Applied Chemistry,

Vol. 12, t\o. I, May ?f1뻐， 97-100

Potassium Permanganate-Sodium Sulfite System을 이용한

Sparfloxacin의 흐름주입 화학발광법적 정량

Seikh Mafiz Alam · 이상학f

경북대학교 화학과

Flow-Injection Chemiluminescence Determination ofSparfloxacin Using Potassium Perrnanganate-Sodium Sulfite

System

Seikh Mafiz Alam . Sang Hak Lee tDepartment of Chemistry , Kyungpook National University ‘ Taegu. 702 - 70 1. Korea

Abstract

A rapid and sensitive chemiluminescence method has been described for thedetermination of sparfloxacin by combining the flow injection technique which is based on

its sensitizing effect on the weak chemiluminescence reaction between sodium sulfite and

acidic potassium permanganate. Under the experimental optimum conditions sparfloxacincan be determined over the concentration range of 1.6 xI 0 R to 2.9 x 10 Ii mo l/L with a

correlation coefficient of 0.9988 and a detection limit of 0.7x 10 8 mal/L (3 σ). The

relative standard deviatian (R.S.D.) far 11 repetitive determinations of 1.0 x 10 Ii mal!Lsparflaxacin is 0.9%.

Keywords: Chemiluminescence. sparfloxacin. KMn01 , NalS03

1. INTRODUCTIONSparfloxacin (5-a띠no - 1-cyclopropyl- 7 (α:，，3， 5 dimethyl-l-piperaziny t) -6.8-difluoro

1.4 -dihydro-4-oxo-3-quinoline carboxylic acid) , a broad spectrum antibacterial

fl l.loroquinolone active against some microorganisms induding Gram-positive and

Gram -negative bacteria [J ‘ 2J , is a new member to the class of fluroquinolones

which is used in the treatment of cuttaneous allergy. lung infection and urinary tract

infection [31. The activity against anaerobes and ilψ cobactel때 has been reported in

the literature [,1].

Several techniques have been reported in the literature for the determination of

sparfloxacin such as HPLC [5] , spectrophotometry [6) , liquid chromatography [7]

and fluorimetry [8].

Chemiluminescence (CL) method has been an important detection method for the

pharmaceutical preparations in recent years [9 ,10] because of promising

advantages of low detection limit, wide linear dynamic range and relatively simple

and inexpensive instrumentation. Acidic potassium permanganate has been is one

of the most important oxidants applied in CL reactions and a great number of

investigations have been published [1 1, 12]. This work describes the sensitizing

effect of sparfloxacin on the CL intensity emitted from the reaction of sulfite with

97

98 Seikh Mafiz Alam . 이상학

acidic KMn04. To our best knowledge , this paper describes the first application of

FIA -CL to the determination of sparfloxacin.

2. EXPERIMENTAL

2.1.Instrumentation

A Spex (Edison , NJ , USA) Model FL 111 spectrofluorimeter was used to

accomplish the chemiluminescence measurements. An Ismatec Model 404

peristaltic pump was used to convey the one CL reagent for initiation of the

reaction. During the measurements , the light source of the excitation

monochromator was switched off. Slit width of emission monochromator was fixed

with 0.25 mm. The photomultiplier tube (PMT) used was a Hamamatsu Model R

928 (Hamamatsu , USA) powered at 950 V. Spectra data were collected by Spex

DM 3000 spectroscopy computer.

2.2.Reagents

Individual standard stock solution of sparfloxacin 0 x lO-:l M) was prepared in

deionised water. 0.1 M HCl solution. Stock solution 0 x lO-:l M) of KMn04 was

prepared in 0.1 M sulphuric acid. Aqueous Na2S0:l solution 0 x 10-2 M) was

prepared in distilled water.

2.3.ProcedureThe basic analysis procedure of the batch type CL consisted (Fig. 1) of addition

of the followingquantities of the equilibrated solutions into the reaction cell: 1.0 ml

KMn04 (3.1 x lO-:l M) solution , 1 ml sparfloxacin 0.0 Xl 0-3 M) solution. The

contents of the reaction cell were allowed to mix for 10 seconds in the cell

compartment prior to injection of 0.5 ml 0.0 x 10-3 M) Na2S03 solution with

peristaltic pump. The analytical signal was taken as the difference in the CL peak

height between a blank and analyte run.

S.....I~

---、~ IDJud8nv야’

C lI.M1er

lI:l‘IDO..

N"2S0~

Fl

p z

T:!; n-••빼

J'1uodlltder

Figure 1. Schematic diagram of the FIA CL manifold employed for the quantitativedetermination of levodopa. PI. P2 ’ Peristaltic pumps; T l. T2: Y- pieces

용용화학， 제 12 권 제 1 호， 2008

FJow- Injection Chemilu미nescence Dctennination of Spa버oxacin Using Potassium P，해nanganate- S떠ium Sulfite System 99

3. Results and discussion

3.1.CL kinetic curve of the system

The CL kinetic curves of KMnO\- NalS03-HlSO~ and sparfloxacin- KMnO~ - Na2S0:1- HlSO •

systems were constructed with the recorder. which are shown in Fig.2

KMn01- Na2S0:1- H2S04 system has an ultra -weak CL. Adding sparfloxacin into the system

largely enhances its CL intensity and the value of enhancement is proportional to the

substances added. By this property. sparfloxacin can be determined sensitively with with

CL method.

1.6x10‘gu 1.“ 10‘홉 1.2x 10‘

훌 1.0x삐x1띠1애o:I 8.0x10’

얻 6.0x10’

들 4.0x10’그 •흩 2.0x10·

를 0.0‘J

b

350 400 450 500 550 800 850

Wavelength , nm

Figure 2.KMn04-NalSO:I-HlS04 (a) and sparfloxacin- KMnOcNa2S03-H2S04 (b)

CL spectra of

3.2.Selection of potassium permanganate concentrationThe effect of KMn04concentration on the CL reaction was examined in the range of

1.0 X 10-3 to 2.5 x 10- r. M. It has been observed from the results (Fig 3) that the CL signal

rapidly increased with increasing in KMn04 concentration up to 3.1 X 10-3 M. Larger

concentrations resulted in a decrease of emission intensity. Therefore. 0.5 x 10-‘’ mollLKMn04 was chosen for subsequent experiments.

2xl0'---‘

‘•,

애

뼈

띠m

애

띠

띠

2

’’’’’9

·au.강

·I·를

-·uC@u·g-E

그=EEu

8x l0' 0.0 0.2 0.4 0.6 0.8Concentration , mM

1.0

Figure 3. The effect of the corκentration of KMn0 1.

Applied Chemistry, Vol. 12, No. I , a:뼈

100 Seikh Mafiz 매am . 이상학

3.3.Selection of sulfite concentrationNo CL signal has been observed in the absence of sodium sulfite. It played an important

role in the reaction system. The variation of the CL emission with sulfite concentration in

the 0.01 to 3.0 xl 0 4 M range was studied. The chemiluminescence intensity increased

with the increase of the concentration of NazS03 when it was lower than 1 x 10-3 mo1/L.

Thus. 1 x 10년 mo1/L mo1/L was chosen as optimum.

3 .4 .Calibration

Under the optimal experimental conditions established above. the calibration graph of the

concentration of gibberellic acid versus peak height was linear in the range of 1.6 x 10 - 8 to

2.9 X10 “ mo1/L. The detection limit was found to be 0.7 x 10 8 mo1/L.

Acknowledgment

Acknowledgement is made to the Korea Research Foundation (KRF-2004-005-C00009)

for the support of this research.

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용용화학， 제 12 권 제 1 호， 2008