

Specificity solution

S/N value D-isomer

(NLT 50)

Resolution

(NLT 2.0)

Pemetrexed disodium

Retention Time (min)

RRT of

D-isomer

As per method

80

3.2

9.18

1.28

Lower column (Temp. 30°C)

82

3.2

9.29

1.30

Higher column (Temp. 40°C)

88

3.3

9.01

1.26

Lower Flow rate (0.4 mL/min.)

86

3.5

11.51

1.29

Higher Flow rate (0.6 mL/min.)

73

3.1

7.63

1.28

Mobile phase organic ratio variation

(275 : 650 : 100 :1.0) %v/v

98

3.3

9.38

1.30

Mobile phase organic ratio variation

(225 : 650 : 100 :1.0) %v/v

59

3.0

8.84

1.27

Mobile phase organic ratio variation

(250 : 715 : 100 :1.0) %v/v

64

2.8

8.36

1.26

Mobile phase organic ratio variation

(250 : 585 : 100 :1.0) %v/v

78

2.9

9.45

1.30

Mobile phase organic ratio variation

(250 : 650 : 110 :1.0) %v/v

121

3.2

9.17

1.29

Mobile phase organic ratio variation

(250 : 650 : 90 :1.0) %v/v

73

3.2

9.28

1.29

Mobile phase organic ratio variation

(250 : 650 : 100 :1.1) %v/v

70

3.2

8.63

1.28

Mobile phase organic ratio variation

(250 : 650 : 100 :0.9) %v/v

61

3.1

9.40

1.29

 

 

Pemetrexed disodium spiked with its D-isomer and related substances

 

Lower flow rate – 0.4 mL/min

 

Higher flow rate – 0.6 mL/min

 

Lower column temperature - 30°C

 

Lower column temperature - 40°C

 

Higher n-Hexane content

 

Lower n-Hexane content

 

Higher Ethanol content

 

Lower Ethanol content

 

Higher Isopropyl alcohol content

 

Lower Isopropyl alcohol content

 

Higher TFA content

 

Lower TFA content

Figure 4 : Representative chromatograms observed during robustness study

 

 

 


          

Assay of Pemetrexed disodium

Two different brands of Pemetrexed disodium formulations were analyzed using the above optimized conditions. Pemetrexed disodium has shown 99.89-100.13 purity range and there is no interference of the excipients with the drug peak.

 

Specificity

Specificity of the method was determined by injecting the analyte spiked with all the known related substances expected to be present in Pemetrexed disodium. Separate solutions of diluent, Pemetrexed disodium standard and known related substances (D-Isomer, Alanine derivative of Pemetrexed, DMF derivative of Pemetrexed, Acid intermediate and Pemetrexed diethyl ester) and a spiked solution containing all the mentioned components were injected at 0.15% level for D-Isomer, Alanine derivative of Pemetrexed, DMF derivative of Pemetrexed, Acid intermediate and Pemetrexed diethyl ester into HPLC. Table 7 shows retention time, RRT and peak purities for D-isomer in the spiked solution. No peaks were observed in the diluent (Figure 5A) at the retention time of D-isomer. D-isomer peak was well resolved (Figure 5C) from nearby peak in spiked solution (Figure 5B) as shown in the chromatogram. The purity angle is less than purity threshold indicating the peak is spectrally pure. Peak purity plots of D-isomer in both standard and spiked solution were shown in Figure 5D and Figure 5E. The LOD and LOQ of Pemetrexed disodium and D-Isomer were shown in Figure F and Figure G.

 

Table 7: Specificity

Component

Retention time

(min)

RRT

Purity

angle

Purity

threshold

D-isomer standard

11.52

-----

3.451

4.138

D-isomer in spiked solution

11.56

1.25

2.111

2.705

Pemetrexed disodium in Spiked solution

9.22

1.00

 

 

Alanine derivative in Spiked solution

12.70

1.38

 

 

DMF derivative in Spiked solution

8.36

0.91

 

 

Acid intermediate in Spiked solution

12.55

1.36

 

 

Pemetrexed diethyl ester in Spiked solution

24.12

2.62

 

 

 

 

 

A.       Blank

B.       Chromatogram of Pemetrexed disodium and D-isomer in combined solution

C.       Chromatogram of D-isomer standard

D.       Purity plot of D-isomer standard

 

E.       Purity plot of D-isomer (combined solution)

F.        LOD for Pemetrexed disodium and D-isomer

G.       LOQ for Pemetrexed disodium and D-isomer

Figure 5: Specificity of Pemetrexed disodium and D-isomer

 

 

CONCLUSIONS:

A new Chiral RP-HPLC method was developed for the separation and quantification of Pemetrexed disodium and its D-isomer in presence of related substances. The method was validated (ICH guidelines) by linearity, precision, accuracy and robustness and it is mostly helpful in the determination of therapeutic activity of the metabolites during the drug absorption as well as in the pharmacokinetic studies. The proposed method is specific and the system suitability parameters are within the acceptable criteria.

 

ACKNOWLEDGEMENT:

The authors are grateful to (Eli Lilly and Company (India) for providing the gift samples of Pemetrexed disodium and its D-isomer in presence of related substances. There is no conflict of interest.

 

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Received on 12.01.2019            Modified on 29.01.2019

Accepted on 04.02.2019           © RJPT All right reserved

Research J. Pharm. and Tech 2019; 12(2):773-786.

DOI: 10.5958/0974-360X.2019.00136.7