RP- HPLC Method for Simultaneous Estimation of Ofloxacin and Ornidazole from Bulk and Tablets

 

RS Jadhav1, PN Kendre2, MH Kolhe1, S N Lateef2, SM Shelke3, RK Godge1*.

1Dept. of Pharmaceutics, Pravara Rural college of Pharmacy, Pravaranagar.

2 Sanjivani college of pharmaceutical Education and Research, Kopargaon.

3 Research Associate Orchid Pharmaceutical Ltd., Chennai.

 

ABSTRACT

A simple, selective, rapid, precise and economical reverse phase high-pressure liquid chromatographic method has been developed for the simultaneous estimation of Ofloxacin and Ornidazole from pharmaceutical formulation. The method was carried out on a Kromasil C18 (5 mm, 25 cm X 4.6 mm, i.d.) column, with a mobile phase consisting acetonitrile: phosphate buffer (pH 2.4) in the ratio 80: 20% V/V at a flow rate of 1.0 ml/min. Detection was carried out at 294 nm. The retention time of Ofloxacin and Ornidazole were 2.773 and 5.448min respectively. The developed method was validated in terms of accuracy, precision, linearity, Limit of detection, Limit of quantitation. The proposed method can be used for estimation of these drugs in combined dosage form for routine analysis.

 

KeywordsOfloxacin, Ornidazole, RP-HPLC.

 

 

INTRODUCTION

Ofloxacin is a synthetic broad spectrum antibacterial agent. Chemically ofloxacin1 a fluorinated carboxyquinolone, is a racemate, (±)- 9-fluro-2, 3-dihydro-3-methyl-10- (4-methyl- 1-piperazinyl)-7-oxo-7H-pyrido [1,2,3-de]-1,4-benzoxazine- 6-carboxylic acid. It is official in BP2, USP3, and EP4. The assay procedure mentioned in these pharmacopoeias uses nonaqueous titration for estimation of ofloxacin. Literature surveys reveals Spectrophotometric method5,6 atomic absorption spectrometry5, spectroflurometry5, HPLC7 and microbiological method8 for its determination.

 

Ornidazole1 is a 5-nitroimidazole derivative used as anti-infective agent. It is not official in any Pharmacopoeia. Literature survey reveals that ornidazole is estimated by voltametry9 and HPLC10 methods for its determination in dosage forms and biological fluids. Ofloxacin and ornidazole in combined tablet dosage form is available in the market, has gained increasing acceptance in diarrhooea, bacterial and protozoal infections. Spectrophotometric11, 12 method have been established for their simultaneous estimation in tablet dosage form. This paper presents a simple, accurate and reproducible HPLC method for simultaneous determination of ofloxacin and ornidazole in tablet dosage form.

 

EXPERIMENTAL

Reagents and Chemicals

Acetonitrile (HPLC grade) and was purchased from Merck specialties pvt. Ltd. (Worli, Mumbai, India) and Water (HPLC grade) was purchased from Loba Chemie (Mumbai, India). Potassium dihydrogen orthophosphate (AR- Grade) was purchased from Sisco research Laboratories Pvt. Ltd. (Mumbai, India). All other reagents used were of HPLC grade. Working standard of Ofloxacin and Ornidazole were provided by Concept Pharma Ltd. Aurangabad, India.

 

Pharmaceutical formulation:

Commercial tablets, each containing Ofloxacin (200mg) and Ornidazole (250mg)  (Oflab – Oz); were procured from the local market.


Method Development

Different mobile phases containing methanol, water, Acetonitrile, and different buffers in different proportion were tried and finally of acetonitrile :phosphate buffer (pH 2.4)in the ratio 80: 20% V/V was selected as moile phase which gave good resolution and acceptable peak parameters for both Ofloxacin and Ornidazole.

 

System Suitability Studies

The resolution, number of theoretical plates and peak asymmetry were calculated for the standard solutions and is as shown in Table 1. The values obtained demonstrated the suitability of the system for the analysis of these drugs in combinations. The typical chromatogram of standard solution is as shown in Fig.1.

 

Apparatus and chromatographic Conditions

Chromatographic separation was performed on a Shimadzu (LC-2010 AHT) and  20ml sample injection loop and U.V. visible absorbance detector. The output signal was monitored and integrated using the Shimadzel CLASS – VP software was used for the separation; mobile phase of a mixture of Acetonitrile and phosphate buffer was delivered at a flow rate of 1.0 ml/min with detection at 294nm. The mobile phase was filtered through a 0.2 m membrane filter and degassed. The injection volume was 20 ml; analysis was performed at ambient temperature.

Table 1: System Suitability Studies

Parameters

Method

Stationary phase (column)

C18 (5um, 25cm X 4.6mm,i.d.)

Mobile phase

Phosphate buffer         (pH= 2.4) : ACN (80:20)

Flow rate (ml / min )

1.0

column temperature (0C)

Ambient

Volume of injection (ml)

20

Detection wavelength (nm)

294

Table 2: Recovery Studies of Ofloxacin and Ornidazole:

Level of

% Recovery

% Mean Recovery*

% R.S.D.

OFLOX

ORNI

OFLOX

ORNI

80

99.87

98.2

0.06993

0.3388

100

98.37

99.41

0.04553

0.4066

120

99.82

98.23

0.0766

0.28283

 

Preparation of Standard Solutions

20 mg of ofloxacillin and 25 mg of ornidazole working standard Weighed into 50 ml of volumetric flask and dilute with mobile phase to 50 ml. Pipette out 5 ml of resulting solution in 50 ml volumetric flask and dilute to 50 ml with mobile phase.

 

Calibration Curve

Linearity of the system was investigated by serially diluting the stock solutions to give concentrations in the range of 20 mg/ml to 100 mg/ml for Ofloxacin and 25 mg/ml to 125 mg/ml for Ornidazole. An aliquot (20 ml) was injected using mixture of Acetonitrile:  phosphate buffer (80:20) v/v, as mobile phase. Calibration curves were obtained by plotting the peak area vs. concentration. The calibration curves are as shown in Fig.2 and Fig.3 for Ofloxacin and Ornidazole respectively. The equations of the regression lines are

For Ofloxacin        y = 81719x – 105961 (R2 = 0.999)

For Ornidazole y =105021x -99999 (R2 = 0.999)

 

Assay

Preparation of Sample Solutions:

Twenty Tablets, each containing 200 mg of Ofloxacin and 250mg Ornidazole were weighed and finely powdered. A quantity of powder equivalent to 50mg of Ofloxacin was weighed and transferred to 50 ml volumetric flask. To this, acetonitrile was added and sonicated for 10 min; the volume was made up to 50 ml with acetonitrile to get solution of 1000 mg/ml. The solution was filtered using whatmann filter paper. From the filtrate appropriate dilutions were made to obtain concentration in the range of 20 to 100mg/ml for Ofloxacin and 25 to 125 mg/ml Ornidazole respectively.

 

With the optimized chromatographic conditions, a steady baseline was recorded, the mixed standard solution was injected and the chromatogram was recorded. The retention time of Ofloxacin and Ornidazole were 2.773 and 5.448min respectively. This procedure was repeated for the sample solution obtained from the formulation. The proposed method was found to be specific and no interference from common tablet excipents like lactose, starch etc was observed. The assay was calculated from the equation of regression line for each drug. The percentage of individual drugs found in formulations was calculated and presented in table 2. The results of analysis shows that the amounts of drugs were in good agreement with the label claim of the formulations.

 

Method Validation

As per the ICH guidelines, the method validation parameters checked were linearity, accuracy, precision, limit of detection, limit of quantitation and robustness.

 

Linearity and Range

The linearity of the method was determined for the formulation at five concentration levels ranging from 20 to 100 mg/ml for Ofloxacin and 25 to 125 mg/m for Ornidazole. The equation for regression line for Ofloxacin was y =81719x – 105961 (R2 = 0.999) and

For Ornidazole y =105021x -99999 (R2 = 0.999).

 

The results show that an excellent correlation exists between Peak area and concentration of drugs within the concentration range indicated above.

 

Fig. 1: Chromatogram of Ofloxacin (2.733 min), Ornidazole 5.403 min respectively.

 


Table 3: Intraday and Interday Precision Studies System precision)

Conc.

(mg/ml)

Ofloxacin

Conc.

(mg/ml)

Ornidazole

% RSD

% RSD

Intra- day

Inter- day

Intra- day

Inter- day

20

0.16

0.22

25

0.53

0.62

40

0.29

0.30

50

0.69

0.76

60

0.2

0.27

75

0.31

0.36

80

0.31

0.25

100

0.92

1.5

100

0.32

0.37

125

0.13

0.2

               RSD = Relative Standard Deviation (n = 3).

 

Table 4: Intraday and Interday Precision Studies (Method precision)

Conc.

(mg/ml)

Ofloxacin

Conc.

(mg/ml)

Ornidazole

% RSD

% RSD

Intra- day

Inter- day

Intra- day

Inter- day

20

0.36

0.52

25

0.45

0.63

40

0.42

0.48

50

0.61

0.76

60

0.56

0.43

75

0.35

0.39

80

0.36

0.21

100

1.2

1.33

100

0.21

0.34

125

0.9

0.37

               RSD = Relative Standard Deviation (n = 3).


 

Fig.2: Calibration curve for Ofloxacin

Fig.3: Calibration curve for Ornidazole.

 

Accuracy and Precision

The accuracy of the method was determined by recovery experiments. The recovery studies were carried out at three levels of 80, 100 and 120% and the percentage recovery was calculated and presented in Table 2. Recovery was within the range of 100 ± 2% which indicates accuracy of the method.

 

The precision of the method was demonstrated by inter day and intra day variation studies. In the intra day studies, 3 repeated injections of standard and sample

 

 

solutions were made in a day and percentage RSD were calculated. In the inter day variation studies, 3 repeated injections of standard and sample solutions were made on 3 consecutive days and percentage RSD were calculated and presented in Table 3 and 4. The data obtained, %RSD not more than 1.5%, indicates that the developed RP-HPLC method is precise.

Limit of Detection and Limit of Quantification

The Limit of Detection (LOD) is the smallest concentration of the analyte that gives the measurable response. LOD was calculated using the following formula 

 LOD = (3.3 x standard deviation)/ Slope of calibration curve

 

The LOD for Ofloxacin and Ornidazole were found to be 0.002 mg/ml and 0.091 mg/ml, respectively.

 

The Limit of Quantification (LOQ) is the smallest concentration of the analyte, which gives response that can be accurately quantified. LOQ was calculated using the following formula

LOQ = (10 x standard deviation) / Slope of calibration curve.

The LOQ was 0.0061 mg/ml and 0.2768 mg/ml for Ofloxacin and Ornidazole respectively.

 

Robustness

Robustness is checked by making slight deliberate change in the experimental procedures. In the present method a deliberate change of Wavelength, pH, and flow rate was made and the effects were noted. The method was found to be robust with respect to change in wavelength, pH, and flow rate.

RESULT AND DISCUSSION

The proposed method was found to be simple and linear in the concentration range of 20 to 100 mg/ml for Ofloxacin and 25 to 125mg/ml for Ornidazole respectively. The method was found to be accurate and precise as indicated by recovery studies and % RSD not more than 1.5. Moreover LOD and LOQ Ofloxacin were found to be 0.002 mg/ml and 0.0061 mg/ml, respectively and for Ornidazole were 0.091 mg/ml and 0.2768 mg/ml, respectively. Thus the method is specific and sensitive.

CONCLUSION:

The proposed RP-HPLC method for the simultaneous estimation of Ofloxacin and Ornidazole in combined dosage forms was found to be sensitive, accurate, precise, simple and rapid. Hence the present RP –HPLC method may be used for routine analysis of the raw materials and formulations.

 

ACKNOWLEDGEMENT:

The author wish to thanks to Concept Pharma Ltd. Aurangabad, India for providing Working standard of Ofloxacin and Ornidazole and also thankful to Dr. S. R. Pattan for providing guidance for carrying research.

 

REFERENCES:

1. Budavari S. Eds. In. The Merck Index. Merck and co., Inc; Whitehouse Station, NJ. 2001; 13th Ed: pp 1213 and 1229.

2. British pharmacopoeia. Licensing division HMSO, Norwich. 2003; pp357

3. United States Pharmacopoeia. United States Pharmacopoeial Convention, Inc. Rockville, 2004; pp 1335.

4. European Pharmacopoeia. EDQM, Council of Europe, Strasbourg, France. 2005; 5th Ed: pp 2131.

5. Hesham Salem. Spectroflurometric, atomic absorption spectrometric and spectrophotometric determination of some fluroquinolones. American Journal of  Applied Sciences.2005; 2: 719-729.

6. Mathur SC, Kumar Y, Murugesan N, Rathode YKS and Sethi PD. Spectrophotometric determination of ofloxacin in pharmaceutical formulation. Indian drugs. 1992; 29: 376-377.

7. Arjekar AP, Kapadia US, Raj SV and Kunjir SS. Quantitative determination of lomefloxacin, ofloxacin, pefloxacin and enrofloxacin in pharmaceutical dosages, bulk drug and processes monitoring of enrofloxacin by HPLC-RP. Indian Drugs.1996; 33: 261-266.

8. Silveria EvL and Schapoval, EES.Microbiological assay for determination of ofloxacin injection. J. Pharm. Biomed. Anal. 2002; 1-2; 91-96.

9. Oexkan SA, Senturk Z and Biryol. Determination of ornidazole in pharmaceutical dosage forms based on reduction at an activated glassy carbon electrode. Int. J. Pharm. 1997; 157: 137-144.

10. Heizmann P, Geschke and Zinapold K.  determination of ornidazole and its main metabolites in biological fluid. J. of Chrom. B. 1990; 534: 233-240.

11. Kasture VS, Bhagat AD, Puro N C, More PS and Bhandari NK. Spectrophotometric method for simultaneous estimation of ofloxacin and ornidazole in tablet dosage form. Indian Drugs. 2004; 41: 51-53.

12. Nagori BP, Shrivastava B, Sharma V and Rajput AS. Spectrophotometric method for simultaneous estimation of ofloxacin and ornidazole in tablet dosage form. Indian Drugs. 2006; 43: 51-53.

 

 

Received on 04.06.2009

Accepted on 22.07.2009   

© A &V Publication all right reserved

Research J.  Science and Tech.  1(1): July-Aug. 2009: 43-46