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A Study of Chemiluminescence from Reaction of Bis(2,4,6-

trichlorophenyl)oxalate, Hydrogen Peroxide and Diethyl-2-
(cyclohexylamino)-5-[(E)-2-phenyl-1-ethenyl]-3,4-furandicarbox ylat...

Article in Journal of the Iranian Chemical Society · June 2010

DOI: 10.1007/BF03246023

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J. Iran. Chem. Soc., Vol. 7, No. 2, June 2010, pp. 376-383.
JOURNAL OF THE
Iranian
Chemical Society

A Study of Chemiluminescence from Reaction of

Bis(2,4,6-trichlorophenyl)oxalate, Hydrogen Peroxide and Diethyl-2-
(cyclohexylamino)-5-[(E)-2-phenyl-1-ethenyl]-3,4-furandicarboxylate as a Novel
Fluorescer

K. Zargoosha, M.J. Chaichib, S. Asgharic, M. Qandaleec and M. Shamsipurd,*

a
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
b
Department of Chemistry, Mazandaran University, Babolsar, Iran
c
Department of Chemistry, Islamic Azad University, Tehran Branch, Tehran, Iran
a
Department of Chemistry, Razi University, Kermanshah, Iran

(Received 24 February 2009, Accepted 16 June 2009)

The chemiluminescence (CL) arising from reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in
the presence of a diethyl-2-(cyclohexylamino)-5-[(E)-2-phenyl-1-ethenyl]-3,4-furandicarboxylate as a novel fluorescer (Flu) has
been studied. The relationship between the chemiluminescence intensity and concentrations of TCPO, sodium salicylate,
hydrogen peroxide and fluorescer is reported. The chemiluminescence parameters including intensity at maximum CL, time at
maximum intensity, total light yield, theoretical maximum level of intensity and pseudo-first-order rate constants for the rise and
fall of the CL burst (kr and kf) were evaluated from computer fitting of the resulting intensity-time plots. The activation
parameters Ea, ΔH‡, ΔS‡ and ΔG‡ for the rise and fall steps were evaluated from the temperature dependence of kr and kf values.

Keywords: Peroxyoxalate-chemiluminescence, Diethyl-2-(cyclohexylamino)-5-[(E)-2-phenyl-1-ethenyl]-3,4-furandicarboxylate,

H2O2, TCPO, Activation parameters

INTRODUCTION the reaction follows a chemically initiated electron exchange

luminescence (CIEEL) mechanism via the formation of high
Peroxyoxalate chemiluminescence (PO-CL) is well known energy intermediate(s) such as 1,2-dioxetanedione [11,12,].
as a powerful technique for the sensitive and some times These meta stable intermediates form complexes with the
selective determination of a large variety of analytes, fluorophore that donates one electron to the intermediate
depending on the roles they play in the CL reaction as [13,14]. This electron is transferred back to the fluorophore
fluorophores [1-4], catalysts [5], quenchers [6-8], oxidants raising it to an excited state and liberating light characteristics
[9,10], etc. In principal, PO-CL involves hydrogen peroxide typical for the fluorophore nature. This phenomenon is
oxidation of an aryl oxalate ester in the presence of a typically depicted in Scheme 1.
fluorophore (activator). Although the reaction mechanism of Although several authors have investigated the kinetics
PO-CL is still under controversy, it has been suggested that and mechanism of the PO-CL reaction, the key pathway(s) and
nature of the reactive intermediate(s) remain highly uncertain
*Corresponding author. E-mail: [email protected] and the intermediate(s) were never directly observed.
 Zargoosh et al.

Cl
O O

TCPO + H2O2 2 Cl OH + EXPERIMENTAL

O O
Cl (1) Reagents and Solutions
Bis(2,4,6-trichlorophenyl)oxalate (TCPO) was prepared
O O O O
from the reaction of 2,4,6-trichlorophenol with oxalylchloride
+ Flu Flu in the presence of triethylamine as described elsewhere [28].
O O O O
(2) Hydrogen peroxide (Merck, Perhydrol Suprapur, 30% in
water) was assayed by permanganate potassium titration [29]
O O and diluted in ethyl acetate. Diethyl-2-(cyclohexylamino)-5-
Flu* + 2 CO2 [(E)-2-phenyl-1-ethenyl]-3,4-furandicarboxylate (Flu) was
Flu
O O synthesized in our laboratories, as described before [30].
(3)
Reagent grade sodium salicylate (SS, Merck) was used as
Flu* Flu + Light (4) received. The stock solution of fluorescer (0.005 M) was
prepared in a calibrated 50-ml flask by dissolving an
Scheme 1 appropriate amount of the reagent in ethyl acetate, and
protected from light. Stock solutions of sodium salicylate
Dioxetanedione was first suggested by Rauhut et al. as a (0.005 M) and the TCPO (0.005 M) in ethyl acetate were
reaction intermediate [15] and then aryl-containing dioxetane prepared shortly before use.
derivatives and six-member intermediate(s) were proposed by
other researchers [11,16,17,18]. Appearance of different Chemiluminescence Measurements
mechanisms and intermediates for PO-CL in the literature
Chemiluminescence measurements were carried out on a
reactions is a result of this assumption that H2O2 or catalyst
homemade apparatus equipped with a phototube (59 RX
may first react with the oxalate ester [12,15].
Kelman). The instrument was covered with a black sheet, in
In recent years, we have studied the chemiluminescence
order to prevent piping of light to the cell. The voltage applied
reactions of peroxyoxalate esters, H2O2 and several
to the phototube was 90 V. The temperature was adjusted to
fluorophores in the presence of suitable basic catalysts such as
the desired values ± 0.1 °C, using a Thermo Mix Broaun
sodium salicylate (SS) and imidazole [19-27]. In this paper,
we report a study of PO-CL reaction of diethyl-2- thermostat (Biotechnology Int.). The apparatus was connected
(cyclohexylamino)-5-[(E)-2-phenyl-1-ethenyl]-3,4-furandi- to a personal computer via a suitable interface (Zag Chem.,
carboxylate (Flu) as a novel fluorescer. The relationship Tehran, Iran). The experiments were carried out with magnetic
between the chemiluminescence intensity and concentrations stirring (500 rpm) in a light-tight flat-bottom glass cell of 10
of TCPO, sodium salicylate, hydrogen peroxide and fluorescer mm diameter.
as well as the influence of temperature on the resulting PO-CL
are reported. Fluorescence Measurements
Steady-state fluorescence spectra were recorded on a
O O
Perkin Elmer, Ls50 spectrofluorimeter instrument. The
CH3CH2O C C OCH2CH3 excitation and emission monochromators were set at 371 and
471 nm, respectively. A spectral bandwidth of 3 nm was used.
All experiments were carried out using freshly prepared
C C
H
O HN solutions containing 5 × 10-4-2.5 × 10-3 M of Flu in an
H
acetonitrile-ethyl acetate (50:50 v/v) solvent mixture, using a
Flu 10-mm quartz cuvett.

377
 A Study of Chemiluminescence

120
RESULTS AND DISCUSSION 1 2

Peroxyoxalate-chemiluminescence reaction (PO-CL) is 90 3

one of the most efficient non-biological light producing

Intensity
systems. The mechanism of PO-CL process has been 60
postulated to involve one or more highly energetic
intermediate(s) (possibly dioxetane species) capable of 30
exciting a fluorescent receptor molecule [31,32], as shown in
the Scheme 1. In preliminary experiments, it was found that
0
the addition of few drops of the stock solution of hydrogen 300 400 500 600
peroxide to an ethyl acetate solution containing TCPO and Wavelength (nm)
fluorescer Flu in the presence of suitable catalyst such as SS
Fig. 1. Fluorescence excitation (1), emission (2) and
results in a very intense blue light. The sensitized PO-CL
chemiluminescence (3) spectra of the fluorescer.
spectrum of Flu together with its fluorescence excitation and
emission spectrums is shown in Fig. 1. As it is apparent from
Fig. 1, since the light emission steps for both
where It is the CL intensity at time t, M is a theoretical
chemiluminescence and fluorescence are essentially
maximum level of intensity if the reactants were entirely
analogous, the emission wavelength maxima in both processes
converted to a CL-generating material and kr and kf are the
are similar (i.e., 471 nm) [19-27,33].
first order rate constants for the rise and fall of the burst of CL,
As expected, the intensity of the PO-CL emission was
respectively.
found be affected by the initial concentration of the reactants
A further advantage of this model is that it not only allows
[20,21,33,]. Thus, in the next steps, the influence of
the determination of parameters M, kr and kf, but also it gives
concentrations of Flu, TCPO, H2O2, and base catalyst SS, as
an estimate of the CL intensity at maximum level (J ), the time
well the effect of temperature on the PO-CL system was
of maximum intensity (Tmax) and the total yield (Y), as
studied. The effects of each of the reagents on the
follows:
chemiluminescence profile and reaction kinetics were
determined under pseudo-first-order condition with hydrogen
J = M (kf/kr)[kf ⁄ ( kr - kf )] (7)
peroxide in large excess over TCPO. In order to investigate
the kinetic profiles of the chemiluminescence process of H2O2-
Tmax = [ln(kf/kr)]/[kf - kr] (8)
TCPO-Flu-SS system from the corresponding CL intensity
versus time profiles, a previously reported simplified model ∞

was employed [18,33,34]:

Y= ∫ 0
Itdt = M ⁄kf (9)

kf
In this work, a non-linear least-squares curve fitting
kr
R X P (5) program KINFIT [35] was used to evaluate the M, kr and kf
values from the corresponding CL intensity-time plots. A
typical computer fit of the CL intensity time plots is shown in
where R, X and P represent pools of reactants, intermediates
Fig. 2. The other parameters J, Tmax and Y were then evaluated
and products, respectively, and both the reaction steps are
from Eqs. (7) to (9) using the kr, kf and M values. The kinetic
irreversible first order reactions. The chemiluminescence
parameters thus obtained for all experiments carried out are
signal is proportional to the concentration of intermediate X
summarized in Tables 1 and 2.
and the integrated rate equation of CL intensity versus time is:
Figure 3 shows typical response curves (i.e., light intensity
versus time) for the PO-CL system of fluorescer Flu (7.5 ×
It = [Mkr⁄(kf - kr)] [exp(-kr t) - exp(-kf t)] (6)
10-5 M) in the presence of varying concentrations of TCPO

378
 Zargoosh et al.

50 a relatively large intercept of about 0.0021 s-1, which is

representative of a first-order reaction that is zero-order in
40
concentration of hydrogen peroxide [18,24]. Meanwhile, the
pseudo-first-order rate constant for the rise step kr increased
Intensity

30
linearly with increasing H2O2 concentration (Table 1). In this
20
case, the linear plot of kr vs. [H2O2] passes through the origin,
10 within the experimental error, which is consistent with the
previously reported mechanism proposed by Hadd et al. for
0 the PO-CL reactions in the organic media [18]
0 100 200 300 400 500
The PO-CL intensity of a 7.50 × 10-5 M solution of Flu,
Time (s)
under the constant concentrations of TCPO (7.50 × 10-4 M)
Fig. 2. Computer fit of the CL intensity-time plot for TCPO- and H2O2 (0.1224 M) was found to increase intensely in the
H2O2-Flu-SS system: (♦) experimental point and (-) presence of sodium salicylate (SS), most probably due to the
calculated point catalytic effect of SS on the PO-CL system studied [21,24,37].
In order to investigate the optimal concentration of SS, the CL
response of the H2O2-TCPO-Flu system was measured against
and excess amounts of H2O2. As seen, the peak intensity the varying concentrations of the base catalyat, and the
increases rapidly after mixing and reaches a maximum in less resulting plot is shown in Fig. 5. As seen, the PO-CL intensity
than 35 s, while the decay of light intensity from the maximum rapidly increased with increasing concentration of SS until a
occurs at much longer periods o time (e.g., > 14 min at a concentration of 2.50 × 10-4 M is reached, the observed
TCPO concentration upper than 5.0 × 10-4 M). As it obvious intensity enhancement being indicative of the catalytic effect
from the inset of Fig. 3, there is a nice linear correlation of the base. However, further addition of sodium salicylate
between the chemiluminescence intensity and the TCPO revealed a gradual decrease in the CL intensity and in total
concentration. The basis for such linear correlation has already yield, Y (see Table 1). This is most probably due to the
been discussed in literature [11,36]. It is interesting to note quenching effect of the base at higher concentrations, which
that both the rate constants kr and kf are more or less begins to decompose the reactive intermediate dioxetane and,
independent of TCPO concentration (within the experimental hence, reduces the PO-CL light [20,21,24].
errors), as it is the limiting reagent in the CL process (Table The effect of Flu concentration, at constant amounts of
1). Such constancy of kr and kf with increasing TCPO TCPO, H2O2 and SS was studied and the results are shown in
concentration confirms that the reaction is pseudo first order in Fig. 6 and Table 1. As it is obvious from Fig. 6, there is a
TCPO when H2O2 is present in large excess [18]. linear increase in CL intensity of the H2O2-TCPO-SS-Flu
The influence of H2O2 concentration on the PO-CL of system with increasing concentration of the fluorescer. In
fluorescer Flu was studied at constant concentrations of Flu addition, Table 1 reveals that although the rate constants kr
(7.50 × 10-5 M), TCPO (7.50 × 10-4 M) and SS (1.25 × 10-4 M) and kf obtained for the PO-CL reaction are more or less
(Fig. 4). It was found that there is a direct linear relationship independent the fluorescer concentration, the CL total yield
between the concentration of hydrogen peroxide and PO-CL increases with increasing fluorescer concentration, which is
intensity of the system, at the concentration ranges of 2.45 × consistent with previous reports [8,11,12]. Such observations
10-2-1.84 × 10-1 M. However, further increase in H2O2 declare the fact that the high-energy cyclic intermediates (i.e.,
concentration (i.e., > 2.45 × 10-1 M) was found to have no dioxetane species) may transfer energy to a fluorophore via
significant effect on the PO-CL intensity. the CIEEL mechanism. Previous kinetic works has shown that
It is interesting to note that, with the excess amount of the charge-transfer steps leading to chemiluminescence are
hydrogen peroxide, the pseudo-first-order fall rate constant, kf, fast relative to the formation of an initial intermediate and, for
increases linearly with increasing H2O2 concentration with a this reason, the final reactions leading to chemiluminescence
regression equation kf = 0.0231[H2O2] + 0.0021 (Table 1) with are kinetically unobservable [11,15,16,36,37].

379
 A Study of Chemiluminescence

Table 1. CL Parameters Evaluated from Computer Fitting of the CL Intensity-Time Plots for H2O2-TCPO-Flu-SS System

Parameter changed Concentration kr kf M Jexp J Texp Tmax Y

(M) (s-1) (s-1) (mV) (s) (s) (mV s-1)
H2O2 2.45 × 10-2 0.056 ± 0. 006 0.0023 ± 0.0004 10.86 ± 0.08 9.38 9.47 69 59.1 4681
-2
6.12 × 10 0.198 ± 0.010 0.0039 ± 0.0005 25.35 ± 0.21 24.51 23.44 23 20.3 6550
-1
1.22 × 10 0.298 ± 0.016 0.0047 ± 0.0005 38.24 ± 0.28 39.34 35.77 15 14.1 8085
-1
1.84 × 10 0.401 ± 0.027 0.0067 ± 0.0009 54.96 ± 0.50 58.51 51.25 10 10.4 8166
-1
2.45 × 10 0.509 ± 0.029 0.0075 ± 0.0011 61.58 ± 0.66 66.93 57.16 10 10 8255

TCPO 2.50 × 10-4 0.152 ± 0.031 0.0034 ± 0.0005 10.85 ± 0.10 10.58 9.95 32 25.7 3220
-4
5.00 × 10 0.129 ± 0.009 0.0037 ± 0.0008 19.00 ± 0.25 19.82 17.11 23 28.4 5163
-4
7.50 × 10 0.184 ± 0.018 0.0047 ± 0.0012 32.16 ± 0.52 35.35 29.22 16 20.5 6857
-3
1.00 × 10 0.180 ± 0.016 0.0049 ± 0.0011 39.32 ± 0.60 42.54 35.57 16 20.6 8091
-3
1.50 × 10 0.178 ± 0.007 0.0074 ± 0.0019 39.45 ± 0.92 36.52 34.36 20 18.6 5310

SS 1.25 × 10-5 0.065 ± 0.004 0.0030 ± 0.0009 18.14 ± 0.29 18.25 15.62 38 49.6 6007
-5
2.50 × 10 0.124 ± 0.011 0.0047 ± 0.0001 30.67 ± 0.59 33.15 26.96 21 27.3 6512
-5
7.50 × 10 0.202 ± 0.014 0.0046 ± 0.0008 35.15 ± 0.40 37.68 32.19 15 19.2 7658
-4
1.25 × 10 0.287 ± 0.014 0.0056 ± 0.0007 41.69 ± 0.37 42.03 38.19 14 15.7 7445
-4
1.75 × 10 0.302 ± 0.013 0.0062 ± 0.0006 44.11 ± 0.28 44.07 40.64 14 13.1 7069
-4
2.50 × 10 0.597 ± 0.003 0.0073 ± 0.0007 48.99 ± 0.32 46.86 46.38 12 7.5 6693
-4
5.00 × 10 0.607 ± 0.015 0.0105 ± 0.0018 59.87 ± 0.71 42.60 55.74 7 6.8 5691

Flu 2.50 × 10-5 0.163 ± 0.008 0.0051 ± 0.0004 23.54 ± 0.52 20.91 19.89 16 24.9 3482
-5
5.00 × 10 0.166 ± 0.016 0.0053 ± 0.0001 26.27 ± 0.46 28.64 2345 17 21.4 4957
-4
1.00 × 10 0.186 ± 0.018 0.0045 ± 0.0001 35.43 ± 0.58 39.40 32.29 16 20.5 7821
-4
1.50 × 10 0.188 ± 0.027 0.0049 ± 0.0001 46.74 ± 0.79 53.8 43.06 13 16.6 9481
-4
2.00 × 10 0.169 ± 0.015 0.0042 ± 0.0001 48.31 ± 0.60 54.84 43.94 16 22.4 11421
-4
2.50 × 10 0.195 ± 0.019 0.0048 ± 0.0001 49.70 ± 0.81 55.99 45.29 14 19.5 10419

Table 2. The CL Parameters Evaluated from Computer Fitting of the CL Intensity-Time Plots for H2O2-TCPO-Flu-SS
System at Various Temperatures

kr kf M Jexp J Texp Tmax Y

T (°C) (s-1) (s-1) (mV) (mV) (mV) (s) (s) (mV s-1)
20 0.093 ± 0.004 0.0018 ± 0.0003 13.53 ± 0.10 13.86 12.50 33 42.9 7353
30 0.139 ± 0.010 0.0036 ± 0.0008 29.65 ± 0.38 31.5 26.90 21 27.0 8236
40 0.204 ± 0.024 0.0070 ± 0.0006 52.49 ± 1.24 57.02 46.57 14 17.1 7498
50 0.297 ± 0.046 0.0105 ± 0.0009 83.16 ± 2.54 91.83 73.57 10 11.7 7920

380
 Zargoosh et al.

50 50 50
4

Intensity
40
Intensity

3 25
30
30
Intensity

0
2 1 3 5 7 9 11 10
20 10 4 [TCPO ] (M) 0 20 40 60
5
1 10 [Sodium salicylate] (M)
10

Fig. 5. Effect of SS on the CL intensity of TCPO-H2O2-Flu-SS

0
system in ethyl acetate solution: [H2O2] = 1.22 × 10-1
0 200 400 600 800
M, [TCPO] = 7.5 × 10-4 M, [Flu] = 7.50 × 10-5 M.
Time (s)

Fig. 3. Effect of TCPO concentration on the CL intensity of 60 60

TCPO-H2O2-Flu-SS system in ethyl acetate solution: 50

Intensity
[H2O2] = 1.22 × 10-1 M, [SS] = 5.00 × 10-5 M, [Flu]
35
40
Intensity

= 7.50 × 10-5 M, TCPO = (1) 2.50 × 10-4 M, (2) 5.00 30 10

× 10-4 M, (3) 7.50 × 10-4 M, (4) 1.00 × 10-3 M.

0 10 20 30
20 10 5 [Flu] (M)
10
75 0
75
0 200 400 600 800 1000
4 50
Intensity

Time (s)
50
25
Intensity

3
0 Fig. 6. Effect of Flu concentration on the CL intensity of
2 0 0.05 0.1 0.15 0.2
25 [H 2 O 2 ] (M) TCPO-H2O2-Flu-SS system in ethyl acetate solution:
1 [H2O2] = 1.22 × 10-1 M, [TCPO] = 7.50 × 10-4 M,
[SS] = 5.0 × 10-5 M, [Flu]: (1) 2.50 × 10-5 M, (2)
0
0 200 400 600 800
5.00 × 105 M, (3) 1.00 × 10-4 M, (4) 1.50 × 10-4 M,
Time (s)
(5) 2.00 × 10-4 M, (6) 2.50 × 10-4 M.

100
4
Fig. 4. Effect of H2O2 concentration on the CL intensity of
TCPO-H2O2-Flu-SS system in ethyl acetate solution: 3
Intensity

[TCPO] = 7.5 × 10-4 M, [Flu] = 7.5 × 10-5 M, [SS] = 50

1.25 × 10-4M, [H2O2] = (1) 2.45 × 10-2 M, (2) 6.12 × 2
10-2 M, (3) 1.22 × 10-1 M, (4) 1.84 × 10-1 M. 1

0
0 250 500
The influence of solution temperature on the Time (s)
chemiluminescence of the H2O2-TCPO-Flu-SS system, at
constant concentrations of all reagents involved, was studied Fig. 7. The CL intensity-time plot for TCPO-H2O2-Flu-SS
and the resulting response curves at 20, 30, 40 and 50 °C are system in ethyl acetate solution at 293 K (1), 303 K
shown in Fig. 7, and the resulting CL parameters for the (2), 313 K (3) and 323 (K) (4).

381
 A Study of Chemiluminescence

Table 3. Activation Parameters of the Rise and Fall Processes for the H2O2-TCPO-Flu-SS System

Step Ea (kJ mol-1) ΔH‡ (kJ mol-1) ΔS‡ (J mol-1 K-1) ΔG‡293K (kJ mol-1)
Rise 30.5 ± 2.0 28.1 ± 3.1 -169 ± 2.2 77.6 ± 2.7
Fall 42.1 ± 2.6 39.7 ± 4.0 -160 ± 4.3 86.5 ± 3.9

-1 -6.5
(A) (C)
-7
-1.5

Ln (Kr /T)
Ln (Kr )

-7.5
-2
y = -3.6505x + 10.081
2 -8 y = -3.343x + 3.3517
R = 0.9997 2
R = 0.9997
-2.5
3 3.1 3.2 3.3 3.4 3.5 -8.5
3 3.1 3.2 3.3 3.4 3.5
1000/T
1000/T
-4
-10.2
(B)
(D)
-5 -10.7
Ln (Kf)

Ln (Kf/T)

-11.2
-6 y = -5.5888x + 12.808 y = -5.2812x + 6.079
2
R = 0.993 -11.7 2
R = 0.992
-7
-12.2
3 3.1 3.2 3.3 3.4 3.5
3 3.1 3.2 3.3 3.4 3.5
1000/T
1000/T

Fig. 8. Arrhenius plots of lnkr vs. 1/T (A) and of lnkf vs. 1/T (B), and Eyring plots of ln(kr/T) vs. 1/T
(C) and of ln(kf/T) vs. 1/T (D) for TCPO-H2O2-Flu-SS system in ethyl acetate solution.

system are summarized in Table 2. As it is illustrated in Fig. 7 transition state theory [39], from the slope and intercept of
and Table 2, the PO-CL intensity increased with increasing linear plot of ln(k/T) vs. 1/T, respectively, for the rise and fall
temperature, although the total light yield (Y) do not show a steps (Fig 8C and 8D). The resulting activation parameters
systematic change with temperature. This is indicative of o the ΔH‡, ΔS‡ and ΔG are also included in Table 3. The activation
fact that the higher CL intensities of the PO-CL at higher parameters thus obtained for both rise and fall steps of the
temperatures are solely due to the rate constants [24]. studied PO-CL system are consistent with the discussions and
The activation energies for the rise and fall steps of the mechanism discussed in the text, and reported before [11-
PO-CL process were obtained from the slope of the 15,18,23,24,31].
corresponding Arrhenius plots of lnkr vs. (1/T) (Fig. 8A) and
lnkf vs. 1/T (Fig. 8B) [38], and the resulting Ear and Eaf values REFERENCES
are compared in Table 3. The thermodynamic parameters of
activation ΔH‡ and ΔS‡ were calculated by using Eyring [1] A. Nishitan, Y. Tsukamoto, S. Kanda, K. Imai, Anal.

382
 Zargoosh et al.

Chim. Acta 251 (1991) 247. [22] M. Shamsipur, M.J. Chaichi, Spectrochim. Acta Part A
[2] B. Yan, S.W. Lewis, P.J. Worsfold, J.S. Lancaster, A. 61 (2005) 1227.
Gachanka, Anal. Chim. Acta 250 (1991) 145. [23] M. Shamsipur, A. Yeganeh-Faal, M.J. Chaichi, M.
[3] P.J. Kwakman, U.A. Brinkman, Anal. Chim. Acta 266 Tajbakhsh, A. Parach, Dyes Pigments 72 (2007) 113.
(1992) 175. [24] M. Shamsipur, A. Yeganeh-Faal, M.J. Chaichi, M.
[4] A.R. Bowic, M.G. Sanders, P.J. Worsefold, J. Tajbakhsh, A. Parach, Specrochim. Acta A 66 (2007)
Biolumin. Chemilumin. 11 (1996) 61. 546.
[5] A.M. Garćýa-Campaña, W.R.G. Baeyens, X. Zhan, in: [25] M. Hosseini, S. Dehghan Abkenar, M.J. Chaichi, M.
A.M. Garc´ýa-Campaña, W.R.G. Baeyens (Eds.), Shamsipur, Acta Chim. Slov. 55 (2008) 562.
Chemiluminescence in Analytical Chemistry, Marcell [26] M. Shamsipur, K. Zargoosh, S.M. Hosseini, C.
Dekker, New York, 2001, p. 41. Caltagirone, V. Lippolis, Spectrochim. Acta A 74
[6] C. Gooijer, M. Volthorst, Biomed. Chromatogr. 4 (2009) 205.
(1990) 925. [27] M. Shamsipur, K. Zargoosh, M.J. Chaichi, M.
[7] M.M. Nakamura, S.A. Saraiva, N. Coichev, Anal. Lett. Tajbakhsh, A. Parach, J. Lum. 130 (2010) 748.
33 (2000) 391. [28] A.G. Mohan, N.J. Turro, J. Chem. Edu. 51 (1947) 528.
[8] M. Shamsipur, M.J. Chaichi, Spectrochim. Acta 57A [29] D.A. Skoog, D.M. West, F.J. Holler, Fundamentals of
(2001) 2355. Analytical Chemistry, 6th ed., Orlando, Saunders HBJ,
[9] K. Nakashima, M. Wada, N. Kuroda, S. Akiyama, K. 1992, p. 860.
Imai, J. Liq. Chromatogr. 17 (1994) 2111. [30] S. Asghari, M. Qandalee, Acta. Chim. Solv. 54 (2007)
[10] M. Stigbrand, E. Ponten, K. Irgum, Anal. Chem. 66 638.
(1994) 1766. [31] A.G. Hadd, J.W. Birks, Selective Detectors in Chemical
[11] C.L.R. Catherall, T.F. Palmer, R.B.J. Cundall, J. Chem. Analysis Series, Vol. 131, Wiley, New York, 1995,
Soc., Faraday Trans. 2, 80 (1984) 823. p.209.
[12] A.G. Hadd, A.L. Robinson, K.L. Rowlen, J.W. Birks, J. [32] S.M. Silva, F. Casallanovo, K.H. Oyamaguchi,
Org. Chem. 63 (1998) 3023. L.F.L.M. Ciscato, C.V. Stevani, W.J. Baader,
[13] T. Wilson, Photochem. Photobiol. 62 (1995) 601. Luminescence 17 (2002) 313.
[14] F.M. Capra, Methods Enzymol. 305 (2000) 3. [33] R.S. Givens, R.L. Schowen, in: J.W. Birks (Ed.),
[15] M.M. Rauhut, L.J. Bollyky, B.G. Roberta, M. Loy, Chemiluminescence and Photochemical Reaction
R.H. Whitman, A.V. Iannotta, A.M. Semsel, R.A. Detection in Chromatography, VCH, New York, Chap.
Clarke, J. Am. Chem. Soc. 89 (1967) 6515. 5, 1989.
[16] R.E. Milofsky, J.W. Birks, J. Am. Chem. Soc. 113 [34] M. Orlovic, R.L. Schowen, R.S. Givens, F. Alvarez, B.
(1991) 9715. Matuszewski, N. Parekh, J. Org. Chem. 54 (1989) 3605.
[17] F.J. Alvarez, N.J. Parekh, B. Matuszewski, R.S. Givens, [35] J.L. Dye, V.A. Nicely, J. Chem. Educ. 48 (1971) 443.
T. Higuchi, R.L. Schowen, J. Am. Chem. Soc. 108 [36] J.H. Lee, J.C. Rock, M.A. Schlautman, E.R. Carraway,
(1986) 6435. J. Chem. Soc., Perkin Trans. 2 (2002) 1653.
[18] A.G. Hadd, A. Seeber, J.W. Birks, J. Org. Chem. 65 [37] C.L.R. Catherall, T.F. Palmer, R.B. Cundall, J. Chem.
(2000) 2675. Soc., Faraday Trans. 2 80 (1984) 837.
[19] M. Shamsipur, M.J. Chaichi, A.R. Karami, [38] C.V. Stevani, D.F. Lima, V.G. Toscano, W.J. Baader, J.
Spectrochim. Acta A 59 (2003) 511. Chem. Soc., Perkin Trans. 2 (1996) 989.
[20] M. Shamsipur, M.J. Chaichi, J. Photochem. Photobiol. [39] S.H. Lin, K.P. Li, H. Eyring, in: H. Eyring, D.
A 155 (2003) 69. Handerson, W. Yost (Eds.), Physical Chemistry, An
[21] M.J. Chaichi, A.R. Karami, A. Shockravi, M. Advanced Treatise, Vol. 2, Academic Press, New York,
Shamsipur, Spectrochim. Acta A 59 (2003) 1145. 1977.

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