A novel validated RP-HPLC-DAD method for the estimation of Eluxadoline in bulk and pharmaceutical dosage form

 

Uttam Prasad Panigrahy1*, A. Sunil Kumar Reddy2,3

1Department of Pharmaceutical Analysis and Quality Assurance, Malla Reddy College of Pharmacy, Maisammaguda, Secunderabad-500014, India

2Department of Pharmaceutical Chemistry, Bharat Institute of Technology-Pharmacy, Ibrahimpatnam, Hyderabad-501510, India

3APL Research Centre-2, Aurobindo Pharma Ltd., Sanga Reddy, Medak, Telengana-502329, India

*Corresponding Author E-mail: uttampanigrahy@gmail.com

 

ABSTRACT:

The present study describes about novel approach to develop and validate a rapid, accurate, precise, simple, efficient and reproducible isocratic Reversed Phase-High Performance Liquid Chromatographic (RP-HPLC-DAD) method for the estimation of Eluxadoline in bulk and pharmaceutical dosage form. Eluxadoline were separated using Hypersil C18 column (250mm×4.6 mm, 5µm particle size), Waters Alliance e2695 HPLC system with 2998 PDA detector and the mobile phase contained a mixture of Acetonitrile and Water (70:30, v/v). The flow rate was set to 1ml/min with the responses measured at 260nm. The retention time of Eluxadoline was found to be 3.481min.Linearity was established for Eluxadoline in the range of 10-125µg/ml with correlation coefficient (r2=0.999). The percentage recoveries were between 99.92% to 100.07%. Validation parameters such as specificity, linearity, precision, accuracy, robustness, limit of detection (LOD) and limit of quantitation (LOQ) were evaluated for the method according to the International Conference on Harmonization (ICH) Q2 R1 guidelines. The developed method was successfully applied for the quantification and hyphenated instrumental analysis.

 

KEYWORDS: Eluxadoline, PDA detector, Hyphenated, ICH.

 

 

 


INTRODUCTION:

Eluxadoline is a novel, orally-active drug for the treatment of diarrhea and abdominal pain in individuals with diarrhea-predominant irritable bowel syndrome. Eluxadoline is a μ-and κ-opioid receptor agonist and δ-opioid receptor antagonist that acts locally in the enteric nervous system, possibly decreasing adverse effects on the central nervous system.[1] Eluxadoline is chemically known as 5-({[(2S)-2-amino-3-(4-carbamoyl-2, 6-dimethylphenyl) propanoyl] [(1S)-1-(4-phenyl-1 H-imidazol-2-yl) ethyl] amino} methyl)-2-methoxybenzoic acid was shown in Figure 1.

 

Literature review reveals that no analytical methods have been reported for the determination of Eluxadoline and few pharmacokinetics and preclinical studies was performed which includes Eluxadoline benefits patients with irritable bowel syndrome with diarrhea in a phase 2 study [2], Drug discovery approaches to irritable bowel syndrome and Eluxadoline approved for irritable bowel syndrome with diarrhea [3,4], Effect of Uptake Transporters OAT3 and OATP1B1 and Efflux Transporter MRP2 on the Pharmacokinetics of Eluxadoline [5] and Molecular characterization of eluxadoline as a potential ligand targeting mu-delta opioid receptor heteromers [6]. The present study was aimed to develop a novel, simple, economic and validated RP-HPLC-DAD method for the estimation of Eluxadoline according to ICH guidelines [7].

 

Figure 1: Chemical structure of Eluxadoline

 

MATERIALS AND METHODS:

Chemicals and Reagents:

Eluxadoline bulk drug were kindly provided as gift sample by Manus Aktteva Biopharma LLP, Ahmedabad, India. HPLC grade of Acetonitrile purchased from Merck Specialities Private Limited, India. HPLC grade of Water purchased from Rankem Ltd., India. Viberzi tablet contain Eluxadoline 100mg is obtained from a local pharmacy manufactured by Actavis Pharma Manufacturing Pvt. Ltd., India.

 

Instrumentation:

The analysis was performed by using a chromatographic system from Waters Alliance e2695 HPLC system with 2998 PDA detector. The HPLC system was equipped with Empower 2 software. Semi-micro analytical balance (India), an Ultrasonic bath sonicator (Frontline FS 4, Mumbai, India), Digital pH meter (Systronics model 802) and Whatman filter paper No. 41 (Whatman International Ltd., England) were used in the study.

 

Chromatographic conditions:

Eluxadoline was analysed in Hypersil C18 (250mm×4.6 mm, 5mm particle size) column for the chromatographic separation. The mobile phase was composed of Acetonitrile and Water (70:30, v/v). Filtered through 0.45µm nylon membrane filter under vacuum filtration and pumped at ambient temperature, at a flow rate of 1 ml/min with UV detection wavelength at 260nm. Injection volume was 20μl. The run time was 5min and the retention time of Eluxadoline was found to be 3.481min.

 

Chromatographic Parameters:

Equipment

:

Waters Alliance e2695 HPLC system

with 2998 PDA detector.

Column

:

Hypersil C18

(250mm×4.6 mm, 5mm particle size)

Flow rat

:

1ml/min

Wavelength

:

260 nm

Injection volume

:

20 ml

Column oven

:

Ambient

Run time

:

5 Minutes

 

 

Preparation of mobile phase:

Acetonitrile HPLC grade and Water HPLC grade were mixed in the proportion of 70:30 v/v and was filtered through 0.45μm nylon membrane filter and degassed by sonication.

 

Preparation of diluent:

Mobile phase was used as diluent.

 

Preparation of standard stock solution of Eluxadoline:

Standard stock solution of Eluxadoline were prepared by dissolving 100mg of Eluxadoline in 100ml of diluent into a 100ml clean dry volumetric flask and the standard solution was filtered through 0.45 μm nylon membrane filter and degassed by sonicator to get the concentration of 1000µg/ml of Eluxadoline.

 

Preparation of standard solution of Eluxadoline for assay:

From the above standard stock solution of 1000µg/ml of Eluxadoline further pipette 0.5 ml and transferred into a 10ml volumetric flask and dilute up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline.

 

Selection of wavelength:

Standard stock solution of Eluxadoline were prepared by dissolving 100mg of Eluxadoline in 100ml of diluent into a 100ml clean dry volumetric flask and the standard solution was filtered through 0.45μm nylon membrane filter and degassed by sonicator to get the concentration of 1000µg/ml of Eluxadoline. From the above standard stock solution of 1000µg/ml of Eluxadoline further pipette 0.5 ml and transferred into a 10ml volumetric flask and dilute up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline. The wavelength of maximum absorption (λmax) of 50µg/ml of Eluxadoline were scanned using UV-Visible spectrophotometer within the wavelength region of 200–400 nm against mobile phase as blank. The wavelength (λmax) was found to be 260nm shown in Figure 2.

 

Figure 2: UV-Spectrum of Eluxadoline at 260nm

Preparation of sample solution of Eluxadoline:

Twenty tablets were accurately weighed and powdered and tablet powder equivalent to 100mg of Eluxadoline were taken into 100ml clean dry volumetric flask, diluent was added and sonicated to dissolve it completely and volume was made up to the mark with the same diluent and filtered through 0.45 μm nylon membrane filter. Further pipette out 0.5ml from the above Eluxadoline sample stock solution into a 10ml volumetric flask and diluted up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline. 20mL from standard and sample solution were injected into the chromatographic system and the peak areas were measured for Eluxadoline was shown in Figure 3 and 4 respectively. The % Assay was calculated by comparing the peak area of standard and sample chromatogram by using the formula given below and the assay result was shown in Table 1.

 

                    AT        WS       DT         P        Avg. Wt

Assay % =------ x ------x ------ x -------x---------------- X 100

                  AS          DS       WT       100      Label Claim

Where:

AT = Average peak area of sample preparation

AS= Average peak area of standard preparation

WS = Weight of standard taken in mg

WT=Weight of sample taken in mg

P = Percentage purity of working standard

DS= Dilution factor for standard preparation

DT=Dilution factor for sample preparation


 

 

Figure 3: Standard chromatogram of Eluxadoline

 

 

Figure 4: Sample chromatogram of Eluxadoline

 

 


Table 1: Assay of marketed formulation of Eluxadoline

Drug

Viberzi Tablet Label Claim (mg)

Amount Found (mg)

% Label Claim ± % RSD (n=3)

Eluxadoline

100

99.97

99.97±0.12

 

 

Validation of the proposed method:

The developed method for the simultaneous estimation of Eluxadoline was validated as per the ICH guidelines for the parameters like system suitability, specificity, linearity, accuracy, precision, ruggedness, robustness, limit of detection (LOD) and limit of quantitation  (LOQ) [7].

 

 

System Suitability:

At first the HPLC system was optimized as per the chromatographic conditions. One blank followed by six replicates of a single calibration standard solution of 50µg/ml of Eluxadoline was injected to check the system suitability. To ascertain the system suitability for the proposed method, the parameters such as retention time, theoretical plates and peak asymmetry were taken and results were presented in Table 2.

 

Table 2: System suitability test parameters for Eluxadoline

Parameter (n=6)

Eluxadoline

Retention Time (Mins)

3.481

Theoretical plates

2985

Tailing factor

1.1

 

Specificity:

The effect of excipients and other additives usually present in the dosage form of Eluxadoline in the determination under optimum conditions was investigated. The specificity of the RP-HPLC method was established by injecting the blank and placebo solution into the HPLC system. The representative chromatogram of blank and placebo was shown in Figure 5 and 6 respectively.

 

 

 

 

 

Linearity for Eluxadoline:

Aliquots of 0.1, 0.25, 0.5, 0.75, 1 and 1.25ml of standard working solution of Eluxadoline was pipetted out from the standard stock solution of 1000µg/ml of Eluxadoline and transferred into a series of 10ml clean dry volumetric flask and make volume up to the mark with the same diluent to get the concentration of 10, 25, 50, 75, 100 and 125µg/ml of Eluxadoline. The calibration standard solutions of Eluxadoline were injected using a 20μl Hamilton Rheodyne injector and the chromatograms were recorded at 260nm and a calibration graph was obtained by plotting peak area versus concentration of Eluxadoline.

 


 

Figure 5: Chromatogram of Blank

 

Figure 6: Chromatogram of Placebo

 


The linearity data is presented in Figure 7 and Table 3. Acceptance Criteria: Correlation coefficient should be not less than 0.999

 

Table 3: Linearity data for Eluxadoline

Linearity of  Eluxadoline

Concentration (µg/ml)

Peak Area

10

141572

25

348774

50

718146

75

1060463

100

1411231

125

1765875

 

 

Figure 7: Linearity graph of Eluxadoline

 

Accuracy studies for Eluxadoline:

The accuracy of the method was determined by calculating recovery of Eluxadoline by the method of standard addition. Known amount of standard solution of Eluxadoline at 50%, 100% and 150% was added to a pre quantified sample solution and injected into the HPLC system. The mean percentage recovery of Eluxadoline at each level was calculated and the results were presented in Table 4.

 

Preparation of pre quantified sample solution for accuracy studies:

Twenty tablets were accurately weighed and powdered and tablet powder equivalent to 100mg of Eluxadoline were taken into 100ml clean dry volumetric flask, diluent was added and sonicated to dissolve it completely and volume was made up to the mark with the same diluent and filtered through 0.45 μm nylon membrane filter. Further pipette out 0.5ml from the above Eluxadoline sample stock solution into a 10ml volumetric flask and diluted up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline.

 

Preparation of standard solution of Eluxadoline for accuracy studies:

Standard stock solution of Eluxadoline were prepared by dissolving 100mg of Eluxadoline in100ml of diluent into a 100ml clean dry volumetric flask and the standard solution was filtered through 0.45μm nylon membrane filter and degassed by sonicator to get the concentration of 1000µg/ml of Eluxadoline.

 

Preparation of 50% standard solution:

From the standard stock solution of 1000µg/ml of Eluxadoline further pipette 0.25ml and transferred into a 10ml volumetric flask and dilute up to the mark with diluent to get the concentration of 25µg/ml of Eluxadoline.

 

Preparation of 100% standard solution:

From the standard stock solution of 1000µg/ml of Eluxadoline further pipette 0.5ml and transferred into a 10ml volumetric flask and dilute up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline.

 

Preparation of 150% standard solution:

From the standard stock solution of 1000µg/ml of Eluxadoline further pipette 0.75ml and transferred into a 10ml volumetric flask and dilute up to the mark with diluent to get the concentration of 75µg/ml of Eluxadoline.

 

Acceptance Criteria: The % Recovery for each level should be between 98.0 to 102.0%.

 

 

Table 4: Recovery study data of Eluxadoline

Sample name

Amount added (µg/ml)

Amount found (µg/ml)

% Recovery

Statistical Analysis

S1:50%

25

24.99

99.96

Mean-99.92

S.D-0.16

%RSD-0.16

S2:50%

25

24.94

99.75

S3:50%

25

25.01

100.06

S4:100%

50

49.98

99.96

Mean-100.06

S.D-0.09

%RSD=0.09

S5:100%

50

50.04

100.09

S6:100%

50

50.07

100.14

S7:150%

75

75.03

100.04

Mean-100.07

S.D-0.05

%RSD-0.05

S8:150%

75

75.10

100.13

S9 :150%

75

75.04

100.05

 

Precision studies for Eluxadoline:

Method precision (Repeatability):

Twenty tablets were accurately weighed and powdered and tablet powder equivalent to 100mg of Eluxadoline were taken into 100ml clean dry volumetric flask, diluent was added and sonicated to dissolve it completely and volume was made up to the mark with the same diluent and filtered through 0.45 μm nylon membrane filter. Further pipette out 0.5ml from the above Eluxadoline sample stock solution into a 10ml volumetric flask and diluted up to the mark with diluent to get the concentration of 50µg/ml of Eluxadoline. A homogenous sample of a single batch analysed six times and was checked whether the method is giving consistent results. The %RSD for the area of six replicate injections was calculated as mentioned in Table 5. Acceptance Criteria: The % RSD for the peak area of six sample injections should not be more than 2%.

 

 

Table 5: Method precision data for Eluxadoline

Eluxadoline

S.

No.

Concentration

(μg/ml)

Retention time

(min)

Peak Area

%

Assay

1

50

3.481

720811

99.97

2

50

3.473

721121

100.01

3

50

3.473

719528

99.79

4

50

3.473

719982

99.85

5

50

3.481

719291

99.76

6

50

3.481

721187

100.02

Average

3.477

720320

99.90

SD

0.004382

828.8208

0.11495

%RSD

0.13

0.12

0.12

 

 

System precision:

The system precision was carried out to ensure that the analytical system is working properly. The standard preparation concentration of 50µg/ml of Eluxadoline was injected six times into the HPLC and the %RSD for the area of six replicate injections was calculated as mentioned in Table 6. Acceptance Criteria: The % RSD for the peak area of six standard injections should not be more than 2%.

 

 

 

 


TABLE 6: System precision data for Eluxadoline

Eluxadoline

S.No.

Concentration (μg/ml)

Retention  time (min)

Peak Area

1

50

3.481

721976

2

50

3.498

720442

3

50

3.498

720177

4

50

3.481

720371

5

50

3.473

721997

6

50

3.473

722911

Average

3.484

721312

SD

0.011419

1131.152

%RSD

0.33

0.16

 

 

TABLE 7: Ruggedness data for Eluxadoline

Ruggedness Data for Eluxadoline

Laboratory-1 (% Assay)-HPLC-1

Laboratory-2 (% Assay)-HPLC-2

 

Analyst-1

Analyst-2

Analyst-1

Analyst-2

Conc. (μg/ml)

Day-1

Day-2

Day-1

Day-2

Day-1

Day-2

Day-1

Day-2

50

99.87

100.04

100.12

100.03

100.06

100.08

100.09

100.07

50

99.90

100.02

99.98

100.01

100.09

100.01

99.89

100.03

50

99.73

99.74

99.76

99.62

99.67

100.07

99.87

99.35

50

99.74

99.83

99.83

99.78

99.84

99.85

100.08

100.02

50

99.75

99.77

99.76

99.74

99.79

99.72

100.04

99.65

50

99.99

100.11

100.12

100.09

100.07

100.06

100.15

99.91

Average

99.83

99.92

99.93

99.88

99.92

99.97

100.02

99.84

SD

0.1079

0.15728

0.16869

0.1906

0.1754

0.148044

0.113313

0.283402

%RSD

0.11

0.16

0.17

0.19

0.18

0.15

0.11

0.28

Intermediate precision within-laboratories variations (n=24)

Laboratory-1 (% Assay)-HPLC-1

Laboratory-2 (% Assay)-HPLC-2

Average

99.89

Average

99.94

SD

0.045461

SD

0.076757

%RSD

0.05

%RSD

0.08

Reproducibility between laboratories (n=48) (% Assay)

Average

99.92

SD

0.035355

%RSD

0.04

 

Table 8: Summary of validation parameter for Eluxadoline

Parameters

RP-HPLC method

Eluxadoline

Linearity range (µg/ml)

10-125

Slope

14128

Intercept

973.6

Correlation coefficient

0.999

LOD (µg/ml)

0.08

LOQ (µg/ml)

0.25

Method Precision (% RSD, n=6)

0.12

System precision (% RSD, n=6)

0.16

Ruggedness (% RSD, n=24)

Lab-1

Lab-2

0.05

0.08

Reproducibility (% RSD, n=48)

0.04

% Accuracy

99.92-100.07

Robustness (% RSD, n=6)

Less Flow rate

More Flow rate

 

0.09

0.03

Less Organic phase

More Organic phase

0.02

0.15

 

 

 

Table 9: Summary of Robustness (Change in Flow Rate) for Eluxadoline

Drug

Change in

Flow rate (ml/min)

Retention

Time

(Mins)

Robustness (0.9 ml/min to 1.1 ml/min)

Average peak area (n=6)

SD

% RSD

USP Plate Count

Asymmetry

Eluxadoline

0.9

3.634

721812

633.013

0.09

2923

1.1

1.0

3.481

721336

1148.885

0.16

2985

1.1

1.1

3.110

721699

233.7991

0.03

2841

1.1

 

 

Table 10: Summary of Robustness (Change in Mobile Phase) for Eluxadoline

Drug

Change in Mobile Phase

Retention Time

(Min)

Change in mobile phase (Acetonitrile and water) (63:37 v/v to 77:23 v/v)

Average peak area (n=6)

SD

% RSD

USP Plate Count

Asymmetry

Eluxadoline

10% less Organic

(63:37 v/v)

3.147

721839

145.3113

0.02

2832

1.1

Actual (70:30 v/v)

3.481

721336

1148.885

0.16

2985

1.1

10% more Organic

(77:23 v/v)

3.510

724352

1072.527

0.15

2758

1.1

 

 

 

Table 11: Summary of solution stability-effect of mobile phase (Acetonitrile and Water (70:30, v/v) for Eluxadoline for 48 hours at room temperature.

 

Solution stability for Eluxadoline

S.No.

Concentration (μg/ml)

Retention time (min)

Peak Area

%Assay

USP Plate Count

Asymmetry

1

50

3.481

721432

100.06

2955

1.1

2

50

3.473

721284

100.04

2971

1.11

3

50

3.473

721120

100.01

2879

1.1

4

50

3.473

719432

99.78

2961

1.11

5

50

3.481

721701

100.09

2946

1.1

6

50

3.481

718057

99.59

2931

1.1

Average

3.477

720504

99.93

2941

1.1

SD

0.004382

1443.526

0.200203

33.05601

0.005164

%RSD

0.13

0.2

0.2

1.12

0.468

 

 

 


Intermediate precision/ruggedness:

The intermediate precision (also known as Ruggedness) of the method was evaluated by performing precision on different laboratory by different analyst and different days. The sample preparation concentration of 50µg/ml of Eluxadoline was injected six times into the HPLC and the %RSD for the area of six replicate injections was calculated as mentioned in Table 7. Acceptance Criteria: The % RSD for the peak area of six standard injections should not be more than 2%.

 

Limit of Detection (LOD) and Limit of Quantification (LOQ):

Limit of Detection (LOD) and Limit of Quantification (LOQ) were calculated as 3.3×SD/S and 10×SD/S respectively as per ICH guidelines, Where SD is the standard deviation of the response (Y-intercept) and S is the slope of the calibration curve.  The LOD is the smallest concentration of the analyte that gives a measurable response (signal to noise ratio of 3). The LOD of Eluxadoline was calculated and shown in Table 8. The LOQ is the smallest concentration of the analyte which gives response that can be accurately quantified (signal to noise ratio of 10). The LOQ of Eluxadoline was calculated and shown in Table 8.

 

Robustness:

As part of the Robustness, deliberate change in the flow rate and mobile phase proportion of ±10% was made to evaluate the impact on the method. The results reveal that the method is robust. The results are summarized in Table 9 and 10.

 

Stability of solution:

The %RSD of the assay of Eluxadoline from the solution stability and mobile phase stability experiments was within 2%. The results of the solution and mobile phase stability experiments confirm that the sample solutions and mobile phase used during the assays were stable upto 48hours at room temperature was calculated and shown in Table 11.

 

RESULTS AND DISCUSSION:

To optimize the RP-HPLC parameters, several mobile phase compositions were tried. A satisfactory separation and good peak symmetry for Eluxadoline were obtained with a mobile phase containing a mixture of Acetonitrile and water (70:30, v/v) was delivered at a flow rate of 1ml/min to get better reproducibility and repeatability. Quantification was achieved with PDA detection at 260nm based on peak area. The retention time of Eluxadoline was found to be 3.481min. Linearity was established for Eluxadoline in the range of 10-125µg/ml with correlation coefficient 0.999 and mean accuracies were found to be is 99.92% to 100.07% for Eluxadoline, which indicates accuracy of the proposed method. The % RSD values of accuracy for Eluxadoline were found to be < 2 %. The % RSD value of method precision was 0.12% for Eluxadoline and % RSD value of system precision was 0.16% for Eluxadoline. The % RSD value of reproducibility is 0.04% for Eluxadoline reveal that the proposed method is precise. LOD value for Eluxadoline was found to be 0.08µg/ml and LOQ value for Eluxadoline were found to be 0.25µg/ml. The % RSD values of robustness studies were found to be < 2% reveal that the method is robust enough. These data show that the proposed method is specific and sensitive for the determination of Eluxadoline.

 

CONCLUSION:

RP-HPLC method for the estimation of Eluxadoline in their bulk and pharmaceutical dosage form was established and validated as per the ICH guidelines. Linearity was achieved for Eluxadoline in the range of 10-125µg/ml with correlation coefficient 0.999. The percentage recovery of drug was achieved in the range of 98-102% which was within the acceptance criteria. The percentage RSD was NMT 2 % which proved the precision of the developed method. The developed method is simple, sensitive, rapid, linear, precise, rugged, accurate, specific, and robust. Hence it can be used for the routine analysis of Eluxadoline in their bulk and pharmaceutical dosage form.

 

ACKNOWLEDGEMENT:

The authors are thankful to Malla Reddy College of Pharmacy for providing the chemicals and instruments and Manus Aktteva Biopharma LLP, Ahmedabad, India and Eisai Pharmaceuticals India Pvt. Ltd, Mumbai, India for providing the samples for research.

 

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5.        Davenport JM, Covington P, Bonifacio L, McIntyre G, Venitz J. Effect of Uptake Transporters OAT3 and OATP1B1 and Efflux Transporter MRP2 on the Pharmacokinetics of Eluxadoline. The Journal of Clinical Pharmacology. 2015; 55: 534–542.

6.        Fujita W, Gomes I, Dove LS, Prohaska D, McIntyre G, Devi LA. Molecular characterization of eluxadoline as a potential ligand targeting mu-delta opioid receptor heteromers. Biochem Pharmacol. 2014; 92: 448-456.

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Received on 02.11.2015             Modified on 18.11.2015

Accepted on 21.11.2015           © RJPT All right reserved

Research J. Pharm. and Tech. 8(11): Nov., 2015; Page 1469-1476

DOI: 10.5958/0974-360X.2015.00263.2