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Spectrophotometric method for determination of certain cephalosporins using 4-chloro-7-nitrobenzo2-oxa-1,3-diazole (NBD-Cl) Rageh et al.-Natural Science 2 (2010) 828-840. Official procedures in pharmaceutical preparations utilize high-performance liquid chromatography (HPLC) which is expensive.
Spectrophotometric method for determination of certain cephalosporins using 4-chloro-7-nitrobenzo2-oxa-1,3-diazole (NBD-Cl) Rageh et al.-Natural Science 2 (2010) 828-840. Official procedures in pharmaceutical preparations utilize high-performance liquid chromatography (HPLC) which is expensive.
Spectrophotometric method for determination of certain cephalosporins using 4-chloro-7-nitrobenzo2-oxa-1,3-diazole (NBD-Cl) Rageh et al.-Natural Science 2 (2010) 828-840. Official procedures in pharmaceutical preparations utilize high-performance liquid chromatography (HPLC) which is expensive.
certain cephalosporins using 4-chloro-7-nitrobenzo- 2-oxa-1,3-diazole (NBD-Cl) Rageh et al.-Natural Science 2 (2010) 828-840 Na-Benzylpenisilin Na-ampisilin Penisilin Na-Kloksasilin Cefalexin Cefradin Cefadroxil The official method of cephalosporin: HPLC using spectrophotometric detector (EP, USP). Sefalosporin C E P H A L O S P O R I N
cephalosporin penicillin P e r b a n d i n g a n
s t r u k t u r
CEFACLOR CEFADROXIL CEFALEXIN CEFOTAXIME CEFRADINE CEFIXIME The official procedures in pharmaceutical preparations utilize high-performance liquid chromatography (HPLC) [3]
which is expensive. Other reported procedures include spectrophotometric [4-9] , spectrofluorimetric [10-13] , chemiluminescence [14-16] , chromatographic [17-20] and electrochemical methods [21-24] and most of them are lengthy (lama) and/or tedious (jenuh).
--- 3- American Pharmaceutical Association. (2008) United States Pharmacopoeia 31 and NF 26. Washington, DC. 4- Abdel-Hamid, M.E. (1998). Il Farmaco, 53(2), 132-138. 10-Aly, F.A., Hefnawy, M.M. and Belal, F. (1996). Analytical Letters, 29(1), 117-130. 14-Li, Y. and Lu, J. (2006). Luminescence, 21(4), 251-255. 17-Shinde, V.M. and Shabadi, C.V. (1997). Indian Drugs, 34, 399-402. 21-zkan, S.A., Erk, N., Uslu, B., Yilmaz, N. and Biryol, I. (2000). J. Pharmaceutical and Biomedical Analysis, 23(2-3), 263-273. C E P H A L O S P O R I N
NBD-Cl The hydrolytic degradation of cephalosporins a preliminary step in the analytical procedure used for their determinations [25-32] . The literature reveals that many spectrophotometric methods based on hydrolysis of these drugs using alkaline degradation and subsequent reaction of the formed sulfide ions with chromogenic reagents [26,27] . NBD-Cl (4-chloro-7-nitrobenzo-2-oxa-1,3- diazole) has been reported as fluorogenic reagent for determination of amines [33] and for spectrophotometric determination of many compounds [34-41] .
--- 25-El-Obeid, H.A., Gad-Kariem, E.A., Al-Rashood, K.A., Al-Khames, H.A., El-Shafie, F.S. and Bawaseer, G.A.M. (1999) Analytical Letters, 32(14), 2809-2823. 26-Mohamed, F.A. (1998). In Proceedings of Assiut University 1st Pharmaceutical Science Conference, Faculty of Pharmacy, Assiut, 1998, 1-18. 33-Omai, K., Toyo'oka, T. and Miyano, H. (1984). The Analyst (London), 109(11), 1365-1372.. 34-Olgun, N., Erturk, S. and Atmaca, S. (2002). J. Pharmaceutical and Biomedical Analysis, 29(1-2), 1-5. C E P H A L O S P O R I N
Thiocompounds have been reported to form intensely colored products in an alkaline medium with NBD-Cl which could be used for their colorimetric determination. On the basis of the aforementioned reasons, it was decided to develop a quantitative method for the determination of the studied cephalosporins based on their alkaline hydrolysis and subsequent reaction of the resulting hydrolysates with NBD-Cl, which may be used for their analysis either in pure forms or in pharm. formulations. This method is selective for cephalosporins, since other - lactam antibiotics such as penicillins do not give sulfide ions under the degradation conditions employed. C E P H A L O S P O R I N
Stock solutions: 100 mg mL -1 of each cephalosporin in double distilled water (methanol was used for cefalexin, cefadroxil, cefaclor, cefradine, cepodoxime proxetil & cefixime). Working standard solutions: 0.5- 2.5 mg mL -1 >cefadroxil and cefalexin, 1-6 mg mL -1 >cefradine, 2-8 mg mL -1 >cefaclor, cefazolin, cefotaxime, ceftriaxone and cefpodoxime proxetil, 2-10 mg mL -1 >cefixime & 2-16 mg mL -1
>cefoperazone and ceftazidime S T A N D A R D
S O L U T I O N
P r e p a r a t i o n
must be freshly prepared Twenty tablets or the contents of 20 capsules were weighed, finely powdered and mixed thoroughly. An accurately weighed amount of the powder obtained from tablets or capsules equivalent to 250 mg of each drug was transferred into a 25-mL volumetric flask, dissolved in about 10 mL solvent, sonicated for 15 min, diluted to the mark with solvent, mixed well and filtered; the first portion of the filtrate was rejected. Further dilutions with the same solvent were made to obtain sample solution containing the specified concentration for each drug as mentioned under the preparation of standard solutions and then the general procedure was followed. T A B L E T S
a n d
C A P S U L E S
P r e p a r a t i o n
An accurately weighed amount of powder equivalent to 250 mg of each drug was transferred into a 25-mL volumetric flask, then the procedure was followed as under tablets and capsules beginning from (dissolved in about 10 mL double distilled water etc.) V I A L S
a n d
P O W D E R S
P r e p a r a t i o n
G E N E R A L
P R O C E D U R E S
Accurately measured one milliliter aliquot volume of the standard or sample solutions was transferred into 10-mL volumetric flask. weighing Five mL of 0.5 M NaOH were added and the flask was heated in a boiling water-bath for 30 min, cooled to room temperature and completed to volume with double distilled water. hydrolysis One milliliter of the resulting drug hydrolysate was pipetted into 10-mL volumetric flask, 1.0 mL of 3 10 -3 M NBD-Cl was added followed by 1 mL of concentrated HCl. working tube The resulting solution was mixed well and the flask was completed to volume with ethanol. The absorbance was measured at 390 nm against reagent blank treated similarly. measure Optimasi Metode The influence of NaOH concentration on producing the maximum absorption intensity was investigated using 0.1-1.0 M NaOH keeping other factors constant. Maximum absorption readings were obtained upon using 0.5 M NaOH; above this concentration and up to 1 M NaOH, the absorbance remains constant.
The effect of hydrolysis time on the absorption intensity was studied using different heating times in a boiling water bath (at 100C) starting from 10 min until 2 hours and the reaction was carried out as usual. The maximum absorption intensity was attained after 20 min and remained stable for at least 100 min. Thirty minutes hydrolysis time was used in all subsequent experiments. N a O H
c o n c e n t r a t i o n
&
H y d r o l y s i s
T i m e
The concentration of NBD-Cl, for the maximum color development was varied in the range of 0.75 10 -3 4 10 -3 M. It was found that 1 mL of 3 10 -3 M NBD-Cl was the most suitable concentration for determination of the studied drugs. Owing to the presence of labile chloride, a daily fresh solution is recommended. Different acids such as sulfuric, hydrochloric, perchloric, nitric and acetic acids were tested to determine the most suitable acid for the reaction. One mL of concentrated hydrochloric acid was selected in this study as it gave the highest absorbance readings taking cefalexin anhydrous (15 g mL -1 ). As a result of the most suitable concentration of hydrochloric acid investigations. E f f e c t
o f
N B D - C l
c o n c e n t r a t i o n
E f f e c t
o f
t y p e
a n d
c o n c e n t r a t i o n
o f
a c i d
The reaction between the investigated drugs hydrolysates and NBD-Cl was very rapid and the interaction colored product can survive before dilution unchanged for at least 1 hour. However, measurements were achieved instantaneously.
Stability time was obtained by following the absorbance readings of the developed reaction product for 24 hours at room temperature (25 5C). It was found that the produced color was stable for 24 hours for all studied drugs. R e a c t i o n
T i m e
&
S t a b i l i t y
o f
c o l o r e d
Different solvents were tested in order to select the most appropriate solvent for optimum color development. The results given in Table 3 show small shifts in the position of the maximum absorption peak. The absorption intensities were slightly influenced. Ethanol was used throughout this work because it gave the highest absorbance readings and the most reproducible results. E f f e c t
o f
d i l u t i n g
s o l v e n t
C A L I B R A T I O N
C U R V E S
M e t h o d
V a l i d a t i o n
S t u d y
LOD and LOQ the limits of detection and quantitation Accuracy by investigating the recovery of each of the studied drugs at three concentration levels Precision the small values of SD and % RSD point to high precision Selectivity the effect of the presence of common excipients was studied Robustness by evaluating the influence of small variation in the experimental parameters A C C U R A C Y
I N T R A -
A N D
I N T E R - D A Y
P R E C I S I O N
I N T R A -
A N D
I N T E R - D A Y
P R E C I S I O N
R O B U S T N E S S
S u g g e s t e d
R e a c t i o n
M e c h a n i s m
The visible spectrophotometric methods for cephalosporins are based on their interaction with different reagents, such as imidazole in the presence of ferrihydroxamate, mercury (II) (2), ninhydrine (3), N,N-dimethyl-D-phenylendiamhe and ferric ions (4), ammonium vanadate (5), phenol with sodium nitroprusside and hypochlorite (6), 4-- dimethylaminocinnam aldehyde (7), 3-bromo-4,4- dimethyl-2-oxazolidinon(8), O-hydroxyhydroquinone phtalein (9), paramolybdate anion (10), sodium nitrite (11), chloranilic acid (12), molybdophosporic acid (13), copper (II) acetate (14), oxidized heamatoxylin (15), 2-nitro-phenyl-hydrazine hydrochloride (16), mercurochrome (17) O t h e r
V i s i b l e
s p e c t r o p h o t o m e t r i c
M e t h o d s
2. Sengun F.I., Ulas K. Talanta. 1986; 33:363 3. MarriniD., DiCoccoM.E. Rass.Chim. 1980;32:231 4. Abdall M.A., Fogg A.G., Burges C. Analyst(London) 1982;107:213 5. Abdel-Khalek M.M., Maihrais M.S. Talanta 1983;30:792 6. Foog A.G., Abdulla A.M. J.Pharm.Biomed.Anal.1985;3:315 7. Rao G.R., Raghweer S. J.Inst.Chem.(India) 1983;55:61 8. Kaminski J.J., Bdoor N. Int.J.Pharm. 1975; 3:151 9. Moris I., Fujita Y., Saraguchi K. Chem.Pharm.Bull. 1982;30:2599 10. Issopoulos P.B. J.Pharm.Biomed.Anal. 1988;6:97 11. Uri J.V., Jain T.C. J.Antibiot. 1986;39:669 12. Sastry C.S.P., Divauor T.E. Chem.Anal.(Warsaw)l987;32:301 13. Issopoulos P.B. Analyst(London) 1988;113:1083 14. Issopoulos P.B. J. Pharm.Biomed.Anal. 1988;6:321 15. Sastry C.S.P., Salyarayana P., Rao A.R., SinghN.R.P. Microchim.Acta. 1989; 1:17 16. Koraky M.A., Abdel-Hay M.H. Bedair M.M. Talanta 1989;36:1253 17. Galal S.M. Acta Pharm.Jugosl.1991;41:25 R E F E R E N C E S
Sepenggal tulisannya: tipe tanpa identitas :
Bu, ibu ada di mana sekarang? Hari ini ke kampus gak bu? Ibu ada di mana???? Ditunggu di kelas xxx sekarang Ibu posisi dimana? saya sudah di kampus dari tadi bu tenia, untuk materi kuliah xxx ada dimana ? A T T I T U D E
B U I L D I N G
A Spectrophotometric Method for The Determination of Penicillin Herriott-J. Biol. Chem. 1946, 164:725-736 Cefalexin Cefradin Cefadroxilxib The official method of aceclofenac, diclofenac, ketorolac was potentiometric titration method with sodium hydroxide, perchloric acid, tetrabutylammonium hydroxide, respectively (Pharmacopoeia, 2004) Sefalosporin Penisilin Na-Benzylpenisilin Na-ampisilin Na-Kloksasilin P E N I C I L L I N
cephalosporin penicillin P e r b a n d i n g a n
s t r u k t u r
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
Spectrophotometric Method for Assay of Penicillins Hiremath & Mayanna-Mikrochim. Acta [Wien] 1986 I, 265--270 PRINCIPLE Ninhydrin in 0.2 M citrate buffer (pH 5) containing SnCl 2 is proposed as a new reagent for spectrophotometric determination of penicillins and analysis of their pharmaceutical formulations. The method is based on acid hydrolysis of penicillins with 5 M HCl and subsequent treatment with ninhydrin. The resulting violet colour exhibits maximum absorption at 570 nm. P E N I C I L L I N
P E N I C I L L I N
On acid hydrolysis (pH <3) penicillin gives penaldic acid and penicillamine [21]. It is known that compounds containing a free amine group react with ninhydrin (I) to give the violet diketohydrindylidene diketohydrindamine (II) [15] only in presence of a reducing agent capable of producing hydrindantin [22]. Others: titrimetric methods have been reported in the literature for the assay of penicillins, based on use of iodine [1], N-bromosuccinimide [2] and chloramine-T [3] as titrants. Conductometric [4], polarographic [5] and HPLC [6] procedures are also employed for the assay of penicillins.
The spectrophotometric methods used are based on determination of the hydroxamic acid formed by reaction with hydroxylamine [8], or the penicillenic acid mercury(II) mercaptides formed by reaction with imidazole in the presence of mercury(II) chloride [9], or involve ammonium vanadate [10], chromium(VI) with metol [11] and Azure B [12]. P E N I C I L L I N
Ninhydrin, on reduction with SnCl 2 [13] at pH 5 or with ascorbic acid [14] gives a colour reaction with amino- acids. The colour is stabilized by using pyridine-phenol [15], cyanide [16] or cyanide/acetate buffer [17]. Ninhydrin has also been used for qualitative detection of penicillin [18] and for spectrophotometric assay of chloramphenicol [19] and D-cycloserine [20].
In several pharmaceutical formulations, penicillin is associated with flavouring agents, diluents, excipients such as sucrose and glucose, colours such as tartrazine and Sunset Yellow FCF, and is buffered with calcium carbonate and sodium phosphate, etc. In preliminary experiments, these compounds were tested with the ninhydrin reagent and found not to interfere in the assay of penicillins. P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
P E N I C I L L I N
Method of quantitative estimation of aceclofenac from tablet formulation using FolinCiocalteu reagent. Aceclofenac forms a blue coloured chromogen with the reagent, which shows absorbance maxima at 642.6 nm and linearity in the concentration range of 80160 gmL -1
of drug (Singhvi and Goyal, 2007).
The extracted complex with orange G shows absorbance maxima at 481 nm and linearity in the concentration range of 1080 g mL -1 . The extracted complex with naphthol green shows absorbance maxima at 633.6 nm and linearity in the concentration range of 0.21.0 g mL -1 (Goyal and Singhvi, 2006). A C E C L O F E N A C