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DMF تحضير ثايودايازول
DMF تحضير ثايودايازول
DMF تحضير ثايودايازول
To cite this article: You-Ming Zhang , Ping Li , Qi Lin , Tai-Bao Wei & Jun-Qiang Li (2011) A Simple
Colorimetric Sensor with High Selectivity for Mercury Cation in Aqueous Solution, Phosphorus, Sulfur,
and Silicon and the Related Elements, 186:12, 2286-2294, DOI: 10.1080/10426507.2011.590166
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Phosphorus, Sulfur, and Silicon, 186:2286–2294, 2011
Copyright
C Taylor & Francis Group, LLC
GRAPHICAL ABSTRACT
Ha
N
N
H
S CH3
S N N
H3 C N S CH3
Hg(CIO4)2
a
N SH
N Hg2+
H3C H N
H3C + 2CIO4-
N N S
H3C S
H N
Na
H
Keywords Mercury cation sensor; mercapto thiadiazole; cation recognition; colorimetic test
kit
INTRODUCTION
In recent years, one of the important research topics in chemistry has been the design
of cheap and easy-to-use molecular receptors for highly toxic element such as mercury.1,2
2286
COLORIMETRIC SENSOR WITH HIGH SELECTIVITY FOR MERCURY CATION 2287
Specifically, Hg2+-sensitive systems have attracted interest in this field given that mercury
is considered as one of the most dangerous and toxic elements.3–6 In view of this, the
rational design and synthesis of efficient chemosensors to selectively and sensitively rec-
ognize Hg2+ are in high demand by organic and analytical chemists.7,8 Recently, a variety
of sensing devices based on fluorescent chemosensors,9,10 organic chromophores,11,12 elec-
trochemical devices,13 and nanomaterials14 have been employed for the selective detection
of Hg2+. However, several significant challenges still exist in these devices for practical
application, such as lower water solubility, cross-sensitivities toward other metal cations,
and especially, expensive and complicated synthesis.15 Therefore, in connection with our
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Scheme 1
Figure 1 (a) Absorption of 2 in DMSO/H2 O (7.5:2.5, v/v) upon addition of 5 equivalent of various perchlorate
metal salts (4.0 × 10−3 M). (b) Optical density of 2 at 438 nm upon the addition of different cations. (c) Solutions
of 2 (c = 2.0 × 10−5 mol L−1) upon addition of different metal ions.
COLORIMETRIC SENSOR WITH HIGH SELECTIVITY FOR MERCURY CATION 2289
for sensor 2 (Figure 1c). These results showed that 2 is a remarkably selective and sensitive
chemosensor for Hg2+.
To establish the selective and sensitive utility of sensor 2 for Hg2+ in practice,
competitive experiments of the sensor 2 (2.0 × 10−5 M) toward various metal cations were
investigated by UV-Vis in DMSO/H2 O (7.5:2.5, v/v) solutions. As shown in Figure 2(c),
chemosensor 2 (2.0 × 10−5 M) showed an obvious color change from yellow to colorless
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Figure 2 (a) Absorption of 2 (c = 2.0 × 10−5 M) in DMSO/H2 O (7.5:2.5, v/v) upon addition of 5 equivalent
of Hg2+ and various perchlorate metal salts (4.0 × 10−3 M). (b) Optical density of 2 at 438 nm with addition of
Hg2+ (4.0 × 10−3 M) in the presence of 5 equivalent of other metal ions. (c) Solutions of 2 (c = 2.0 × 10−5 mol
L−1) upon addition of 5 equivalent of Hg2+ and other different perchlorate metal ions.
2290 Y.-M. ZHANG ET AL.
0.8
0 equiv.
0.6
0.2
0.0
Figure 3 Titration curves of chemosensor 2 in DMSO/H2 O (7.5:2.5, v/v) (c = 4.0 × 10−5 M) upon addition of
Hg2+ (0–31.4 equivalent).
F − F0 [C]
= = K[M]n (1)
Fm − F [D]
where F o , F, and Fm are the corrected UV-Vis emission intensities of the complex at
initial, interval, and the final states at which the complex was fully formed upon addition
of metal ion, respectively. The binding constant K was determined from the plot of the
linear regression of log[(F – F 0 )/(Fm – F)] versus log[M] in Equation (2),27 derived from
COLORIMETRIC SENSOR WITH HIGH SELECTIVITY FOR MERCURY CATION 2291
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Figure 4 (a) 1H NMR spectra of chemosensor 2 (0.005 mM) upon addition of 0.2 and 1.0 equivalent of Hg2+ in
DMSO-d6 . (b) The proposed structure of the sensor 2 with Hg2+.
Figure 5 Photographs of the colorimetric test kits with 2 for detecting Hg2+ ion in aqueous solution.
equivalent of Hg2+, the signal of the S–Ha proton disappeared completely and a weak signal
peak appeared at δ 9.67 ppm, which attributed to the NH proton. Thus, the 1H NMR study
tends to confirm the inclusion complex formation, while the 2:1 binding stoichiometry was
confirmed using proton NMR titration spectra. The experimental results suggest a possible
interaction mode between the sensor 2 and Hg2+, in which Hg2+ was coordinated with the
S on mercapto group (Figure 4b).
To investigate the practical application of chemosensor 2, colorimetric test strips were
prepared by immersing filter papers into a DMSO/H2 O (7.5:2.5, v/v) solution of 2 (0.01
M) and then drying it via vacuum (Figure 5a). The test strips containing 2 were utilized
to sense different metal ions. After several drops of different metal ions (4.0 × 10−3 M)
were added, the obvious color change from yellow to colorless was observed only with
mercury cation solution (Figure 5b) and no significant color change was observed in the
others (Figure 5a). Accordingly, the colorimetric test strip can easily and rapidly detect
mercury cations.
CONCLUSION
A simple colorimetric chemosensor was synthesized by coupling p-
dimethylaminobenzaldehyde with 2-amino-5-mercapto-1,3,4-thiadiazole to form
Schiff-base structure with the enhanced intramolecular charge transfer. The selectivity and
sensitivity of 2 to Hg2+ over other metal ions in aqueous solution were demonstrated by
its optical response, which ascribed to the mercapto thiadiazole group. The chemosensor 2
showed remarkably anti-interference ability toward other metal cations and the detection
limit toward Hg2+ was 1.5 × 10−5 M, which indicates that this sensor could potentially be
used as a probe for monitoring Hg2+ in physiological and environmental systems. On the
basis of the colorimetric response of 2 to Hg2+, test strips containing 2 were fabricated,
which also shows a high sensitivity to Hg2+. The qualitative detection of Hg2+ using these
test strips was attempted.
COLORIMETRIC SENSOR WITH HIGH SELECTIVITY FOR MERCURY CATION 2293
EXPERIMENTAL
Materials and Methods
Melting points were measured on an X-4 digital melting point apparatus and were
uncorrected. UV-Vis spectra were recorded on a Shimadzu UV-2550 spectrometer. 1H NMR
spectra were recorded on a Varian Mercury Plus-400 MHz spectrometer with DMSO as a
solvent and tetramethylsilane as an internal reference.
General Procedure for UV-Vis Experiments. All the UV-Vis experiments were
carried out in DMSO or DMSO/H2 O binary solution on a Shimadzu UV-2550 spectrometer.
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Any changes in the UV-Vis spectra of the synthesized compound were recorded on addition
of perchlorate salt while keeping the ligand concentration constant in all experiments.
Perchlorate metal salts of cations (Zn2+, Pb2+, Cd2+, Ni2+, Co2+, Hg2+, Ag+, Ca2+, Mg2+,
and Cr3+) were used for the UV-Vis experiments.
General Procedure for 1H NMR Experiments. For 1H NMR titrations, two
stock solutions were prepared in DMSO-d6 , one of them containing host only and the
second one containing an appropriate concentration of guest. Aliquots of the two solutions
were mixed directly in NMR tubes.
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