modified glassy carbon electrode를이용한 thiamine의 …mir az깅am kha뻐nπ....

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Applied Chemistry, Vol 12, No.1 , May :IDS. Modified Glassy Carbon Mir Electrochemical method for determination of thiamine using modified glassy carbon electrode Mir Azam Khan. Saikh Mohammad Wabaidur , Wook Hvun Kim , Sang Hak Lee Department of Chemistry. Kyungpook National University Taegu. 702 - 70 1. Korea Abstract Glassy carbon electrode (GCE) modified with poly(4-(2-pyridylazo)-resorcinoI) (PAR) film was used for the determination of thiamine. Thiamine was accumulated at the PAR modified GCE surface under open circuit condition. Thiamine givessensitive oxidation peaks at 160 mV upon using the differential pulse voltammetry (DPV) technique. Experimental conditions such as supporting electrolyte. pH value and accumulation time were optimized for the investigated method. Thiamine gives linear response over the range of 0.030 mM to 1. 1 mM. The lower detection limits were found to be 0.008mM for thiamine. The investigated electrochemical method was successfully applied for the determination thiamine in pharmaceutical formulation. Keywords: -r escrcirn I) , CarIXn I , Introduction The chemical name for thiamine is 2-[3-[(4-amino-2-methyl- pyrimidin-5-yl) methyl]- 4-methy!-thiawl-5-yI] ethanol which consists of a pyrimidine- and a thiazole moiety by a methylene bridge. Vitamin B, is necessary for the proper functioning of the nervous (1) and cardiovascular (2) systems of the body. Severe dietary deficiency of vitamin B, (vitamin B1) can result in beriberi or the Wemicke-Korsakoff syndrome (3). Scientific literature reports many methods for the determination of thiamine , e.g. titrimetric (4) , electrochemical analysis (5) , gas chromatography (6) , high performance liquid chromatography (7) , and spectrophotometry (8) etc. Poly (4- (2-pyridylazo) -resorcino l) (PAR) modified electrode has been reported for the electrochemical determination of various compounds (9 , 10), In the current study , PAR polymer film modified GeE is described for the determination of 77

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Page 1: Modified Glassy Carbon Electrode를이용한 Thiamine의 …Mir Az깅am Kha뻐nπ. Sa마i“싸‘kl배‘이써h Mo야이ha‘amm , 정북대학교 화학과 Electrochemical method

Applied Chemistry,

Vol ‘ 12, No.1 , May :IDS. η-80

Modified Glassy Carbon Electrode를 이용한

Thiamine의 전기화학적 정량

Mir Az깅am Kha뻐nπ. Sa마i“싸‘kl배‘이써h Mo야이ha‘amm,

정북대학교 화학과

Electrochemical method for determination of thiamine usingmodified glassy carbon electrode

Mir Azam Khan. Saikh Mohammad Wabaidur , Wook Hvun Kim , Sang Hak Lee •

Department of Chemistry. Kyungpook National University ‘ Taegu. 702 - 70 1. Korea

Abstract

Glassy carbon electrode (GCE) modified with poly(4-(2-pyridylazo)-resorcinoI)

(PAR) film was used for the determination of thiamine. Thiamine was accumulatedat the PAR modified GCE surface under open circuit condition. Thiaminegivessensitive oxidation peaks at 160 mV upon using the differential pulsevoltammetry (DPV) technique. Experimental conditions such as supportingelectrolyte. pH value and accumulation time were optimized for the investigatedmethod. Thiamine gives linear response over the range of 0.030 mM to 1. 1mM. The lower detection limits were found to be 0.008mM for thiamine. Theinvestigated electrochemical method was successfully applied for the determinationthiamine in pharmaceutical formulation.

Keywords: Th~ 허ectroclHrical ~th:피,p.:jy(4-(2-pyriφr\azo) -rescrcirnI) ,

명assy CarIXn 러ectrode

I , Introduction

The chemical name for thiamine is 2-[3-[(4-amino-2-methyl- pyrimidin-5-yl) methyl]­

4-methy!-thiawl-5-yI] ethanol which consists of a pyrimidine- and a thiazole moiety

Ii따ed by a methylene bridge. Vitamin B, is necessary for the proper functioning of the

nervous (1) and cardiovascular (2) systems of the body. Severe dietary deficiency of

vitamin B, (vitamin B1) can result in beriberi or the Wemicke-Korsakoff syndrome (3).

Scientific literature reports many methods for the determination of thiamine , e.g.

titrimetric (4) , electrochemical analysis (5) , gas chromatography (6) , high

performance liquid chromatography (7) , and spectrophotometry (8) etc.

Poly (4- (2-pyridylazo) -resorcinol) (PAR) modified electrode has been reported

for the electrochemical determination of various compounds (9 ,10), In the current

study , PAR polymer film modified GeE is described for the determination of

77

Page 2: Modified Glassy Carbon Electrode를이용한 Thiamine의 …Mir Az깅am Kha뻐nπ. Sa마i“싸‘kl배‘이써h Mo야이ha‘amm , 정북대학교 화학과 Electrochemical method

78 Mir Azam 싸lan . Saikh Mohammad Wabaidur . 김욱현 • 이상학

thiamine. Theproposed method possesses many advantages such as low detection

limit , fast response. simple and inexpensive instrumentation.

2. Experimental

Reagents and solutions

All reagents wereof analytical grade. Thiamine (Sigma. USA) was used as

standard. Stock solution (l x 10-2 M) and working standard of thiamine was

prepared in distilled water. Poly (4- (2-pyridylazo) -resorcino l) (PAR) was

purchased from Aldrich (USA). 1 mM PAR solution was prepared by dissolving

appropriate amount in pH 5 phosphate buffer solution. NaHιP04.H20 (Merck ,

Germany) and Na2HP0 4.2H20 (Merck. Germany) were used for phosphate buffer

solution. The sample solutions were prepared by dissolving the tablets with water

and diluted to the desired concentration level in the calibration range.

Apparatus

All electrochemical measurements were carried out using computer-controlled

portable Potentiostat (RS- PDA 1, Palm 1nstruments. Netherland)' A conventional

three-electrodessystem was used throughout the experiments. The working

electrode was a bare or PAR modified GCE (3.0 mm in diameter). The auxiliary

electrode was a platinum wire and an AgIAgCl electrode was used as a reference.

pH meter (Mettler Toledo MP220 , UK)was used for pH measuremen t.

Preparation of poly PAR modified GeE

The GeE surface was initially polished with fine emery paper followed by 0.3 Om

and 0.05 Om alumina powder and finally sonicated with Milli-Q water for 3-5

minutes. The GCE was modified as reported previously [9.10]. Before

electropolymerization the polishedelectrode was electrochemically pretreated in 0.1

M PBS pH 5.0 by scanning 20 times between electrode potential of -0.5 V and

1.8 V at scan rate of 100 mVIs. The PAR film was deposited on the pretreated

surface by scanning 20 times of the corresponding monomer in 1 mM PAR underthe same conditions as those in the pretreated procedure. The film deposited

electrode was washed with distilled water.

General procedure

The PAR-coated GCE was first activated in pH 6 phosphate buffers by cyclicvoltammetric sweeps between 0.0 and 0.6 V until stable cyclic voltammogramswere obtained. After obtaining the stable cyclic voltammogram the PAR-coatedGCE 、、las transferred into new cell containing pH 6 phosphate buffer and certainconcentration of analyte. After 1 minute of open-circuit accumulation. thedifferential pulse voltammogram from - 0.2 to +0.7 V at a scan rate 40 mV/swasrecorded for the analyte. Upon using the DPV technique the peak position forBZ and LD appeared at 160 mY. After every measurement , the PAR-mod

웅용화학, 제 12 권 제 1 호, 2α18

Page 3: Modified Glassy Carbon Electrode를이용한 Thiamine의 …Mir Az깅am Kha뻐nπ. Sa마i“싸‘kl배‘이써h Mo야이ha‘amm , 정북대학교 화학과 Electrochemical method

Electroche매C외 method for determination of thiamine using m띠ified glassy carbon electr따e 79

each experiment ;) successive cyclic voltammetric sweeps was done in purephosphate buffer (pH 6).

3. Results and discussion

Electrochemical behavior of thiamine on PAR modified GCE.

Initially the cyclic voltammogram was investigated for the poly - PAR modified GCE

in pure phosphate buffer pH 6. Within the potential window from - 0.2 to +0.7 V,

no observable redox peaks appeared. However, a well- shaped and highly sensitive

oxidation peak appears at 160 mV after adding 100 OM of thiamine. On the

reverse potential scan from - 0.2 to +0.7 V, there was no corresponding

reduction peak, suggesting that the electrode reaction of thiamine at the

poly-PAR modified electrode is totally irreversible.

The oxidation peak current for thiamine in the second cyclic voltammetric sweep

decreases as compared to the first peak , indicating the adsorption of thiamine on

PAR film. The electrode surface was cleaned by washing with distilled water

followed by dipping for few seconds in 0.1 M NaOH solution to remove the

adsorbed substances for reproducible results.

Parameter optimization for tho떠mine at PAR moditi낭d electrodeAccumulation time in the range of a to 2 minutes was optimized for thiamine and

accumulation of thiamine at the modified GCE was performed under open-circuit

condition. The optimum scan rate for CV and DPV was 100 and 40 mV/s

respectively. The best oxidation response was obtained in pH 6 phosphate buffer

since the peak current is the highest and the peak shape is well-defined.

Calibration curve

DPV technique was applied to real sample due to good discrimination against

background current and low detection limits. The linear increase in the current

response for concentration of thiamine using DPV is shown in fig 1. Using

optimum conditions linear calibration curves were obtained for thiamine over the

range of 0.030 mM to 1.1 mM. The lower detection limits were found to be 0.008

mM for thiamine.SimilarlY calculated limit of quantification were 0.02 mM.

Determination of thiamine in pharmaceutical preparation.

The proposed electrochemical method was applied to the determination of vitamin

B, in commercial vitamin Bltablets (Biphane , Yuhan , Co. Korea). Standard

calibration curve was used for the determination of vitamin Bl. The summarized

results for the analysis of thiamine in pharmaceutical preparations are shown in

table- 1.The results show that the proposed method can be successfully applied

for the determination of thiamine in pharmaceutical preparation.

S뻐I때e Oaimedlta빼et Proposed me삐lOd

Biphane (vitamin B, tablet) 8.0 mg 8.34 mgTable 1. Assay of vitamin B1 in the commercial vitamin B, tablets

Applied Chemis며, Vol. 12, No. I, 2008

Page 4: Modified Glassy Carbon Electrode를이용한 Thiamine의 …Mir Az깅am Kha뻐nπ. Sa마i“싸‘kl배‘이써h Mo야이ha‘amm , 정북대학교 화학과 Electrochemical method

80 Mir Az뻐1 때1an • S히kh Mohammad Wabaidur' 김욱현 •이상학

z5

20

‘i훌 15

5‘j

,。

0.2 。 ‘ 0.' 。. 1.0

Thl.m In. Concentr.tlonlm M

Fig 1. Calibration curve for the electrochemical determination of Thiamine

4. Conclusion

An electrochemical method was developed and successfully applied for thedetermination of thiamine using poly (4- (2-pyridylazo) -resorcinol) (PAR)

modified glassy carbon electrode. In the anodic sweep from -0.2 to 0.7 Y,

thiamine adsorbed at the PAR polymer film modified electrode surface and

oxidized at 160 mY using DPVmethod. The investigated electrochemical method is

simple , sensitive , easy to apply and economicalfor routine analysis. The developedmethod was applied for the determination of thiamine using DPV method in

pharmaceutical formulations.

Acknowledgements

This research was supported by Kyungpook National University Research Fund

2007.

References

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47(2006) 354.3. Depeint F , Shangari N, Furrer R, Bruce WR, 0 ’Brien PJ , Nutr. Res. 27 (2007)

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4. Chang W, Wang L. Huaxue Shω~ 47 (2006) 589.

5. Jiang X, Sun T. Anal. Lett. 40 (2007) 2589.

6. Velisek J , Davidek J , Mnukova J , Pistek T. J. Micronutrient Anal. 2 (1 986) 73.

7. Furlani RPZ , Godoy HT. Food Chem. 106 (2007) (VoI2008): 816.

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용용화학, 제 12 권 제 1 호, 2008