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Development of aChemiluminescence Methodfor the SimultaneousDetermination of Ascorbicand Tartaric Acids BasedUpon Their Reaction withCerium(IV) in the Presence ofRutheniumtrisdipyridineZhike He a , Xiaoyan Li a , Hui Meng a , Shaofang Lu a

, Gongwu Song a , Liangjie Yuan a & Yune Zeng aa Department of Chemistry , Wuhan University ,Wuhan, PRC, 430072Published online: 22 Aug 2006.

To cite this article: Zhike He , Xiaoyan Li , Hui Meng , Shaofang Lu , Gongwu Song ,Liangjie Yuan & Yune Zeng (1998) Development of a Chemiluminescence Method forthe Simultaneous Determination of Ascorbic and Tartaric Acids Based Upon TheirReaction with Cerium(IV) in the Presence of Rutheniumtrisdipyridine, AnalyticalLetters, 31:9, 1553-1561, DOI: 10.1080/00032719808002889

To link to this article: http://dx.doi.org/10.1080/00032719808002889

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ANALYTICAL LETTERS, 31(9), 1553-1561 (1998)

DEVELOPMENT OF A CHEMJLUMINESCENCE METHOD FOR THE

SIMULTANEOUS DETERMINATION OF ASCORBIC AND TARTARIC

ACIDS BASED UPON THEIR REACTION WITH CERIUM(1V) IN THE

PRESENCE OF RUTHENIUMTRISDIPY RlDINE

Keywords: Simultaneous determination; Ascorbic acid: Tartaric acid;

Chemiluminescent andysis

Zhike He*, Xiaoyan Li, Hui Meng, Shaofang Lu,

Gongwu Song, Liangjie Yuan and Yun'e Zeng

Department of Chemistry, Wuhan University, Wuhan(PRC), 430032

ABSTRACT

A time-resolved chemiluminescent method for the determination of ascorbic

and tartaric acid has been developed. The method is based on the differential rate of the

chemiluminescent reaction of Ru(bipy),2f, ascorbic and tartaric acid with Ce(1V). The

ascorbic acid system gives the highest chemiluminescence intensity at 2s, whereas the

tartaric acid system gives its most intense chemiluminescence emission at 40s.

Ascorbic acid ( 1 . 7 ~ - 1.4. lom6 M) i~ - 5 . 2 ~ lo-* M) and tartaric acid ( 1 . 4 ~

*Corresponding author.

Copyright 0 1998 by Marcel Dekker, Inc.

1553

www.dekker.com

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1554 HE ET AL.

wines were detennined simuItaneously with rerative standard deviations of better than

5944~-5). The detection limit of ascubic acid and tartaric acid were 4 . 8 ~ M and

8 . 4 ~ M, respectively.

Ascorbic acid plays an important role in maintaining human health. Many

methods for the determination of ascorbic acid have been reported. Of these, the

titration and microfluorometric methods are time-consuming due to the extractioR

process'. The electrochemical method suffers from problems due to coexisting

impurities having oxidation potentials close to that of ascorbic acid2. Enzymatic' and

spectrophotometric'" methods have limited sensitivities. The most frequently used

method for the determination of tartaric acid is chromatography(high-performance

liquid chromatography) which allows for the determination of this and other organic

acids in wines6.'. However, the sensitivities are 2-3 orders of magnitude lower than

our proposed new method.

The chemiluminescence(C1) method using tris(bipyridyl)ruthenium(K)

(Ru(bipy)32') has become an attractive detection means for biochemical substances,

such as amines"or amino acids' due to its low detection limits and wide linear w o r m

ranges, with relatively simple instnunentation. CL was observed by Bard et al. lo with

some organic acids such as pyruvic, malonic or lactic, when the intermediates produced

on their oxidation by Ce(1V) reacted Ru(bipy),2+. No previous report has focused on

the application of this system for the simultaneous CL determination of ascorbic acid

and tartaric acid. In this paper, a time-resolved CL method for such a determination of

ascorbic acid and tartaric acid is reported.

EXPERJMENTAL

Apparatus

LKB-1251 luminometry based upon collection of all light emitted(no

wavelength discrimination), dispenser SVD and dispenser controller DC(Pharmacia

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ASCORBIC AND TARTARIC ACIDS 1555

LKB Biotechnology AB, Sweden), with a Epson LX-800 printer(Seik0 Epson Cop.

Japan) were used.

Reagents

A 3.7 mM stock solution of tartaric acid was prepared by dissolving 55mg

C,H,O, in lOOmL water. A I.Omg/mL stock solution of R~(bipy)~Br~(synthesised in

our laboratory) was prepared by dissolving I.0g R ~ ( b i p y ) ~ B r ~ in water and diluting

with water to IL. A 6.OmM sfock solution of ascorbic acid was prepared daily by

dissolving 107mg ascorbic acid in lOOrnL water. All other reagents were analytical

grade or better. All water used was doubly distilled from a fused-silica apparatus.

Procedures

A 0.4mL portion of a mixed solution containing 2.1 x M ascorbic acid,

1 . 8 ~ 1 0 ~ M tartaric acid and 0.4mL 2.0~10" dmL Ru(bipy)32f, were pipetted into the

sample cuvettes and then pIaced into the measuring chamber of the luminometry with

a constant temperature of z98R. The CL reaction was initiated by the automatic

injection of 0.ZmL of 1.8m Ce(IV)(O.O71M H2S0,) into the reaction cuvettes and

the CL profile was measured as a function of time. Ascorbic and tartaric acid showed

maximum intensity at 2s and 40s, respectively (see Fig. 1).

RESULTS AND DISCUSSION

Optimization of conditions

Effect of concentration of Ku(bipy)32+

The study was conducted by monitoring the CL time profile for solutions

containing variable amounts ( 7 . 8 ~ loe7 M to 5% lo-' M) of Ru(bipy)32', 8.4~10-' M

ascorbic acid, 7 . 2 ~ l o5 M tartaric acid and 0.36mM Ce(IV)(O.O142M H2S04). The CL

intensity increased with increasing R u ( b i p ~ ) ~ ~ ' both in the presence of ascorbic, tartar

acid and in their absence. This implies that the luminophor is Ru(bipy)g2+11. The

maximum signal to background ratio was obtained at 8.0~ M concentration.

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1556 HE ET AL.

3001 1 I I I I i

0 10 20 30 40 50 60

t/S

Figure 1 CL intensity vs. time profile obtained in the determination of 8.4~ loa7 M ascorbic acid and 7 . 2 ~ 10-5M tartaric acid. Conditions: 8.0~ 10-5M Ru(bipy),2+, 3 . 6 ~ rO%f Ce(1V) an&0,0142M H2S0,

Effect of the concentration of H2S0,

The CL emission depends on the Concentration of H,SO,. This study was

carried out in the range of 0.004 to 0.0142M H,SO, under the standard conditions

noted above. The maximum intensity was obtained at 0.0 t42M H,SO,, A plot of CL intensity 1 vs. 1/[H,SOJ2 gave a straight line which indicates that the rate of reaction

is inversely propohanal to the square of the concentration of sulphuric acid. This is

consistent with a prior literature report12.

Effect of the concentration of Ce(1V)

The CL light intensity also depends on the concentration of Ce(1V). The CL

intensity was measured for soIution in which C e w concentration was varied from

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ASCORBIC AND TARTARIC ACIDS 1557

I.Zx 104 to 5.3 lo4 M under the standard conditions previously noted. The maximum

intensity was obtained at 3 . 6 ~ I04M Ce(1v).

Comparison the Kinetic Property of Ascorbic Acid and Tartaric Acid

The general CL intensity vs time profile for the reaction of ascorbic and tartaric

acid with cerium(1V) in the presence of Ru(bipy),2+ was initially obtained(Figure 1).

This CL system exhibits two peaks, one due to the presence of ascorbic acid(maximm

CL intensity observed at about 2 sec) and another for tartaric acid(peak CL after about

40 sec). This time differential observed for the attainment of the maximum CL due to

the presence of these two analytes provides the basis for development and optimization

of a simultaneous CL method for their determination. The time required to achieve

maximum CL intensity in the presence of ascorbic acid is less than that in the presence

of tartaric acid. Accordmg to our CL mechanism, this arises due to the fact that tartaric

acid cheIates with Ce(1V) in d i i e n t forms and their disproportionation pathways are

different. This is consistent with a prior report in the Iiiterat~re'~.

Comparison with Other Methods

The resolution and accuracy of this method depend on the concentration of

ascorbic acid and tartaric acid. Under the optimum conditions, the proposed method

allows for the determination of ascorbic acid and tartaric acid with a 2-3 orders of

magnitude greater sensitivity than other reported analyhcal method (see Table 1).

CaIibration and Detectioa

Under the optimum conditions, responses were linear between 1 . 7 ~ 1 0 - ~ and

5 . 2 ~ lo-' M ascorbic acid and from 1.4.104 to 1 . 4 ~ 1 0 ~ M tartaric acid. The linear

regression equations were y=219+2.89~ 108C for ascorbic acid and y=34+1.67~ 10-7C

for tartaric acid, respectively. The detection limit(S/N=3) of ascorbic acid and tartaric

acid are 4 . 8 ~ lo-' M and 8 . 4 ~ lo7 M, respectively. The relative standard error of

ascorbic acid ( 8 . 4 ~ 1 0 - ~ M) and tartaric acid (7.2~14 M) are 4.8% and 1.7%,

respectively (n=ll). The plot of 1/I vs. l/[ascorbic acid] or ]/[tartaric acid] is a straight

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1558 HE ET AL.

Table 1 Linear dynamic range for ascorbic and tartaric acid achieved with the proposed CL method in comparison to other reported methods

Methods Dynamic linear range M Reference

Ascorbic acid

CL

CL

Selective electrode

CL

Proposed CL method

Tartaric acid

CL

FI

Selective electrode

Polarography

Proposed CL method

0.02-0.4g/mL

1 . 3 ~ 104-2.6x 10"

2 . 0 ~ 10-4-6.0x 10"

6 . 6 ~ I0-'-6.6~

1 . 4 ~ 1 0-6- I .4x 1 0-4

14

15

16

17

this method

18

19

20

21

this method

line which intersects I/I axis. This suggests that the formation of activated complex

between Ce(rv) and ascorbic acidj'tartaric acid. This is consistent with the experimental

results in the absence of R~t{biPy>~~+.

Effect of Other Species

The experimental results revealed that a 1000-fold excess of K+, Na+, AP',

Znz+, C1-, SO:-, NO,: alcohol, 500-fold Mn*+, Fe3', NiZ+, Co2+, Br-, 100-fold Ba".

NH4+, glucose, 50-fold F-, urea, uric acid, 10-fold I- had no effect on the determination

of ascorbic acid(2.0~ M) or tartaric acid(4.0r 10 -' M).

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ASCORBIC AND TARTARIC ACIDS 1559

Table 2 Determination of ascorbic acid(AA) and tartaric acid(TA) in wines

AA added TA added AA recovered Recovery TA recovered Recovery

(M) (M) (MI (“A) (Pg) (“A)

O.ll(0.23) 10.0(3.0) 0.10 90.1 9.2 92.0

0.44(0.23) 40.0(3.0) 0.41 93.2 40.4 101

0. I I(0.41) 10.0( 16.4) 0.12 109 9.6 96.0

0.44(0.41) 40.0(16.4) 0.43 97.7 42 105

Mechanistic Study of the CL Reaction

In the absence of Ru(bipy)j2+, kinetics of oxidation of ascorbic7 and tartaric6]

acids by Ce(1V) have been studied. The mechanism involves the rapid formation of a

Ce(IV) activated compIex foIIowed by its dower decomposition. In the presence o€

Ku(phen)32’; kinetics of oxidation of 16 organic acids by Ce(1V) were investigated”.

It was found that all of the acids examined form activated complexes and enhance the

light emission. A detiuled mechanism for the over-all process in accord with the above

observations will be reported in another pape?2.

Determination of Ascorbic and Tartaric Acid in Wines

The developed method was appIied to the determination of ascorbic and tartaric

acid in wines. The blank wines yielded a high signal(z0.34mg/mL ascorbic acid and

4.8mdmL tartaric acid, respectively). Thus, it was necessary to subtract this signal

from the total signal. Recoveries of 90. I% (n=5) and 109% (n=5)(see Table 2) were

obtained. It is likely that the effect of interferents present in wines can be circumvented

by using liquid chromatography with chemiluminescence detection, as was used for

pyruvic acid23.

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1560

ACKNOWLEDGMENT

HE ET AL.

The authors gratefuny acknowledge the support for this research by the Nature

Science Foundations from the State and Hubei Province.

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