Chemiluminescence characteristics of Furan derivatives as blue fluorescers in peroxyoxalate-hydrogen peroxide system

Article abstract of DOI:10.1007/s10895-012-1060-2

Furan derivatives (synthesized and purified in organic laboratories) are a great interest as fluorescent emitters for peroxyoxalate chemiluminescence. Reaction of peroxyoxalates such as bis-(2,4,6-trichloro-phenyl) oxalate with H²O² can transfer energy to fluorophore via formation of dioxetanedione intermediate. Furan derivatives used as a novel fluorescer in this study which produces a blue light in the chemiluminescence systems. The relationship between the chemiluminescence intensity and concentrations of TCPO, sodium salicylate, hydrogen peroxide and the fluorescer has been investigated. The linear ranges for Furan derivatives were 0.25-5×10^-4 M and 0.1-5×10^-4 M (A and B compounds, respectively). Kinetic parameters for the peroxyoxalate-chemiluminescence were also calculated from the computer fitting of the corresponding chemiluminescence intensity/time profiles. Springer Science+Business Media, LLC 2012.

Full text of DOI:10.1007/s10895-012-1060-2

J Fluoresc (2012) 22:1209–1216
DOI 10.1007/s10895-012-1060-2
ORIGINAL PAPER
Chemiluminescence Characteristics of Furan Derivatives as Blue
Fluorescers in Peroxyoxalate-Hydrogen Peroxide System
M. J. Chaichi & S. N. Azizi & M. Heidarpour &
O. Aalijanpour & M. Qandalee
Received: 22 October 2011 /Accepted: 3 May 2012 /Published online: 9 June 2012
#
Springer Science+Business Media, LLC 2012
Abstract Furan derivatives (synthesized and purified in
organic laboratories) are a great interest as fluorescent
emitters for peroxyoxalate chemiluminescence. Reaction
of peroxyoxalates such as bis-(2,4,6-trichloro-phenyl)
oxalate with H O can transfer energy to fluorophore
(CIEEL) [1], Mechanism with proven high quantum yields
[2]. This system consists of a base-catalyzed reaction of
activated oxalic phenylesters with hydrogen peroxide in
the presence of highly fluorescent aromatic hydrocarbons
with low oxidation potentials as chemiluminescent activa-
tors. Mechanistic studies using various oxalic esters and a
variety of experimental conditions led to the determination of
rate constants for several reaction steps as well as the proposal
of different high-energy intermediate structures [3–5]. The
increasing interest in the peroxyoxalate-chemiluminescence
(PO-CL) system is due to its high ability for the detection of
quenchers and analytical applicability as a sensitive tool for
studying and quantifying numerous analytes [6–12].
The development of reactions to produce heterocyclic
compounds is of vital importance in organic synthesis, es-
pecially the heterocycles which can be found in naturally
occurring products. A number of heterocyclic compounds
such as furan, and pyran rings are found in natural systems.
Furan rings, one example of five-membered heterocycles,
are found in many naturally occurring products [13]. The
furan ring is not only present as key structural unit in
naturally occurring products, but it is also important in the
pharmaceutical chemistry [14, 15].
2
2
via formation of dioxetanedione intermediate. Furan
derivatives used as a novel fluorescer in this study
which produces a blue light in the chemiluminescence
systems. The relationship between the chemilumines-
cence intensity and concentrations of TCPO, sodium
salicylate, hydrogen peroxide and the fluorescer has
been investigated. The linear ranges for Furan deriva-
−
4
−4
tives were 0.25–5×10 M and 0.1–5×10 M (A and
B compounds, respectively). Kinetic parameters for the
peroxyoxalate-chemiluminescence were also calculated
from the computer fitting of the corresponding chemilu-
minescence intensity/time profiles.
.
.
Keywords Peroxyoxalate chemiluminescence Fluorescer
.
.
TCPO Hydrogen peroxide Furan derivative
Introduction
In this paper, we report the study of chemilumines-
cence from the reaction of bis-(2, 4, 6-trichlorophenyl)
oxalate (TCPO) and hydrogen peroxide with three furan
derivatives as an efficient fluorescence brightener, in the
presence of sodium salicylate as a base catalyst. Three
Furan derivatives of Dimethyl 2-[(2,6-dimethylphenyl)
amino]-5-[(E)-2-phenyl-1-ethenyl]–3,4-furan dicarboxy-
late (A), Dimethyl 2-[(t-buthyl)amino]-5-[(E)-2-phenyl-
The peroxyoxalate-hydrogen peroxide system is the only
chemiluminescent reaction supposed to involve an intermo-
lecular chemically initiated electron exchange luminescence
:
:
:
M. J. Chaichi (*) S. N. Azizi M. Heidarpour O. Aalijanpour
Faculty of Chemistry, Mazandaran University,
Babolsar, 47416-95447, Islamic Republic of Iran
e-mail: jchaichi@yahoo.com
1
-ethenyl]-3,4-furan dicarboxylate (B) and Dimethyl 2-
[
(2,6-dimethylphenyl)amino]-5-[(E)-1-methyl-2-phenyl
M. Qandalee
vinyl]-3,4-furan dicarboxylate (C) were used (Fig. 1).
Tow Furan derivatives (A and B) are found intense
Department of Biology, Garmsar Branch, Islamic Azad University,
Garmsar, Iran

1
210
J Fluoresc (2012) 22:1209–1216
a
b
c
from the computer fitting of the corresponding chemilumines-
cence intensity-time plots.
Me
Me
O
O
O
O
H
Experimental
H
N
Me
O
Reagents
H
Me
TCPO was prepared from the reaction of 2,4,6-trichlorophe-
nol with oxalylchloride in the presence of triethylamine as
described elsewhere [16]. Hydrogen peroxide (Merck; Perhy-
drol Suprapur, 30 % in water) was assayed by permanganate
potassium titration [17]. The fluorescer was synthesized and
purified in organic laboratories. We described in detail the
preparation of polyfunctionalized furan ring by reaction of
alkyl isocyanides with dialkyl acetylenedicarboxylate in the
presence of trans-cinnamaldehyde. The yield of reaction for
production of the furan derivative was about 65 % [18]. The
mechanism of preparation of furans derivatives showed
Scheme 1.
Me
Me
O
O
O
O
H
H
N
O
H
tBu
Chemiluminescence Measurements
Me
Me
O
O
Chemiluminescence detection was performed with a home-
made apparatus equipped with a model BPY47 photocell
O
O
(
Leybold, Huerth, Germany). The apparatus was connected
H
H
N
Me
to a personal computer via a suitable interface (Micropars,
Tehran, Iran) as shown in Fig. 2 [19]. Experiments were
carried out with magnetic stirring (500 rpm) in a light-tight
flattened bottom glass cell of 15 mm diameter at room
temperature. The fluorescence spectra were recorded on a
Model LS-3B Perkin-Elmer instrument.
O
Me
Me
Fig. 1 Molecular structure of a Dimethyl 2-[(2,6-dimethylphenyl)
amino]-5-[(E)- 2-phenyl-1-ethenyl]-3,4-furan dicarboxylate b Dimeth-
yl 2-[t-buthyl amino]-5-[(E) 2-phenyl-1-ethenyl]-3,4-furan dicarboxy-
late c Dimethyl 2-[(2,6-dimethylphenyl)amino]-5-[(E)-1-methyl-2-
phenyl vinyl]-3,4-furan dicarboxylate
Procedures
Solution I was made with mixing 2 ml of TCPO (0.044 M)
and 0.05 ml of fluorescer (various concentrations in ethyl
acetate). Solution II contained 2 ml of 1.62 M hydrogen
peroxide and the 1 ml of sodium salicylate (0.04 M) in
methanol. Solution I was transferred into the instrument
quartz cuvette via polypropene syringes. Then 200 μl of
solution II was injected into the quartz cuvette and the
chemiluminescence spectrum was recorded after mixing of
the reagents in the cell.
and useful fluoropher compounds containing aromatic func-
tional group with low energy п→п* transition level (blue
light emission). Particularly, compounds A and B are suitable
for chemiluminesce proses as a fluorophore. But, exist one
CH group in a molecule C causes a quenching in chemilu-
3
minescence system. Kinetic parameters for the peroxyoxalate-
chemiluminescence of Tow Furan derivatives were calculated
Scheme 1 The mechanism of
preparation of furans
derivatives
MeO C
CO Me
2
2
H
O
CO Me
H
2
+
-
C
R'
Ph
H
+
+
R'
N
Ph
O
N
H
R
R
CO Me
Me
Me
2
t-Bu ,
R = H, Me
R' =

J Fluoresc (2012) 22:1209–1216
1211
Fig. 2 Shematic representation
of batch system for measuring
visible chemiluminescence
Results and Discussion
The final step is the emission of light energy by returning
the excited fluorophore molecule to the ground state. The
florescence spectra of compounds A and B are shown in
Fig. 3. The fluorescence and chemiluminscence of the
compound A is higher than that of B, at the same con-
ditions. The phenyl moiety on the nitrogen atom of A can
increase the resonance forms of it not only by additional
six π electrons in the benzene ring but also by the electron
with drawing properties of the ring. Overlap of p orbital
with the π bond results in the longer conjugated system in
A. With increasing of π conjugation, the energy difference
between HOMO and LUMO decrease, and led to the
feasibility of absorption and fluorescence of A.
The possible mechanisms of the PO-CL reaction with con-
sidering what reported in the literature are imaged in
Scheme 2 [7, 20, 21]. The intensity, duration and color of
emission of the PO-CL systems are of great importance [7].
In the first step, an aryl oxalate ester like TCPO reacts with
H O to produce a key chemical intermediate of 1,2- dioxe-
2
2
tandione (C O ) as an excitation source. The second step,
2
4
excited cyclic C O intermediate transfers its energy to fluo-
2
4
rophore (here Furan derivatives were used as fluorophore).
Cl
The displacement of hydrogen atom B with methyl group
in C led to the increasing steric hinderance near the furan
moiety. Flattering of a molecule has an important rule in the
conjugation of the delocalized π electrons especially in the
aromatic molecules. The methyl group can distort the bond
between double bond and the furan nucleous in the C
derivative. The plain contain phenyl and double bond with
methyl group in C must be rotate and therefor decrease the π
conjugation in C.
O
O
TCPO
+
H O
Cl
OH
R
+
2
2
O
O
Cl
R'
R
R'
O
O
O O
+
O
R''
R'''
O
R''
R'''
O
O
O
O
Charge transfer complex
Decreasing of π conjugation in C can cause to decrease
of resonance forms and lower fluorescence intensity of it.
Figures 4 and 5 show chemiluminescence intensity as a
function of time (intensity/time emission profile) for the
PO-CL system in the presence of varying concentrations
of furan derivatives A and B, respectively. Plot of chemilu-
minescence intensity as a function of fluorophore concen-
tration (compounds A and B) is inserted on top of right hand
side of Figs. 4 and 5 respectively. However, the plot of
reciprocals of CL intensity against furan derivatives resulted
in a linear calibration graph (Fig. 6), the linear ranges for
.
+
+
*
R'
R
. -
CO2
R'
R
electron
transfer
+
2 CO2
O
R''
CO
2
R'''
O
R''
R'''
R'
*
R
R'
R
hv
+
O
R''
O
R''
R'''
R'''
−4
compound A and B predicted 0.25–5×10 M and 0.1–5×
−4
Scheme 2 The mechanism of PO-CL reaction
10 M, respectively [6].

1
212
J Fluoresc (2012) 22:1209–1216
Fig. 3 The fluorescence
emission spectra of Dimethyl 2-
[
(2,6-dimethylphenyl)amino]-
5
3
-[(E)- 2-phenyl-1-ethenyl]-
,4-furan dicarboxylate (a) and
Dimethyl 2-[t-buthyl amino]-5-
(E) 2-phenyl-1-ethenyl]-3,4-
furan dicarboxylate (b) at same
[
–5
concentration of 5.0×10
M
with λex0330 nm
Plot of chemiluminescence intensity as a function of
fluorophore concentration (compounds A and B) is inserted
on top of right hand side of Figs. 4 and 5 respectively.
Correlation between the CL intensity and the TCPO con-
centration for both fluorophore is listed in Tables 1 and 2.
The influence of H O concentration on the PO-CL for both
sodium salicylate, the CL response of the H O , TCPO,
2
2
fluorescers system were measured against the varying con-
centrations of the base and the resulting plot is shown in
Fig. 8. The PO-CL intensity increased with increasing con-
centration of sodium salicylate until a concentration of 1.0×
−
3
10 M is reached, the observed intensity enhancement
being indicative of the catalytic effect of the sodium salicylate.
However, further addition of sodium salicylate revealed a
gradual decrease in the CL intensity. This is most probably
due to a quenching effect of the base at higher concentrations,
which begins to decompose the reactive intermediate, dioxe-
tane dione, and hence reduces the PO-CL light [22].
2
2
compounds A and B was studied at constant concentrations
of other reagents and presented in Tables 1and 2.
Figure 7a and b show the influence of H O concentra-
2
2
tion on the PO-CL of fluorescer, there is a direct linear
relationship between the concentration of hydrogen perox-
ide and CL intensity of the system. It is noteworthy that
further increase in H O concentration was found to have no
The results show that the concentration of TCPO and
fluorescer have a more significant influence on the chemi-
luminescence system, than the concentrations of H O and
2
2
measurable effect on the PO-CL intensity [7].
The observed behavior is clearly indicative of the cata-
lytic effect of sodium salicylate on the PO-CL system stud-
ied [3]. In order to investigate the optimal concentration of
2
2
sodium salicylate i.e., on the rise (k ) and fall (k ) rates
r
f
constants. In the former case, by increasing concentration
Fig. 4 Chemiluminescence emission intensity as a function of time for
Fig. 5 Chemiluminescence emission intensity as a function of time for
the TCPO-H
2
O
2
-furan derivatives (and sodium salicylate) system with
the TCPO-H
2 2
O -furan derivatives (and sodium salicylate) system with
−
2
−2
–2
−2
constant concentration of TCPO (3.2×10 ), H
O
2 2
(8.0×10 ), sodium
constant concentration of TCPO (3.2×10 ), H O (8.0×10 ), sodium
salicylate (1.0×10 ), and varying concentrations of of Dimethyl 2-[t-
2 2
salicylate (1.0×10− ), and varying concentrations of Dimethyl 2-[(2,6-
3
−3
dimethylphenyl)amino]-5-[(E)- 2-phenyl-1-ethenyl]-3,4-furan dicar-
buthyl amino]-5-[(E) 2-phenyl-1-ethenyl]-3,4-furan dicarboxylate: (1)
−
4
−4
−4
−5
−4
−4
−4
−5
−5
boxylate: (1) 5×10 (2) 2.5×10 (3) 1.0×10 (4) 7.5×10 (5) 5×
5×10 (2) 2.5×10 (3) 1.0×10 (4) 7.5×10 (5) 5×10 (6) 2.5×
−
5
−5
−5
1
0
(6) 2.5×10
10

J Fluoresc (2012) 22:1209–1216
1213
In order to evaluate the kinetic data for the PO-CL system
studied from the resulting CL intensity–time plots, a pooled
intermediate model was used [23, 24]. According to this
model, the CL reaction is simplified as:
kr
Kf
Aꢀꢀ ꢀꢀ ! Bꢀꢀ ꢀꢀ ! C
ð1Þ
where A, B and C represent pools of reactants, intermediates
and products, respectively, and both reaction steps designated
by the rate constants k and k are irreversible first order
r
f
reactions. The integrated rate equation for the CL intensity
versus time is:
ꢀ
ꢁ
M
ꢄ
ꢂ
ꢃꢅ
Fig. 6 Effect of furan derivatives concentration on the CL intensity of
It ¼
expðꢀk tÞ ꢀ exp ꢀk t
ð2Þ
r
f
a TCPO-H
phenyl-1-ethenyl]-3,4-furan dicarboxylate- Sodium salisylate and b
TCPO -H -/Dimethyl 2-[t-buthyl amino]-5-[(E) 2-phenyl-1-
2
O
2
-/Dimethyl 2-[(2,6-dimethylphenyl)amino]-5-[(E)- 2-
kf ꢀ kr
2
O
2
where I is the CL intensity at time t, M is a theoretical
maximum level of intensity if the reactants were entirely
t
ethenyl]-3,4-furan dicarboxylate- Sodium salisylate system
converted to a CL-generating material, k and k are, respec-
r
f
tively, the first order rate constants for the rise and fall of the
burst of CL. A further advantage of this model is that it not
only allows the determination of parameters M, k and k , but
of TCPO, the values of fall rates constant (k ) become larger,
on the other hand, enhancing concentration of fluorescer
caused to decrease of kf .
f
r
f
also it permits an estimate of the intensity at maximum level
Table 1 CL parameters calculated from computer fitting of the CL intensity-time plots for TCPO-H2O2- Dimethyl 2-[(2,6-dimethylphenyl)
amino]-5-[(E)-1-methyl-2-phenylvinyl]-3,4-furan dicarboxylate sodium salicylate system
−
1
−1
Parameter changed
Concentration
M)
K
r
(min
)
K
f
(min
)
M
J
T
(min)
ex
τ
max(min)
Y
I
(
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
2
2
2
2
2
2
2
2
2
2
3
3
4
4
4
4
H
2
O
2
8×10
4.40±0.20
4.05±0.23
4.35±0.19
3.92±0.15
3.82±0.14
5.64±0.28
5.07±0.23
4.41±0.16
5.38±0.21
4.36±0.14
4.23±0.25
4.80±0.27
4.73±0.24
4.65±0.22
4.57±0.21
3.72±0.20
4.56±0.21
4.51±0.20
4.01±0.41
3.84±0.21
2.45±0.18
2.30±0.36
0.48±1.83
0.27±1.35
0.39±1.54
0.41±1.48
0.62±1.88
0.64±0.02
0.47±1.74
0.34±1.18
0.37±1.26
0.24±0.02
0.62±0.76
0.76±3.32
0.58±2.31
0.38±1.69
0.40±1.60
1.12±4.69
0.70±0.25
0.85±0.21
1.21±0.11
1.84±0.31
2.45±0.32
2.30±0.36
2683.10±11.23
2149.16±39.59
1915.00±7.56
730.69±13.09
307.56±5.86
2340
2015
1520
560
0.33
0.27
0.43
0.35
0.45
0.43
0.31
0.46
0.35
0.41
0.42
0.29
0.28
0.27
0.32
0.29
0.32
0.28
0.29
0.28
0.28
0.24
0.46
0.42
0.46
0.48
0.52
0.37
0.51
0.52
0.45
0.49
0.48
0.34
0.32
0.47
0.52
0.35
0.47
0.37
0.41
0.32
0.37
0.23
3104.16
2872.33
2242.41
1358.11
491.35
2490
2230
1760
625
6
4
2
1
×10
×10
×10
×10
216
244
TCPO
3.2×10
3072.73±74.36
2014.78±39.08
1098.66±16.85
886.78±13.93
530.02±74.36
3045.72±52.86
2141.10±90.44
2310.27±55.13
1892.83±39.60
816.24±16.02
489.37±15.90
3210.01±620
2843.01±78.60
1718.66±84.30
1584.27±43.20
1224.35±242.90
891.55±77.70
2321
1780
880
3752.40
2285.95
1194.14
943.60
2960
1990
1230
780
1
0
0
0
.6×10
.8×10
.4×10
.2×10
820
446
730.39
466
Sodium salycilate
1.2×10
2354
1896
2020
1710
676
3269.13
2800.00
2650.00
2010.00
820.00
2460
2120
2450
1940
790
1
8
6
4
.0×10
.0×10
.0×10
.0×10
Dimethyl 2-[(2,6-dimethyl
phenyl)amino]-5-[(E)-1-
methyl-2-phenylvinyl]-
2.0×10
312
340.00
360
−4
5
2
1
7
5
2
.0×10
.5×10
.0×10
.5×10
.0×10
.5×10
3123
2620
1312
993
2931.32
2351.12
1731.15
1547.14
915.56
3084
1998
1550
1008
884
−
−
−
−
−
4
4
5
5
5
3
,4-
724
523
406.97
695
Statistical parameters R00.964 F0266.390 correlation is significant at the 0.01 level

1
214
J Fluoresc (2012) 22:1209–1216
Table 2 CL parameters calculated from computer fitting of the CL intensity-time plots for TCPO-H
2 2
O - Diethyl 2-[(t-buthyl amino)]-5-[(E)-1-
methyl-2-phenylvinyl]-3,4-furan dicarboxylate sodium salicylate system
−1
−1
Parameter changed
Concentration (M)
K
r
(min
)
K
f
(min
)
M
J
Tex (min)
τ
max (min)
Y
I
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
2
2
2
2
2
2
2
2
2
2
3
3
4
4
4
4
H
2
O
2
8×10
4.119±0.19
4.08±0.17
4.298±0.19
3.79±0.15
4.28±0.16
5.69±0.31
5.07±0.23
4.15±0.18
3.22±0.30
3.97±0.31
4.01±0.19
4.83±0.24
4.06±0.19
4.02±0.19
3.98±0.21
2.63±0.27
4.49±0.22
4.42±0.23
4.30±0.31
3.24±0.26
3.15±0.28
2.95±0.28
0.55±1.93
0.38±1.36
0.39±1.60
0.46±1.61
0.29±1.13
0.67±0.83
0.47±1.741
0.34±1.37
0.28±0.31
0.24±0.02
0.56±0.76
0.49±2.02
0.52±2.65
0.68±2.28
1.69±3.41
2.63±0.27
0.62±0.25
0.701±0.21
1.33±1.02
3.24±0.26
3.15±0.28
2.95±0.23
2554.22±78.39
1976.67±35.11
1395.28±12.87
1024.21±19.41
704.89±56.57
3072.73±74.36
2014.78±39.08
1598.66±16.85
886.78±13.93
530.02±74.36
3045.72±52.86
3111.47±71.94
2525.25±63.92
1804.11±42.34
1230.23±35.32
959.81±79.00
3355.01±62.00
2724.70±72.60
1783.60±83.20
1582.49±153.00
926.95±126.00
755.95±224.00
1976
1572
912
0.44
0.34
0.33
0.36
0.36
0.28
0.31
0.44
0.29
0.23
0.42
0.40
0.37
0.33
0.30
0.34
0.32
0.27
0.27
0.27
0.27
0.26
0.56
0.43
0.42
0.48
0.45
0.33
0.34
0.54
0.30
0.24
0.48
0.50
0.49
0.47
0.42
0.37
0.43
0.36
0.34
0.30
0.31
0.33
3326.33
2387.71
1802.72
1049.28
846.62
3050
2330
1510
750
6
4
2
1
×10
×10
×10
×10
711
294
315
TCPO
3.2×10
2218
1780
1075
670
3012.00
1957.00
1689.00
943.00
3390
2150
1172
759
1
0
0
0
.6×10
.8×10
.4×10
.2×10
359
478.00
450
Sodium salycilate
1.2×10
2354
2660
1990
1340
990
3269.13
3386.96
2697.82
1996.53
1746.23
978.64
2460
3230
2180
1590
1160
670
1
8
6
4
.0×10
.0×10
.0×10
.0×10
Diethyl 2-[t-buthyl amino]-5-[(E)-
-methyl-2-phenylvinyl]-3,4
furan dicarboxylate
2.0×10
663
1
-
−4
5
2
1
7
5
2
.0×10
.5×10
.0×10
.5×10
.0×10
.5×10
3298
2230
1355
993
4159.35
3285.16
1338.91
979.33
3950
2664
1997
1158
860
−4
−4
−5
−5
−5
863
532.60
502
475.20
452
Statistical parameters R00.965 F0272.059 correlation is significant at the 0.01 level
Fig. 7 Dependence of the H
TCPO-H - Dimethyl 2-[(2,6-dimethylphenyl)amino]-5-[(E)- 2-
phenyl-1-ethenyl]-3,4-furan dicarboxylate -Sodium salisylate system, b
on the CL intensity of TCPO-H -Dimethyl 2-[t-buthyl amino]-5-[(E)
-phenyl-1-ethenyl]-3,4-furan dicarboxylate -Sodium salisylate system
2
O
2
concentration a on the CL intensity of
Fig. 8 Dependence of the Sodium salicylate concentration a on the CL
intensity of TCPO-H Dimethyl 2-[(2,6-dimethylphenyl)amino]-5-[(E)-
2-phenyl-1-ethenyl]-3,4-furan dicarboxylate -Sodium salicylate system, b
on the CL intensity of TCPO-H - Dimethyl 2-[t-buthyl amino]-5-[(E) 2-
phenyl-1-ethenyl]-3,4-furan dicarboxylate -Sodium salicylate system
2
O
2
2 2
O
O
2
2 2
O
2
2

J Fluoresc (2012) 22:1209–1216
1215
Fig. 9 A typical computer fitting of the CL intensity-time plot TCPO-
dimethylphenyl)amino]-5-[(E)- 2-phenyl-1-ethenyl]-3,4-furan
−
4
−2
H
2
O
2
- Dimethyl 2-[(2,6-dimethylphenyl)amino]-5-[(E)- 2-phenyl-1-
ethenyl]-3,4-furan dicarboxylate -Sodium salicylate system. [H ]0
.08 M, [Sodium salicylate]01.0×10−3 M, Dimethyl 2-[(2,6-
dicarboxylate05×10 M and [TCPO]03.2×10 M: (X) experimen-
tal point; (o) calculated point; (0) experimental and calculated points
are the same within the resolution of the plot
2 2
O
0
(
J), the time of maximum intensity (τmax) and the total light
typical computer fit of the CL intensity time plots is shown
in Figs. 9 and 10. The other parameters J, τmax and Y were
then evaluated from Eqs. (3) to (5) using the k , k and M
yield (Y), as follows:
r
f
ꢆ
ꢇ½kf =ðkf ꢀkrÞꢁ
values. The kinetic parameters thus obtained for all experi-
ments carried out are summarized in Tables 1 and 2.
kf
J ¼ M
ð3Þ
ð4Þ
kr
2
The statistical results (R and F) obtained by application
ꢂ
ꢃ
of SPSS indicate that, there is a satisfactory agreement
between the calculated (J) and experimental (Imax) values
of the intensity at the maximum CL (Tables 1 and 2).
ln kf =kr
kf ꢀ kr
tmax
¼
Z
1
M
Y ¼
Itdt ¼
ð5Þ
Conclusion
kf
0
In this work, a non-linear least-squares curve fitting pro-
The present study describes a chemiluminesecence system
of H O - bis-(2,4,6-trichlorophenyl) oxalate (TCPO) using
gram KINFIT [25] was used to evaluate the M, k and kf
r
2 2
values from the corresponding CL intensity–time plots. A
furan derivatives as fluorescer. In this system, the blue
Fig. 10 A typical computer fitting of the CL intensity-time plot
TCPO-H - Dimethyl 2-[t-buthyl amino]-5-[(E) 2-phenyl-1-
ethenyl]-3,4-furan dicarboxylate -Sodium salicylate system.
buthyl amino]-5-[(E) 2-phenyl-1-ethenyl]-3,4-furan dicarboxylate0
−
4
−2
2
O
2
5×10 M and [TCPO]03.2×10 M: (X) experimental point; (o)
calculated point; (0) experimental and calculated points are the same
within the resolution of the plot
2 2
[H O
]00.08 M, [Sodium salicylate]01.0×10− M, Dimethyl 2-[t-
3
(

1
216
J Fluoresc (2012) 22:1209–1216
9
. Hadd AG, Birks JW (1995) Chemical analysis. Selective detectors.
Wiley, New York, p 209
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higher than that of B, at the same conditions. Also, the
results indicated that how concentrations of the components
involved in CL influence on the light emission. Kinetic
parameters for the peroxyoxalate-chemiluminescence of
fluorescer were calculated from the corresponding chemilu-
minescence intensity-time plots. A non-linear least-squares
curve fitting program KINFIT was used to evaluate the
theoretical maximum level of intensity (M), the first order
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1
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r
f
The furan studied derivatives were found to be an intense
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1
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