The Influence of Khat on the In-vitro and In-vivo availability of Tetracycline-HCl

 

Farah Hamad Farah1*, Omer Ali Attef2 and Abdul-Azim Ahmed Ali3

1Department of Pharmaceutics, College of Pharmacy and Health Sciences, Ajman University of Science and Technology, UAE.

2Department of Pharmaceutical Chemistry, College of Pharmacy and Health Sciences, Ajman University of Science and Technology, UAE

3Department of Pharmaceutics, College of Pharmacy and Health Sciences, Ajman University of Science and Technology, UAE,

*Corresponding Author E-mail: f.hamad@ajman.ac.ae., attef@hotmail.com, ajac.azim@ajman.ac.ae.

 

 

ABSTRACT:

The influence of khat on both in-vitro and in-vivo availability of tetracycline-HCl has been evaluated. The in-vitro availability data have reflected a statistically significant interaction between khat extract and tetracycline-HCl in two buffer solutions simulating intestinal and gastric media (phosphate buffer-pH 7 and 0.1 HCl-pH 1.2 respectively). In the in-vivo availability studies, ten adult healthy Yemeni volunteers participated. The obtained in-vivo availability data indicated a statistically significant reduction in most pharmacokinetics parameters. A statistically significant % reduction in the maximum plasma tetracycline-HCl concentration (Cmax) and absorption rate constant (Ka) as well as a significant enhancement of time to reach the peak plasma concentration (Tmax), were observed as a result of taking tetracycline-HCl just before khat chewing (trial B) and more pronounce during khat chewing (trial D) compared to the control (trial C). In addition a statistically significant % reduction in area under curve (AUC0→∞)  has been observed reflecting a reduction in the extent of in-vivo tetracycline-HCl availability as a result of khat chewing. Statistically significant % reductions in the biologic half-life (t½)  and elimination rate constant (Kel) were also observed.The reduction in tetracycline-HCl concentration when mixed with khat extract, as shown by in-vitro data, may reflect a possible formation of tetracycline-HCl complexes with one or more of khat constituents. The reduction in the rate and extent of in-vivo tetracycline-HCl availability as a result of khat chewing, may be due to the possible formation of non-absorbable tetracycline-HCl complexes with one or more of khat constituents or possible delaying of gastric emptying induced by khat that may prolong the resident time of tetracycline-HCl in the stomach leading to its possible degradation into the less antimicrobial active form epitetracycline.

 

KEYWORDS: availability, pharmacokinetics parameters, tetracycline-HCl, khat.

 


INTRODUCTION:

There is no doubt that the habit of khat chewing  remains a major problem in Yemeni society and the number of khat chewers seems to be increasing[1,2]. Several reports have been published worldwide revealing the medical effect of khat (Catha edulisForsk.) [1,3,4] , but little is known about the possible interactions between khat constituents and drugs.

 

The most important khat leaves constituents include more than six alkaloids that are the main determinants of the khat CNS effects, tannins, flavonoids and polyvalent cations, such as calcium, magnesium, iron, cadmium, lead, copper, and zinc [3,4,5,6].On the other hand antibiotic use in Yemen is high and the statistics of the Ministry of Public Health and Population showed that the antibiotics group was the third group which was imported through the years 2002 and 2003 with percentages of 13.7% and 13.0% respectively from the total number of imported drugs [7,8 ]. Also a study performed in different general public health facilities in Yemen showed that 61%  of the prescribed drugs were antibiotics [9]. These findings emphasize the need for conducting  research on the influence of khat chewing on the in-vivo availability of antibiotics. A previous study on the effect of khat chewing on the bioavailability of two β-lactam antibiotics, namely ampicillin and amoxicillin, revealed that khat chewing significantly reduces most pharmacokinetics parameters [10]. It has been concluded that tannins represent the most likely component, which could be responsible for the observed effects of khat on β-lactam antibiotics absorption [10]. The present study was carried out to investigate the possible effect of khat on the in-vitro and in-vivo availability of tetracycline-HCl.

 

MATERIALS AND METHODS:

MATERIALS:

Tetracycline-HCl capsules (Tetracaps® 500mg; Lab. Wolves N. V., Antwerb, Belgium; Batch 98E21; Exp. date 03/2015) were kindly donated by the local agent. Tetracycline-HCl standard reference was kindly supplied by the national quality control laboratory of the Ministry of Public Health, Sana’a, Republic of Yemen, Jenway 6405 UV/VIS Spectrophotometer, Jenway Ltd., England. Khat (Catha edulisForsk.) was purchased from the local market.  The type and quantities of khat taken by all volunteers throughout the trials were kept the same. The khat used was one of the commonest type in Yemen, locally known as “Sauty”.

 

Methods:

(i) In-vitro availability studies:

Two buffer solutions (phosphate buffer pH 7 and 0.1 HClpH 1.2) were prepared to simulate the gastrointestinal physiological fluids. 10 g ground fresh khat leaves were separately extracted with 200ml of each buffer solution and shaken for 1 hr then filtered. Finally, activated charcoal was added to decolorize the filtrate and then filtered again. Serial concentrations of tetracycline- HCl standard reference were prepared in both buffer solutions in a concentration range of 0.01-2.0mg/ml. Using a spectrophotometer (Jenway 6405 UV/VIS Spectrophotometer, Jenway Ltd., England), the absorption of tetracycline-HCl solutions was measured at the wavelengths (λ 361nm; and λ 380nm) with and without khat extract.  Calibration curves were constructed in both buffer media and at the same wavelengths.

 

 

(ii) In-vivo availability studies:

Ten adult healthy male Yemeni volunteers participated in the trials (average age: 24 years; average body weight: 57 kg). The trials were conducted using a cross-over design with a wash-out period of 7 days. The volunteers did not take any drugs a week before and during the trials. They only drink 750 ml of water during khat chewing session, which lasted for 4 hours. A 500mg single dose of tetracycline-HCl capsule was administered orally after an overnight fast on an empty stomach. Tetracycline-HCl was taken on three different occasions as follows:

 

Trial B: drug was taken just before khat chewing.

Trial C: drug was taken alone without khat as control.

Trial D: drug was taken halfway during the 4-hours khat chewing session.

5ml blood samples were collected at: 0.0, 0.5, 1.0, 2.0, 2.5, 3.0, 4.0, 6.0, 8.0 and 24.0 hours post tetracycline-HCl administration. The blood samples were centrifuged immediately after collection to separate plasma. Plasma samples were kept at 40C awaiting analysis. The official microbiological assay according to USP XXIII [11] has been used for sample analysis. Calibration curve for tetracycline-HCl standard reference was constructed in a concentration range of 0.3-5 µg/ml. The mean calibration factor was 1.667. Pharmacokinetics parameters were used to describe the rate and extent of the antibiotic bioavailability.

 

Statistical analysis

Standard curves were subjected to regression analysis. The percentage reductions ofTetracycline-HCl inboth in-vitro and in vivo availability studies were analyzed using the Studentst-Test for Paired Data [12].

 

RESULTS AND DISCUSSION:

(A) Results obtained from in-vitro availability studies:

Data obtained from in-vitro availability studies are shown in tables 1-4. Statistical analysis of the in-vitro tetracycline-HCl khat extract mixture in phosphate buffer (pH7.0) at λ 361nm (Table 1) and at λ380nm(Table 2), and in 0.1N HCl (pH1.2) at λ361nm (Table 3) and at λ380nm (Table 4),all exhibit significant% reductions in tetracycline-HCl concentrations compared with the drug alone.

 

 


Table 1: The effect of khat extract on the in-vitro availability of tetracycline-HCl (TC) in phosphate buffer (pH 7.0) at λ361nm.

Sample Conc.

[mg/ml]

TC without  Khat extract

[mg/ml]

TC with Khat extract

[mg/ml]

TC Conc. difference

[mg/ml]

TC Conc. difference  

[%]

0.020

0.0281

0.0161

0.0120

42.64

0.032

0.0336

0.0241

0.0095

28.31

0.050

0.0510

0.0313

0.0197

38.71

0.063

0.0561

0.0530

0.0031

5.51

0.125

0.0645

0.0593

0.0052

8.04

0.250

0.0649

0.0593

0.0055

8.53

0.500

0.0651

0.0595

0.0056

8.63

1.000

0.0656

0.0598

0.0057

8.74

 

 

 

mean: 0.0083

mean; 18.46%

Variance=0.000045     t=3.057   SE=0.002     p<0.02

 

Table 2: The effect of khat extract on the in-vitro availability of tetracycline-HCl (TC) in phosphate buffer (pH=7.0) at λ380nm.

Sample Conc.

[mg/ml]

TC without Khat extract

[mg/ml]

TC with  Khat Extract

[mg/ml]

TC Conc. difference

[mg/ml]

TC Conc. difference

[%]

0.020

0.0256

0.0155

0.0100

39.20

0.032

0.0304

0.0242

0.0062

20.41

0.050

0.0493

0.0313

0.0180

36.44

0.063

0.0616

0.0600

0.0016

2.60

0.125

0.0914

0.0878

0.0036

3.89

0.250

0.0963

0.0941

0.0022

2.33

0.500

0.0966

0.0945

0.0021

2.15

1.000

0.0973

0.0951

0.0022

2.22

 

 

 

mean: 0.0057

mean:  13.66%

Variance=0.000046     t=1.918   SE=0.002    p<0.05

Table 3: The effect of khat extract on the in-vitro availability of tetracycline-HCl (TC) in 0.1N HCl (pH=1.2) at λ361nm

Sample Conc.

[mg/ml]

TC without Khat Extract

[mg/ml]

TC with Khat Extract

[mg/ml]

TC Conc. difference

[mg/ml]

TC Conc. difference

[%]

0.020

0.0254

0.0205

0.0049

19.40

0.032

0.0412

0.0243

0.0169

41.10

0.050

0.0467

0.0365

0.0102

21.82

0.063

0.0569

0.0511

0.0058

10.20

0.125

0.0602

0.0555

0.0047

7.81

0.250

0.0603

0.0557

0.0046

7.66

0.500

0.0605

0.0557

0.0048

7.95

1.000

0.0607

0.0558

0.0049

8.08

2.000

0.0612

0.0559

0.0053

8.62

 

 

 

mean: 0.0069

mean: 14.74%

Variance=0.000020      t=4.403   SE=0.001         p<0.002

 

Table 4: The effect of khat extract on the in-vitro availability of tetracycline-HCl (TC) in 0.1N HCl (pH=1.2) at λ380nm.

Sample Conc.

[mg/ml]

TC  without  Khat  Extract

[mg/ml]

TC with  Khat Extract [mg/ml]

TC Conc. difference

[mg/ml]

TC Conc. difference

[%]

0.020

0.0215

0.0181

0.0034

15.99

0.032

0.0371

0.0211

0.0160

43.04

0.050

0.0430

0.0332

0.0097

22.68

0.063

0.0650

0.0563

0.0087

13.41

0.125

0.0877

0.0845

0.0032

3.68

0.250

0.0967

0.0934

0.0033

3.46

0.500

0.0972

0.0937

0.0035

3.58

1.000

0.0976

0.0938

0.0038

3.92

2.000

0.0982

0.0921

0.0061

6.21

 

 

 

mean:  0.0060

mean:12.89%

Variance=0.000021     t=3.954   SE=0.001     p<0.01

 


 

The mean % reduction of tetracycline-HCl concentration in phosphate buffer (pH7.0) at λ361nm  and at λ 380nm were

18.64% (p<0.02) and 13.66% (p<0.05) respectively (Tables 1 and 2).  The mean % reduction of tetracycline-HCl concentration in 0.1N HCl (pH1.2) at λ 361nm and at λ 380nm were 14.74% (p<0.002)and 12.89% (p<0.01) respectively (Tables 3 and4). There were no clear differences in the mean %reduction of tetracycline-HCl concentration in both media. The in-vitro availability data reflects a significant tetracycline HCl-khat extract interaction in both media. Such tetracycline-HCl-khat extract interaction may be attributed to one or more of the following assumptions: a-As khat contains among its other constituents polyvalent cations (calcium, magnesium, iron, cadmium, lead, copper, and zinc) [3,4,5,6], then there is a possibility of tetracycline chelation with these polyvalent cations[13,14,15]. b-Possible complexation of tetracycline with tannic acid available as a major constituent in khat[3,4,5] through hydrogen bonding. c-Possible complexation of tetracycline with cathinone, cathine, or pseudoephedrine available in khat[1,3,4,5]  via hydrogen bonding. d-Possible binding of tetracycline with proteins available in small concentrations in khat[5]. Another important observation is that high tetracycline-HCl concentrations in the range of (0.06-1.0mg/ml) in both media and at both λ 361nm and λ380nm, showed almost similar %reduction of tetracycline-HCl concentration when mixed khat extract (Tables 1-4), indicating that some sort of saturation process is taking place. Such saturation could be explained on the basis that an adsorption process might also be occurring beside complexation. The major constituent in khat that is capable of being an adsorption and is available in high concentration of 7-14% is tannic acid [1,3,4,5]. This may indicate that tetracycline-HCl-khat extract interaction is not only due to complexation but also adsorption may be involved. Further in-vitro tetracycline tannic acid interaction experiments are needed to validate such assumptions.

 

(B) Results obtained from in-vivo availability studies

The effect of khat chewing on the bioavailability of a 500mg single oral dose of tetracycline-HCl capsule was also studied in ten healthy, adult Yemeni male volunteers with similar age and weight group to correlate it with the in-vitro availability studies data. Reduced and % reduced tetracycline-HCl concentrations in plasma when the drug is taken just before  Khat chewing session trial (B) and during Khat chewing session trial (D) compared with the control trial (C) as well as statistical  analysis data of the differences between trial (B) and (D) compared with the control trial (C) are shown in Table 5. Pharmacokinetics parameters calculated from plasma tetracycline-HCl concentration-time curve are shown in table 6.


 

Table 5: Reduced and % reduced tetracycline-HCl (TC) concentration in plasma when the drug is taken before (Trial B) and during  Khat chewing session (Trial D) against the control (Trial C)

Time [hr]

Trial C

[µg/ml]

Trial B

[µg/ml]

Trial D

[µg/ml]

Reduced TC conc. between: Trial C and Trial B (Trial C-Trial B)  [µg/ml]

Reduced [%] (1) TC conc. between: Trial C and Trial B (Trial C-Trial B)

Reduced TC conc. between: Trial C and Trial D (Trial C-Trial D) [µg/ml]

Reduced [%] (2) TC conc. between: Trial C and Trial D (Trial C-Trial D)

0.0

0.000

0.000

0.000

0.000

0.00

0.000

0.00

0.5

1.984

1.389

0.574

0.595

29.97

1.410

71.06

1.0

2.842

2.284

1.967

0.558

19.65

0.875

30.79

2.0

2.927

2.575

2.184

0.352

12.03

0.743

25.38

2.5

3.121

2.667

2.434

0.454

14.54

0.687

22.02

3.0

3.092

2.726

2.484

0.367

11.86

0.608

19.68

4.0

3.084

2.559

2.417

0.525

17.03

0.667

21.62

6.0

3.017

2.492

2.317

0.525

17.40

0.700

23.20

8.0

2.842

2.317

2.067

0.525

18.48

0.775

27.27

24.0

1.875

1.395

0.574

0.491

26.17

1.301

69.38

 

 

 

 

mean:0.439

mean:16.71%

mean:0.777

mean:31.04

(1)Variance=0.007 t=6.434  SE=2.60%  p<0.001 

(2) Variance=0.049  t=4.418  SE=7.03%  p<0.002     m

 

Table 6: Observed changes in pharmacokinetics (PK) parameters after a 500mg single oral dose of tetracycline-HCl taken before (Trial B) and during Khat chewing session (Trial D) against the control (Trial C)

Parameters

Measured

PK parameters in Trial C

Measured

PK parameters

 in Trial B

Measured

PK parameters

 in Trial D

Differences

between: Trial C and Trial B

[%] differences

between: Trial C and Trial B

Differences

Between:

Trial C and Trial D

[%] differences

Between:

Trial C and Trial D

1Cmax [µg/ml]

3.651

3.188

2.906

0.463

-12.68

0.745

-20.4

2Tmax [hr]

2.5

3.0

3.0

-0.5

+20

-0.5

+20

3Ka [hr-1]

1.01

0,847

0.762

0.164

-16.2

0.248

-24.6

4AUC0→24[µg hr/ml]

70.64

53.37

44.38

17..27

-24.5

26.26

-37.2

5AUC0→∞

[µg hr/ml]

121.4

78.47

52.78

42.93

-35.4

86.62

-56.7

6Kel [hr-1]

0.0646

0.0432

0.08

0.02

-46.3

0.037

-85.2

7t½ [hr]

16.04

10.73

8.66

5.31

-33.1

7.38

-46.0

 

 


1Cmax= maximum plasma tetracycline-HCl concentration. 2Tmax= time to reach the peak plasma concentration. 3Ka = absorption rate constant. 4AUC0→24= area under plasma drug versus time curve from t=0 to t=24 hrs. 5AUC0→∞ = area under plasma drug versus time curve from t=0 to t=∞.  6Kel= elimination rate constant. 7t½= the biologic half-life. Consistent with in-vitro data, in-vivo findings of pharmacokinetics parameters indicated statistically significant % reduction in Cmax of 12.68% (SD=0.3274; t=14.77; p<0.05) when the drug is taken just before Khat chewing and a % reduction in Cmax of 20.40%  (SD=0.7455; t=8.795; p<0.05)when the drug is taken during Khat chewing compared with the control (Table 6).

 

There was also statistically significant enhancement of Tmax of 20% in both cases of taking  the drug just before and during Khat chewing compared with the control(Table 6).Statistically significant % reduction in Ka of 16.2% and 24.6% were also observed for taking the drug just before and during Khat chewing respectively compared with the control (Table 6).

 

The reduction in Cmax and Ka and the enhancement of Tmax, all indicate that khat Chewing significantly reduces the rate of absorption of  tetracycline-HCl. With regard to AUC0→∞ that describes the extent of absorption of tetracycline-HCl, statistically significant % reduction inAUC0→∞ of 35.4% and 56.7% were observed when the drug is taken just before and during Khat chewing respectively compared with the control (Table 6).This reflects a clear reduction in the extent of absorption of  tetracycline-HCl. The reduction in the rate and extent of tetracycline-HCl absorption as a result of khat chewing, may be due to one of the following assumptions: a- Possible interaction of tetracycline-HCl with certain khat constituents, such as polyvalent cations (calcium, magnesium, iron, cadmium, lead, copper, and zinc), tannic acid, cathinone, cathine and pseudoephedrine that may lead to the formation of non-absorbable complexes. b- Possible delaying in gastric emptying induced by khat chewing [16] may reduce the rate of tetracycline-HCl absorption. In addition  delaying gastric emptying prolongs the resident time of the drug in the acidic pH of the stomach that may perhaps lead to its possible degradation into the less antimicrobial active for mepitetracycline[17]. It worth mentioning that in this in vivo study, microbiological assay procedure has been used to determine tetracycline-HCl serum concentration. The biologic half-life (t½)  and elimination rate constant (Kel) both exhibit statistically significant % reduction of 33.1% and 46.3% respectively when taking tetracycline-HCl just before khat chewing and a % reduction of 46.0% and 85.2% respectively when the drug is taken  during Khat chewing compared with the control (Table VI). t½  and Kel are generally influenced by dose size, age, protein binding, variations in urinary excretion and metabolic rates and co-administration of drug that  influence urinary excretion and metabolic rates as well as liver and kidney diseases [18].  The reduction in t½ and Kel of tetracycline-HCl as a result of khat chewing may be attributed to one or combination of the following assumptions: a-Possible enhancement of urinary excretion of tetracycline-HCl through changing urinary pH by khat constituents into somewhat acidic pH that increases the concentration of the ionizable form of the drug, hence reducing tubular reabsorption and lowering the concentration of the drug in the blood as tetracycline-HCl is passively excreted.  b-Certain Khat constituents may induce certain microsomal enzymes that may degrade  tetracycline-HCl. These assumptions needed to be further experimentally validated. Other factors that influence t½  and Kel , such as age and dose size are excluded in this study, since all volunteers were of the same age group and the same dose of the drug is used. Concerning protein binding as one of the factor affecting t½ , protein binding usually leads to the displacement of a drug by another drug or substance resulting in the prolongation not reduction in t½[18]. It should be mentioned that the calculated values of pharmacokinetics parameters of  tetracycline-HCl alone (control) i.e. Cmax, Tmax, and AUC 0→24were comparable with literature values, while t½ , Kel and AUC 0→∞ values were slightly different from literature values [19].

 

CONCLUSION:

Tetracycline-HCl-khat interaction has been evaluated both in-vitro and in-vivo. In-vitro studies have indicated a statistically significant interaction between tetracycline-HCl and khat in both phosphate buffer(pH7.0) and 0.1N HCl (pH1.2). Such interaction may be attributed to possible complexation between tetracycline-HCl and certain khat constituents, such as polyvalent cations, or possible complexation and/or adsorption of tetracycline-HCl with and/or onto tannic acid. Other possible complication may also occur with other khat constituents such as cathinone, cathine and pseudoephedrine. In-vivo data on the other hand was consistent with the in-vitro findings. In-vivo bioavailability data indicated a statistically significant% reduction in Cmax, Ka as well as a significant enhancement of Tmax, were observed a result of taking tetracycline-HCl just before khat chewing and more pronounce during khat chewing compared to the control. All the above three pharmacokinetics parameters reflect reduction in the rate of tetracycline-HCl absorption. In addition a statistically significant % reduction in AUC 0→∞has been observed, reflecting reduction in the extent of tetracycline-HCl absorption. Such reduction in the rate and extent of tetracycline-HCl absorption as a result of chewing khat may be attributed to the formation of non-absorbable complexes of tetracycline HCl with one or more of khat constituents as explained previously or possible delaying in gastric emptying induced by khat that may prolong the resident time of the drug in the stomach leading to its possible degradation into the less antimicrobial active for mepitetracycline. Statistically significant % reductions in t½  and Kel were also observed reflecting a possible enhancement of renal excretion rate of tetracycline-HCl, perhaps by possibly urinary pH modification by certain khat constituents ora possible enhancement of tetracycline-HCl metabolism via enzyme induction by one or more khat constituents. These assumption needed to be experimentally validated.

 

ACKNOWLEDGMENT:

The authors are grateful to the national quality control laboratory, Ministry of Public Health, Sanaa, Yemen, for donating the tetracycline-HCl standard reference. Special thanks are due to the ten volunteers for their effective contribution and patient during in-vivo studies.

 

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Received on 21.11.2014       Modified on 15.12.2014

Accepted on 05.01.2015     ©A&V Publications All right reserved

Res. J. Pharm. Dosage Form. & Tech. 7(1): Jan.-Mar. 2015; Page 01-06

DOI: 10.5958/0975-4377.2015.00001.4