Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130

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Journal of Photochemistry and Photobiology B: Biology

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A novel development of dithizone as a dual-analyte colorimetric

chemosensor: Detection and determination of cyanide and cobalt (II)
ions in dimethyl sulfoxide/water media with biological applications
Hossein Tavallali , Gohar Deilamy-Rad, Abolfath Parhami, Seyede Zahra Mousavi
Department of Chemistry, Payame Noor University, 71955-1368 Shiraz, Islamic Republic of Iran

a r t i c l e i n f o a b s t r a c t

Article history: The behavior of dithizone (DTZ), an easily available dye has been studied for the rst time in chromogenic
Received 30 January 2013 sensing of CN as an anionic species and for Co2+ as a cationic species in DMSO/H2O media. So employing
Received in revised form 27 May 2013 DTZ an efcient colorimetric chemosensor was afforded with a chromogenic selectivity for Co2+ over
Accepted 29 May 2013
other cations with detection limit of 0.04 lmol L1. The complex of Co2+ with DTZ also displayed ability
Available online 7 June 2013
to detect up to 0.43 lmol L1 CN (K+ salts) among other competing anions through a fast response time
of less than 30 s which is much lower than most recently reported chromogenic probes. The linear
Keywords:
dynamic ranges for the determination of Co2+ and CN were 0.34.4 and 3.358.6 lmol L1 respectively.
Colorimetric chemosensor
Naked-eye detection
This method could have potential application in a variety of cases requiring rapid and accurate analysis of
Dithizone Co2+ and CN for human serum and water samples.
Cyanide 2013 Elsevier B.V. All rights reserved.
Cobalt (II)

1. Introduction utilization of hydrogen bonding in the development of receptors

There is an increasing interest in the development of a new gen-
eration of molecules for the sensing of target chemical species of
environmental or biological interest. Among them, chromogenic
receptors are especially attractive because the recognition process
is accomplished with an easy-to-detect perceptible color evolution.
Signicant efforts have been carried out in the last years for under-
standing the theoretical basis of the chromogenic guest recognition
and a number of selective chemosensors for anions, cations, and
neutral species have been designed and synthesized [1,2].
The determination of trace amounts of cobalt in water is of
great interest because cobalt is important for living species as com-
plexed Vitamin B12. The deciency of cobalt in humans and ani-
mals results in anemia [3], while large amounts of cobalt lead to
toxic effects (vasodilatation, ushing and cardiomyopathy), usually
after occupational exposure to cobalt dusts (cobalturia, cobalt-
emia) [4]. Since one of routes of incorporation of cobalt into the hu-
man body is by ingestion, therefore its determination in drinking
water becomes very important. Because the cobalt concentration
levels are very low in water samples, sensitive analytical tech-
niques are required to obtain low detection limits.
Anions play important role in chemical, biological and environ-
mental processes. An important aspect of modern chemistry is the
Corresponding author. Tel.: +98 917 315 3520; fax: +98 711 622 2249.
E-mail addresses: Tavallali@pnu.ac.ir, Tavallali@yahoo.com (H. Tavallali).
for recognition of anions [5]. Although cation receptors have been
studied for more than four decades but the development of anion
receptors received less attention. Several reasons why reliable
sensing of anions is a particularly challenging area of research
are: (i) anions are larger than isoelectronic cations and, therefore,
have lower charge-to-radius (surface) ratio, a feature that makes
the electrostatic binding of anions to the receptors less effective
[6], (ii) anions have a wide range of geometries and are often pres-
ent in delocalized forms, which results in higher complexity in de-
sign and synthesis of receptors and (iii) pH sensitivity. Therefore, to
achieve the desired selectivity, the combination of electrostatic
attraction, hydrogen bonding and a suitable framework onto which
these structural components can be assembled needs to be taken
into consideration when designing articial anionic hosts [7].
Among various anions, cyanide is one of the most concerned an-
ions because it is being widely used in synthetic bers, resins, her-
bicide, and the gold-extraction process [8]. Unfortunately, cyanide
anion is extremely detrimental, and could be absorbed through
lungs, gastrointestinal track, and skin, leading to vomiting, convul-
sion, loss of consciousness, and eventual death [9]. According to
the World Health Organization (WHO), only water with cyanide
concentration lower than 1.9 lM is drinkable [10]. Thus, there ex-
ists a need for an efcient sensing system for cyanide to monitor its
concentration from contaminant sources.
As a result, the detection of cyanide has attracted considerable
attention in recent years, and many cyanide sensors have been

1011-1344/$ - see front matter 2013 Elsevier B.V. All rights reserved.
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122 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130
developed [1115]. Several strategies for detecting cyanide have
been developed based on uorogenic and chromogenic organic
dyes [11], semiconductor nanoparticles [12], chromatography
[13], electrochemical sensors [14] and polymers [15]. Colorimetric
chemosensors are particularly attractive because they can be read
by the naked eye, and in some cases at the point of use.
To date, many of the reported cyanide anion receptors have re-
lied on hydrogen-bonding motifs and, as a consequence, have dis-
played poor selectivity in aqueous media [16]. To overcome this
limitation, reaction-based receptors have been developed recently
[17,18]. This reaction-based recognition mode takes advantage of
the particular feature of the cyanide ion: its good nucleophilic
character and little competition from the aqueous media. However,
many receptors for cyanide reported [1618] so far, they have sev-
eral limitations such as poor selectivity over F or AcO, or utiliza-
tion of expensive instruments, complicated synthesis, and many of
receptors are reported to work only in organic media. According to
the literature, there are a few methods able to detect the cyanide
anions in pure water [1925] using water soluble polymers [20],
glycoconjugation [21,22], glycerilation [23], surface functional
modication of nanocrystalline TiO2 lms or membrane anchored
with an azo dye [24] and the biosourced plastic lm starting from
starch [25].
During last thirty years, these receptors and other many organic
based synthetic anion receptors that have been reported [26,27],
are rather difcult to synthesize or require expensive instruments
for detections. Taking this dilemma into consideration recently, we
have undertaken an extensive research program to explore bromo
pyrogallol red (BPR) as an easily available dye demonstrated a high
chromogenic receptor for cations and anions [2830]. In this work,
we report new applications of dithizone (DTZ). DTZ is considered
as a selective and sensitive ligand to prepare specic sorbents for
heavy metal removal and preconcentration. Polymeric supports
loaded with dithizone were used for preconcentration of mercury
from seawater but with little success [31].
This dye demonstrates a high chromogenic sensing ability for co-
balt (II) in DMSO/H2O (75:25 v/v) media and in continuation, we
wish to report a new probe molecule ([Co(DTZ)2]2+ complex) for
highly selective cyanide detection in the same media. This chemod-
osimeter has shown a selective and sensitive response to cyanide an-
ion over other various anions through a nucleophilic addition
reaction of the cyanide to the probe molecule. The strong nucleophi-
licity of cyanide will make the described cyanide-probe more feasi-
ble working as a reaction-based chemodosimeter. The mode of
interaction of cyanide was also studied by UVVis, 1 H NMR and IR
spectroscopy to be via the nucleophilic attack to the N atom (azo
group) on the chemosensor. According to our knowledge, DTZ has
not still been used for determination of anionic species.
2. Experimental
2.1. Reagents
Reagents with analytical grades and demineralized water were
used for preparing the solutions. DTZ (dithizone; (E)-1, 5-diph-
enylthiocarbazone) was purchased from Merck, and used without
further purication. Stock solutions (1.0  101 mol L1) of Na+,
K+, Co2+, Rb+, Ba2+, Mn2+, Cr3+, Al3+, Zr4+, Ce3+, Mg2+, Cd2+,W6+,
Bi3+, Ag+, Hg+, Cu2+ and Sn2+ were prepared by direct dissolution
of proper amounts of nitrate salts of Na+, K+, Ba2+, Mn2+, Cr3+,
Ce3+, Cd2+, Mg2+, Bi3+, Ag+, Hg+ and Cu2+ chloride salts of Co2+,
Sn2+ and Rb+, zirconium oxychloride and phosphotungestic acid
(were purchased from Merck) in deionized water. Stock solutions
(1.0  101 mol L1) of anions were prepared by direct dissolution
of proper amounts of potassium salts of anions. Working standards
were prepared daily by serial dilutions from the 1.0  101 -
mol L1. DMSO was dried with CaH2 and then distilled in reduced
pressure.
2.2. Apparatus
A Shimadzu 1601 PC UVVis spectrophotometer with a quartz
cuvette (path length = 1 cm) was used for recording all spectra
and absorbance measurements are in the wavelength range of
200700 nm. FT-IR spectra were recorded on a Bruker Vector 22
Fourier Transmission Infrared spectrometer with wave numbers
in the range of 4004000 cm1. Elemental analyses were per-
formed by a VARIO EL-III (German) element analytical instrument.
ICP-AES Varian, Vista-pro (Salt lake city, Australia) was used for
measuring the concentration of Co (II). 1H NMR spectra were
measured with Varian unity plus 400 MHZ spectrometer using
tetramethylsilane (TMS) as an internal standard. A Jenway 3510
pH-meter which calibrated against two standard buffer solutions
at pH 4.0 and 10.0 was used to measure the pH of the solutions.
A Hamilton syringe (10 lL) was used to deliver small volumes of
reagent into the cell. DMSO/H2O (75:25 v/v) was used as the
solvent in the reference cell. All measurements were made in the
absorbance mode.
2.3. pH measurement procedure
The pH was measured in aqueous organic solvents, taking into
account the reference pH values of primary standard buffer solu-
tions, pHS, for the standardization of potentiometric sensors in or-
ganicwater mixtures. The knowledge of pHs values allows one to
perform pH measurements in a mixed solvent as easily as in water
taking into account the operational denition of pH [32]:
pHX pHS ES  EX =K g 1
where the unknown pH of solution X, pHX, is related to the pH of a
standard reference solution, pHS, and the emf values of the potenti-
ometric cell contain the standard, ES, and the unknown solution, EX.
Kg must be used for practical measurements (Kg = (ln 10) RT/F), usu-
ally carried out in cells with glass electrodes, and corresponds to the
practical slope of the E verses pH function. Thus, the availability of
standard buffer solutions of known pH (Phosphate buffer: KH2PO4
(0.025 mol L1) + NaH2PO4 (0.025 mol L1) in DMSO/H2O media),
in the desired solvent mixture, is the key to pH measurements in
these media [32].
2.4. General methods
All titration experiments were carried out at 298.2 K, unless
otherwise mentioned. 2.5 mL solution of DTZ (1.0  104 mol L1)
in DMSO/H2O (75:25 v/v) was transferred to the quartz cuvette
and the absorption spectra was recorded immediately. Changes
in the UVVis absorption spectrum of DTZ upon addition of
2.0  1077.8  105 mol L1 of chloride salt of Co(II)
(5.0  105 mol L1) were used for complexation studies.
The presence of Co2+ resulted in the red shift in wavelength of
maximum absorption from 475 to 482 nm and reduced the absor-
bance intensity in both 475 and 610 nm (Fig. 1a), which resulted
in a color change of the solution from green to red (Fig. 1b). The
[Co(DTZ)2]2+ has been proved to be suitable chromogenic chemo-
sensor for anion sensing. Thus, changes in the visible spectrum were
recorded in DMSO/H2O (75:25 v/v) solution of this receptor upon
addition of 1.0  102 M of F, Cl, Br, I, HSO  
4 , CH3COO (AcO ),
C6H5COO (BzO), NO3, H2PO4, CN, and SCN anions as their
potassium salts in water solutions. Titration of [Co(DTZ)2]2+ complex
with CN resulted in the blue shift in wavelength of maximum
absorption from 482 to 475 nm and reduced the absorbance
 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130
Fig. 1. (a) Changes in the UVVis absorption spectrum of DTZ (1.0  104 mol L1)
in DMSO/H2O (75:25 v/v) upon addition of 07.8  105 mol L1 Co(Cl)26H2O in
pH = 5.7. Inset: the stoichiometry analysis of Co2+ complex by Job plot analysis; at
298 0.1 K, (kmax = 610 nm) and (b) Color change 1.0  104 mol L1 DTZ in DMSO/
H2O (75:25 v/v) and after addition of 7.8  105 mol L1 Co2+ ([Co(DTZ)2]2+
complex). (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.)
intensity in 610 nm for [Co(DTZ)2]2+, as this was the only anion
which produced a color change from red to orange. The solutions
of cobalt (II) chloride and potassium cyanide with known concentra-
tions are used as spiked real samples.
2.5. Sample preparation
Water samples were collected from three main sources in May
2012: (1) tap water used as drinking water in Shiraz, Iran (2) run-
ning water from Ghare Aghaj River Firooz Abad, Iran and (3) rain
water from precipitation in Shiraz, Iran. The water samples ana-
lyzed were collected in pre-washed (with detergent, tap water, di-
lute HNO3 and doubly deionized distilled water, respectively)
polyethylene bottles. Before the analysis, the samples were ltered
through a cellulose membrane lter (Millipore) of pore size
0.45 lm. The organic content of the water samples was then oxi-
dized in the presence of 1% H2O2 (30%) and through the addition
of concentrated nitric acid. After acidication to 1% with concen-
trated nitric acid, they were stored in pre-washed polyethylene
bottles in the refrigerator. Standard solution 1.0  101 mol L1
of CN and Co(II) were prepared through dissolution of specied
amounts of potassium cyanide and Co(II) chloride salts in 100 mL
of deionized water. Working standards were prepared daily by se-
rial dilutions from the 1.0  101 mol L1 concentrate. The solu-
tions of potassium cyanide and Co(II) chloride salts with known
concentrations are used as spiked real samples.
The serum sample was prepared from hospital (Namazi, Shiraz).
A 0.5 mL of serum sample was spiked with suitable amount of
standard stock solution of sodium cyanide and analyzed by the
123
proposed method. Recovery experiments were carried out by spik-
ing the samples at three CN levels, namely 25, 50 and 100 lg L1.
3. Results and discussion
3.1. Colorimetric analysis
3.1.1. Cation sensing
The sensing ability of DTZ in DMSO/H2O (75:25 v/v) towards
cations such as Na+, K+, Co2+, Rb+, Ba2+, Mn2+, Cr3+, Al3+, Zr4+, Ce3+,
Mg2+, Cd2+, W6+, Bi3+, Ag+, Hg+, Cu2+ and Sn2+ were tested by color-
imetric analysis. In naked-eye inspection, the color of DTZ changes
from green to red upon the addition of 7.8  105 mol L1 of Co2+
(Fig. 1b). It is noteworthy, that no signicant color changes were
observed in presence of other cations. The dramatic color change
reveals the complex formation between the cation and the recep-
tor, thus, resulting in visual examination.
3.1.2. Anion sensing
The sensing ability of Co2+DTZ complex in DMSO/H2O (75:25
v/v) towards anions such as F, Cl, Br, I, HSO  
4 , AcO , BzO ,
   
NO3 , H2 PO4 , CN , and SCN were studied by colorimetric
(naked-eye) and UVVis studies. In colorimetric analysis, to a mix-
ture including 2.5 mL solution of DTZ (1.0  104 mol L1 in DMSO/
H2O 75:25 v/v) and 0.81 mL of Co2+ (5.0  105 mol L1), was
added different amounts of potassium salts of anions (5.0  101 -
mol L1) in water. In visual investigation, the red solution of
[Co(DTZ)2]2+ complex changes to orange on the addition of CN
ion. The receptor did not show any color change for other anions.
Thus the [Co(DTZ)2]2+ could sense CN ion selectively in the pres-
ence of other anions. The observed selectivity is suggested to be
due to the stronger nucleophilicity of cyanide regarding other an-
ions which make the cyanide-probe complex more feasible and of-
ten work as a chemodosimeter.
3.2. UVVis studies
3.2.1. Cation sensing
The visible spectrum of the DTZ in DMSO/H2O (75:25 v/v) is
characterized by two main bands at about 475 and 610 nm, which
are responsible for the green color of the solution. Titration of DTZ
with Co2+ resulted in the red shift in wavelength of maximum
absorption from 475 to 482 nm as well as decreasing the absor-
bance intensity in both 475 and 610 nm (Fig. 1a), which caused
the color change of the solution from green to red (Fig. 1b). The
intensity of the band in 475 nm was monitored upon addition of
Co2+, which allowed us to determine the complex stability con-
stants. Co2+ is able to change the color of the DTZ probably by a
suitable coordination with nitrogen and sulfur atoms of DTZ as
the only coordinating atoms present in the compound. It is conjec-
tured that the connection of cobalt with DTZ can be attributed to
the formation of penta-heterocycles chelating complex between
Co2+ and dithizone molecule, where nitrogen and sulfur atoms
serve as donors as illustrated in Scheme 1.
Titration of DTZ with Co2+ indicated the formation of the 2:1
(DTZ:Co2+) binding ratio by Jobs plot analysis. The measured
absorbance variation at 610 nm (DA = Aabs  Ai) reaches to a max-
imum when the molar fraction of ([Co2+]/[Co2+] + [DTZ]) is 0.33,
conrming the 2:1 (DTZ:Co2+) stoichiometry (inset Fig. 1a). The
association constants were determined by nonlinear tting analy-
sis of the titration curves according to the hostguest complexa-
tion [33]. The calculated Kass was 2.51(0.18)  109 (L mol1)2 for
the formation of [Co(DTZ)2]2+ complex. In fact, Co2+ ions, among
the metals studied here gives the strongest complexes with DTZ.
For more condence we studied the stability of the receptor
124 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130

Scheme 1. The proposed host-guest binding mode in the presence of Co2+ and cyanide ion in DMSO/H2O (75:25 v/v) media.

complex versus pH by drawing the A/A0 parameter at 610 nm. The

results showed maximum stability around pH = 5.7 (Fig. 2). It is
interesting that the initial pH is 5.7 just after addition of Co2+
and DTZ in DMSO/H2O (75:25) and so there is no need to adjust
pH before subsequent addition of anions.

3.2.1.1. Sensing in the presence of competing cations. To enquire the

selectivity for measurement of Co2+ in the presence of other cat-
ions, the competition experiments were conducted in the presence
of Co2+ (250.0 lg L1) mixed with 250.0 lg L1 of other cations
involving Na+, K+, Rb+, Ba2+, Mn2+, Cr3+, Al3+, Zr4+, Ce3+, Mg2+,
Cd2+, W6+, and 150 lg L1 interfering ions involving Bi3+, Ag+,
Hg+, Cu2+ and Sn2+. Subsequently the absorbance was measured
at 610 nm. It is gratifying to note that all the selected cations have
no interference (Fig. 3).

3.2.2. Anion sensing

The UVVis absorption is one of the most interesting output sig-
Fig. 3. Absorbance responses of DTZ (1.0  104 mol L1 in DMSO/H2O (75:25 v/v))
nals not only because the instrumentation is widely available, but to Co2+ (250 lg L1) in the presence of mixed cations (250.0 lg L1 of Na+, K+, Rb+,
also because it would be possible to sense target species with the Ba2+, Mn2+, Cr3+, Al3+, Zr4+, Ce3+, Mg2+, Cd2+, W6+, and 150 lg L1 interfering ions
naked eye. In order to gain systematic knowledge on the effect of involving Bi3+, Ag+, Hg+, Cu2+ and Sn2+).
water on the binding afnity and selectivity for cyanide, we choose
482 nm being signicantly increased, whereas AcO and BzO an-
either pure DMSO or DMSO/H2O (75:25 v/v), respectively, as sol-
ions showed less effect to the band (Fig. 4). However, to our de-
vents. The anions of present interest, namely, F, Cl, Br, I,
light, a remarkably higher selectivity for CN over the other
HSO      
4 , AcO , BzO , NO3 , H2 PO4 , CN , and SCN as their potassium
anions was obtained in DMSO/H2O (75:25 v/v), and AcO and BzO
salts were added to the solution of [Co(DTZ)2]2+ complex, respec-
anions did not cause any signicant changes in the absorption
tively. The corresponding UVVis absorption spectra upon addition
intensity (Fig. 5). The effect of water on the reactivity of
of different anions in DMSO and DMSO/H2O (75:25 v/v), are shown
in Figs. 4 and 5. In pure DMSO, titration of [Co(DTZ)2]2+ complex
with CN caused the absorbance intensity for [Co(DTZ)2]2+in

Fig. 2. Effect of pH on the complexation reaction of Co2+ with DTZ at 610 nm Fig. 4. UVVis changes of [Co(DTZ)2]2+ (DTZ 1.0  104 mol L1 and 4.05  108 -
(4.05  108 mol L1 Co(Cl)26H2O) and [Co(DTZ)2]2+ with CN(5.0  101 mol L1 mol L1 of Co(Cl)26H2O) operated in DMSO media) after addition of 5.0  101 -
of potassium salt) at 482 nm on the UVVis spectrum changes. mol L1of potassium salts of AcO, BzO, CN and F.
 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130 125

Fig. 5. UVVis changes of [Co(DTZ)2]2+ (DTZ 1.0  104 mol L1 and 4.05  108 -
mol L1 of Co(Cl)26H2O) operated in DMSO/H2O (75:25 v/v) media) after addition
of 5.0  101 mol L1of potassium salts of AcO, BzO, CN and F.

[Co(DTZ)2]2+ complex with anions is reported in Table 1. As stated

above, [Co(DTZ)2]2+ react with the anions CN, F, AcO and BzO
in pure DMSO solution. Up to 25 vol% of water, [Co(DTZ)2]2+ is
remarkably selective to cyanide.
The above results indicate that the selectivity for CN is greatly
inuenced by water. In DMSO/H2O (75:25 v/v), anions such as AcO
and BzO could interact with the aqueous medium through hydro-
gen-bonding, and this solvation leads to a decrease in their basicity,
thus, resulting in the poor hydrogen bonding interaction with DTZ. Fig. 6. (a) Titration of [Co(DTZ)2]2+ complex (DTZ 1.0  104 mol L1 and
In contrast, cyanide has much weaker hydrogen-bonding ability in 4.05  108 mol L1 of Co(Cl)26H2O) with potassium salt of cyanide 05.0  101 -
comparison with AcO and BzO but has stronger nucleophilicity, mol L1 in pH = 5.7, Inset: the stoichiometry analysis of CN complex [(Co(DTZ)2)
(CN)] by molar ratio titration, at 298 0.1 K, (kmax = 482 nm); and (b) Color change
which results in the addition reaction of CN to DTZ ligand.
1.0  104 mol L1 DTZ in DMSO/H2O (75:25 v/v) after addition of 4.05  108 -
To quantitatively study the cyanide-sensing ability of mol L1 Co2+ ([Co(DTZ)2]2+ complex) and [Co(DTZ)2]2+ complex after addition of
[Co(DTZ)2]2+ complex in DMSO/H2O (75:25 v/v), UVVis monitor- 5.0  101 mol L1 potassium salt of CN.
ing was performed by using a solution of [Co(DTZ)2]2+ complex.
Titration of [Co(DTZ)2]2+ complex with CN resulted in the blue  h i1=2 
shift in wavelength of maximum absorption from 482 to 475 nm Alim  A0 C H C G 1=K ass  C H C G 1=K ass 2  4C H C G
and reduced the absorbance intensity in 610 nm for [Co(DTZ)2]2+ A A0 2
2C H
(Figs. 6a and 7), as this was the only anion which produced a color
change from red to orange (Fig. 6b). The isobestic point at 536 nm
indicated a clean conversion throughout the titration process.
Interestingly, the color of the solution changed from its initial where CG and CH are the concentration of guest and host, respec-
red to orange color. To corroborate 1:1 ratio between [Co(DTZ)2]2+ tively and A is the intensity of absorbance at certain concentration
complex and CN, mole ratio plot analysis was also executed. The of host and guest. A0 is the intensity of absorbance of host only and
measured absorbance at 482 nm reaches to a maximum when the
molar fraction of [CN]/[Co(DTZ)2]2+ is conrming the 1:1 stoichi-
ometry (inset Fig. 6a). The suitable scheme indicating the proposed
mode of interaction between receptor, cation and anions with the
described stoichiometry has been inserted in the Scheme 1.

3.2.2.1. Association constants. The association constants were deter-

mined by nonlinear tting analysis of the titration curves accord-
ing to the Eq. (2), for 1:1 hostguest complexation [34].

Table 1
Association constants (Kass, L mol1) of [Co(DTZ)2] with anions at 298.2 0.1 K.
Average of three measurements (S.D.)

%H2Oa CN ACO BZO F

8 4 4
0 2.67(0.16)  10 5.17(0.35)  10 3.16(0.17)  10 <100
10 1.02(0.28)  108 2.01(0.12)  104 1.48(0.45)  104 <100
25 1.26(0.23)  107 1.38(0.35)  103 6.29(0.62)  102 <100
50 2.39(0.15)  105 <100 <100 <100
100 3.48(0.60)  103 <100 <100 <100 Fig. 7. Comparison of UV/Vis spectra of DTZ (1.0  104 mol L1) and [Co(DTZ)2]2+
a
(DTZ 1.0  104 mol L1 and 4.05  108 mol L1 of Co(Cl)26H2O) and [Co(DTZ)2]2+
% Water in DMSO/water mixtures (v/v).
potassium cyanide (5.0  101 mol L1) in DMSO/H2O (75:25 v/v) media.
126 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130

Table 2 miscellaneous competitive anions did not lead to any signicant

Analytical features of the developed and some of the reported spectrophotometric spectral and color changes.
methods for the cyanide determination.

Reagents kmax pH Detection limit Refs. 3.3. Fast response

(nm) (lmol L1)
Oxazine 411 7.6 1.00 [35] As known, chemosensors always have a problem of long re-
Nickel (2+) murexide complex 476 9.0 40.00 [36]
sponse time [4547]. The response times of chemosensors includ-
sAuNPs/Cu2+/phenanthroline 524 7.0 14.00 [37]
complex ing DTZ and [Co(DTZ)2]2+ respectively with Co2+ and CN are very
Amine-substituted heptamethine 718 7.4 5.00 [38] fast (Fig. 9). When DTZ titrated with cobalt (II) chloride and
cyanine dye [Co(DTZ)2]2+ with potassium cyanide, changes in absorbance ap-
Cyanine dye Cy5 637 9.5 2.00 [39] peared very rapidly within 30 s, and the absorbance values remain
Photochromic phenoxyquinone 434 7.4 27.50 [40]
Optical sensor 598 7.0 63.00 [41]
quite stable from 30 s to 30 min. As a consequence, changes in
BF2-curcumin dyes 497 22.00 [42] absorbance at these wavelengths are immediate, thus providing
Glycoconjugated N-acetylamino 317 7.0 1.29 [43] new real-time methods for cobalt and cyanide detection.
aldehyde hydrazone azo
1,3-Bis(4-N,N-diethylamino-2- 823 9.0 5.00 [44]
hydroxyl-phenyl) croconine 3.4. pH effect
Cobalt (II) dithizone complex 482 5.7 0.43 Present
work Subsequently and to accentuate on the studies performed on
pH-effect, as one may relate the color change into pH-uctuations
concomitant with addition of anions, we have also studied the
interference effect of pH by measuring pH value. The initial and -
Alim is the maximum intensity of absorbance of host when guest is
nal pH values were compared to investigate the degree of pH uc-
added. Kass is the afnity constant of hostguest complexation.
tuation during the process. As it was clear from the results (shown
Calculated Kass was 1.26(0.23)  107 (L mol1) for the forma-
in Fig. 10), no pH change was observed upon titrating DTZ with
tion of the ([Co(DTZ)2]CN) complex by nonlinear tting analyses
cobalt (II) and [Co(DTZ)2]2+ with anions (05.0  101 mol L1
of the titration curves for 1:1 hostguest complexation. As it is
of cobalt (II) chloride and potassium salts of anions) in DMSO/
apparent from the calculated Kass the described cobalt (II) complex
H2O (75:25 v/v) (Fig. 10). For more condence we studied the
can act as an efcient and selective chromogenic reagent for CN
stability of the receptor complexes as well as the DTZ with Co(II)
sensing.
and [Co(DTZ)2]2+ with CN adduct by drawing the A/A0 parameter
A comparison of the main analytical features of the proposed
at 610 and 482 nm respectively for species versus pH. The results
method was made with many of the previously published spectro-
showed maximum stability around pH = 5.7 (Fig. 2).
photometric methods [3544]. The results are summarized in Ta-
ble 2. The previous methods exhibited low detection limit (about
3.5. Possible binding mode, FT IR and 1H NMR studies
1.0040 lmol L1) and serious interferences by halides ions [40].
Thus, it can be concluded that, the developed chromogenic
Elemental analysis of the product deduces a formula of
[Co(DTZ)2]2+ complex is more selective and sensitive than the re-
[Co(DTZ)2]2+ for the complex, since the mass percent of C:N:H:S
ported methods.
is: 54.52:19.51:4.33:11.33, and a thereby determined molar ratio
of S:Co is 2:1. To further conrm the structure of the complex,
3.2.2.2. Sensing in the presence of competing anions. The selectivity and also to investigate more with the mode of interaction between
of the system for cyanide was then examined by competition complex and anion (CN), a characterization was performed by FT-
experiments. Fig. 8 shows UVVis absorption intensity of IR with a pure DTZ for reference, which is shown in Fig. 11. In the
[Co(DTZ)2]2+ complex changes upon addition of cyanide when
1.5 mg L1 of F, Cl, Br, I, HSO    
4 , AcO , BzO , NO3 , H2 PO4 and

SCN are also present. It is noticeable that the absorption intensity
was almost identical to that obtained in the absence of anions. The

Fig. 9. Absorbance changes at 610 and 482 nm for DTZ (1.0  104 mol L1) and
Fig. 8. Absorbance responses of [Co(DTZ)2]2+ (DTZ 1.0  104 mol L1 and [Co(DTZ)2]2+ (DTZ 1.0  104 mol L1 and 4.05  108 mol L1 of Co(Cl)26H2O)
4.05  108 mol L1 of Co(Cl)26H2O) operated in DMSO/H2O (75:25 v/v) to CN after addition of Co(Cl)26H2O (4.05  108 mol L1) and potassium cyanide
(1.5 mg L1) in the presence of mixed anions (1.5 mg L1). (5.0  101 mol L1) in a mixture of DMSO/H2O (75:25 v/v) respectively.
 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130 127

Fig. 10. Changes in the pH value of DTZ (1.0  104 mol L1) in DMSO/H2O (75:25
v/v) upon addition of 05.0  101 mol L1 Co(Cl)26H2O and potassium salts of all
other anions.

spectra, it is found that there are some changes ranging from 1100
to 2100 cm1 between the prepared complex as well as its related
adducts with anion and the pure DTZ. Obviously, the frequency of
the C@S stretching vibration in pure DTZ extremely shifted from
1220 and 1151 to 1208 cm1 and 1139 cm1 in [Co(DTZ)2]2+
(Fig. 11b). The decreasing frequencies of the C@S stretching vibra-
tion imply that pure DTZ uses the sulfur atom to coordinate with
the metal ion. At the same time, the strong absorption peaks of
pure DTZ at 1519 cm1, of N@N bond was also shifted to
1507 cm1. The shifts can be attributed to the change of bond char-
acter of the N@N group bonding with the metal ion. The results Fig. 12. 1H NMR spectra of DTZ (1.0  102 mol L1) upon the sequential addition
of Co(Cl)26H2O and KCN in DMSO-d6 at 25 C. (A) DTZ, (B) DTZ + 5.0  103 mol L1
convince the formation of the complex (Scheme 1) in such a reac-
Co2+ and (C) DTZ + 5.0  103 mol L1 Co2+ + 1.0  102 mol L1 CN.
tion system. Meanwhile, the existence of NAH stretching bands
(3333 cm1), and NAH bending (1507 cm1), in the [Co(DTZ)2]2+

Table 3
Analytical characteristics of presented method.

Analytical Co2+ CN

parameter
Linear range 0.34.4 3.358.6
(lmol L1)
Regressions A610nm = 96.61CCo(II) + 1.92 A482nm = 2.27CCN + 1.39
equation
(C:mmol L1)
R2 0.9987 0.9978
Limit of detectiona 0.04 0.43
(lmol L1)
R.S.D. (%) (n = 6) 1.3 (C = 1.2 lmol L1) <1.0 (C = 10.2 lmol L1)
a
Determined as 3SB/m (where SB and m are the standard deviation of the blank
signal and the slope of the calibration graph, respectively).

Fig. 11. (a) Standard FT-IR spectrum of DTZ; (b) FT-IR spectrum of [Co(DTZ)2]2+ and
(c) standard FT-IR spectrum of [Co(DTZ)2]2+ and cyanide ion.
give a support that both NH groups are free and do not participate
in coordination with metal ion. Moreover the disappearance of
N@N vibration in complex-anion adduct (see spectrum Fig. 11c)
and also simultaneous appearance of multiple CN vibrations in
2066, 2120 and 2161 cm1 indicates covalent bond formation be-
tween CN and the azo group as illustrated in scheme. Therefore
the binding mechanism of anion to the complex is proved to be
through N-atom and not to the metal center.
As an additional piece of evidence conrming the proposed
mode of interaction, the blue shift observed upon addition of
CN (610482 nm) is investigated that indicates fading of conjuga-
tion between azo double bond and thione group. It is suggested to
be as a result of nucleophilic attack performed on azo double bond
128 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130

Table 4 were obtained from plot of absorbance intensity with the single
Determination of Co2+ some water samples by proposed method. stage addition of known various standard concentrations of Co2+
Samplea Co2+ (lg L1) Co2+ (lg L1)b R% Relative and CN. These curves were obtained by injecting standard solu-
Found Found by Added error (%) tions of Co(II) chloride in aqueous media to DTZ (measuring absor-
reference 25 lg L1 Co2+ bance at 610 nm) and potassium cyanide prepared in DMSO/H2O
method
(75:25 v/v) media to [Co(DTZ)2]2+ (measuring absorbance at
Drinking waterc 30.5 31.2 97.7 2.2 482 nm). The detection limit for the interaction of receptor (DTZ)
River waterd 59.8 61.5 97.2 2.7
Spring watere 55.0 53.4 103.1 +3.0
and Co2+ is 0.04 lmol L1 and for the interaction between complex
of [Co(DTZ)2]2+ is 0.43 lmol L1 CN in DMSO/H2O (75:25 v/v)
a
Average of three measurements(S.D.). media (3SB/m blank). The results are shown in Table 3, which indi-
b
ICP-AES method.
c cate wide linear range and applicability of method for detection of
From drinking water system of Shiraz, Iran.
d
River water which supplies water to Ghare Aghaj River Firoozabad, Iran. Co2+ and CN.
e
Samples were collected at Shiraz, Iran.

which converts it into hydrazo single bond and interrupts the de-
scribed resonance between azo and thione double bonds.
To investigate more exactly, the complex formation between
Co2+ ions with DTZ and the subsequent interaction of the resulting
complex with CN ions, we have compared 1H NMR spectrums of
DTZ, [Co(DTZ)2]2+ and [Co(DTZ)2]2+-CN (Fig. 12). As it is clear the
results supports the formation of the complex and the succeeding
attachment of CN through covalent bonding. The aromatic pro-
tons in both spectrums, [Co(DTZ)2]2+ and [Co(DTZ)2]2+-CN indicates
much more protons compared with DTZ which usually shows only
three aromatic protons. This is owing to decreasing in symmetrical
order of DTZ after the formation of the complex and attachment of
CN to the complex. In addition, appearance of two peaks for NH
protons in the [Co(DTZ)2]2+ is expected as the metal coordination
violates the identity of both protons. Also the existence of four
NH peaks in [Co(DTZ)2]2+-CN violates the identity of both DTZs
coordinated to the metal center and therefore makes the NH pro-
tons different.
3.6. Analytical characterization of Co2+ and CN
As mentioned before, DTZ can be used as a novel receptor sys-
tem for determination of Co2+ and CN by absorbance intensity
changes in DMSO/H2O (75:25 v/v) solutions. Calibration curves
4. Analytical application
4.1. Analysis of Co2+ in water samples
The applicability of the developed novel sensor was tested for
analysis of natural waters. Using a calibration curve for Co2+ in
DMSO/H2O (75:25 v/v) media (described in Section 3.6), concen-
tration of Co2+ in water samples can be determined by the addition
real samples into the solution of the DTZ in DMSO/H2O (75:25 v/v)
and the subsequent measuring the absorbance changes at 610 nm
against a blank reagent DMSO/H2O (75:25 v/v). The results are
shown in Table 4, together with the results of a recovery test. A
standard method using ICP-AES was used as reference method.
The results are also shown in Table 4.
4.2. Analysis of CN in real samples
Nevertheless, it is not easy to develop cyanide probes that are
operable in water. The charged cyanide anion has high solvation
in water. Thus, it should be desolvated from the surrounding water
molecules for the anion to combine with an appropriate probe.
Generally, the thermodynamic factor, particularly the enthalpy,
for the cyanide-probe complex formation is not favorable for
reversible chemosensors [48]. To overcome the enthalpic cost for
the cyanide-probe complexation, two novel strategies are utilized

Table 5
Determination of cyanide ion in human serum and some water samples by proposed method.

Samplea CN (lg L1) CN (lg L1) R% CN (lg L1)b Relative error (%)
Added Found Found by reference method
Drinking waterc 0.0 BDLd BDL
25.0 25.7 102.8 25.5 +0.8
50.0 50.6 101.2 51.2 1.2
100.0 96.3 96.3 99.3 3.0
River watere 0.0 BDL BDL
25.0 25.2 100.8 25.8 2.3
50.0 49.1 98.2 50.1 2.0
100.0 98.6 98.6 96.9 +1.8
Rain waterf 0.0 BDL BDL
25.0 25.4 101.6 25.9 1.9
50.0 48.7 97.4 49.7 2.0
100.0 97.9 97.9 95.8 +2.2
Human serumg 0.0 BDL BDL
25.0 25.3 101.2 25.8 2.3
50.0 48.8 97.6 49.3 1.0
100.0 97.3 97.3 96.8 +0.5
a
Average of three measurements(S.D.).
b
EPA 9014-1 method.
c
From drinking water system of Shiraz, Iran.
d
BDL below detection limit.
e
River water which supplies water to Ghare Aghaj River Firoozabad, Iran.
f
Rain water which supplies from Shiraz, Iran.
g
Prepared from Namazi hospital, Shiraz, Iran.
 H. Tavallali et al. / Journal of Photochemistry and Photobiology B: Biology 125 (2013) 121130
for researchers who try to develop luminescent probes for the toxic
cyanide anions in aqueous solution [49]. One is to employ the in-
nate nucleophilicity of cyanide anions [50]. The strong nucleophi-
licity of cyanide will make the cyanide-probe complex more
feasible and often work as an irreversible probe, a reaction-based
chemodosimeter.
The proposed method was applied to the determination of cya-
nides in real samples. Samples were collected, treated and stored
as mentioned in Section 2.5. The experimental results are tabulated
in Table 5. No cyanides were detected in either sample, while each
sample was analyzed in triplicate. The accuracy of the analytical
procedure was therefore evaluated by recovery experiments after
spiking the human serum, drinking, river and rain water samples
at three cyanide concentration levels, namely 25, 50 and
100 lg L1. The rst two levels are below or equal to the E.U. limit
in drinking waters [51], while the latter level is below the U.S. EPA
limit [52]. Percent recoveries also shown in Table 5 were
acceptable in all cases, ranging between 96.3% and 102.8%. In order
to further prove the accuracy of the procedure, the same samples
were analyzed by a spectrophotometry approved method (EPA
9014-1), that is the most classic and widely applied technique
among ofcial methods for the determination of cyanides in envi-
ronmental samples, offering a quantitation limit of 5 lg L1[53].
The experimental results are also included in Table 3. The relative
errors were in the range of 3.0% to +2.2% in all cases. The results
are given in Table 5. The results show that this method is suitable
for determination of cyanide concentrations in such samples.
5. Conclusions
In summary, we have demonstrated the use of readily accessi-
ble DTZ for highly selective and sensitive sensing of Co2+ in aque-
ous medium. The resulting complex [Co(DTZ)2]2+ formed in situ,
can be used to detect the CN among other inorganic anions and
detection can be considered as an alternative approach for the
naked-eye colorimetric sensing of CN in DMSO/H2O (75:25 v/v)
medium. The results have provided a new opportunity to detect
CN through the use of a cationic chemosensor. There are several
advantages associated with this chemosensor for cyanide detec-
tion: such as (i) our probe is commercially available; (ii) works in
aqueous DMSO solution; (iii) has high selectivity over uoride, ace-
tate and benzoate and (iv) possess long-wavelength absorption.
The detection limit (signal-to-background, S/B) of [Co(DTZ)2]2+
was estimated to be 0.43 lmol L1. The sensitivity is close to the
maximum permissive level in drinking water, which is
1.9 lmol L1 according to the World Health Organization (WHO).
It can be used as a convenient and effective method to detect cya-
nide in aqueous media.
Acknowledgement
The authors wish to acknowledge the support of this work by
Shiraz Payame Noor University Research council (Grant No D/7/
69604).
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