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Recent progress in the development of fluorometric

and colorimetric chemosensors for detection of
Cite this: DOI: 10.1039/c4cs00008k
cyanide ions
Fang Wang,ab Li Wang,b Xiaoqiang Chen*b and Juyoung Yoon*a

The presence of cyanide ions in surface water is not only caused by industrial waste but also by bio-
logical processes. Owing to the extreme toxicity of cyanide in physiological systems and its widespread
presence in the environment, considerable attention has been given to the development of methods for
the detection of cyanide. Among the most simple, inexpensive and rapid methods to detect cyanide
Received 6th January 2014 ions are chemosensors that rely on fluorometric and colorimetric responses. This review, which focuses
DOI: 10.1039/c4cs00008k on CN fluorescence and colorimetric chemosensors that have been developed since 2010, follows a
format in which the sensors are classified according to their structural features and reaction mechanisms.
www.rsc.org/csr Finally, a general overview of the design of fluorometric and colorimetric chemosensors for CN is provided.

Key learning points

(1) Importance of sensing cyanide.
(2) Strategy for design of cyanide selective fluorescence and colorimetric chemosensors.
(3) Sensing mechanisms of various cyanide selective optical chemosensors.
(4) Applications of cyanide selective fluorescent probes for bio-imaging.
(5) Applications of cyanide selective chemosensors to environmental purposes.

1. Introduction of the function of this enzyme, resulting in cytotoxic hypoxia

and cellular asphyxiation. On the other hand, anaerobic meta-
Cyanide ion containing salts present in surface water not only bolism induced by cyanide leads to accumulation of lactate in
originate from industrial waste but also from biological pro- the blood. The combined effects of hypoxia and lactate acidosis
cesses.1,2 In addition, cyanide is released from natural substances disturb the central nervous system, resulting in respiratory
found in some foods and in certain plants such as cassava, lima arrest and death.3 The LD50 (estimated dose that is lethal to
beans and almonds. The seeds of several fruits, including apricots, 50% of the exposed population) of hydrogen cyanide has been
apples, and peaches, contain substantial amounts of biochemicals reported to be 2500–5000 mg min m3 (ref. 4) and according to
that release cyanide when metabolized. Cyanide is also present the World Health Organization, the maximum acceptable
in cigarette smoke and the combustion products of synthetic concentration level of cyanide in drinking water is 1.9 mM.5
materials owing to the fact that it is utilized in paper, textiles, Given the widespread occurrence and extreme toxicity of
and plastics manufacturing processes, as well as in metallurgy for cyanide, many conventional detection methods, which are
electroplating, metal cleaning, and extracting gold. based on potentiometric, electrochemical, voltammetric, titri-
Cyanide in the bloodstream of humans can form a stable metric and other techniques, have been developed for its
complex with cytochrome c oxidase, which leads to inhibition quantitative analysis.6,7 However, as a consequence of their
often complex and time consuming nature and their reliance
a
Department of Chemistry and Nano Science, Global Top 5 Research Program, on instrumentation, the utilization of these methods is limited.
Ewha Womans University, Seoul 120-750, Korea. E-mail: [email protected]; Among the less conventional methods devised for sensing
Fax: +82-2-3277-2384; Tel: +82-2-3277-2400
b
cyanide ions, those which utilize chemical reactions that pro-
State Key Laboratory of Materials-Oriented Chemical Engineering,
College of Chemistry and Chemical Engineering, Nanjing Tech University,
duce fluorometric and colorimetric responses have proven to be
Nanjing 210009, China. E-mail: [email protected]; Fax: +86-25-8358-7856; the most convenient owing to their simplicity, high sensitivity
Tel: +86-25-8358-7856 and inexpensive nature.8 Therefore, strategies to design these

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types of chemosensors have attracted significant attention over

the past few years.
Even though reviews summarizing studies of chemosensors
for cyanide, including one we contributed in 2010,9 have been
published, the large number of important recent studies in this
area have not been discussed in a review format.10,11 As a result, Fig. 2 Reaction of 2 with CN.
this review gives major attention to fluorescence and colori-
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metric chemosensors for the detection of CN that have been

point at 488 nm. A color change from green to blue also takes
described since 2010. Discussion of these sensors is organized
place. The colorimetric and fluorescent changes are attributed
according to the structural class of the key substance used and
to the formation of 2-I through nucleophilic addition of CN to
the mechanism of its reaction with CN. Accordingly, the
the o-aldehyde group in 2, which leads to inhibition of the
sections of this review are devoted to discussions of probes
ESITP process. Analysis of the cyanide concentration depen-
based on organic small molecules, metal complexes, polymers
dence of the emission intensity ratio I436nm/I521nm gave a 1.6 mM
and nanoparticles, using a format in which focus is given to the
cyanide detection limit for this sensor.
design and application of the chemosensors.
Reactions of carbonyl compounds with CN are enhanced
when electron-withdrawing groups (such as CF3) are attached
2. Organic small molecule based to the carbonyl carbon. Inspired by this phenomenon, Guo
et al. developed a rhodafluor based colorimetric and fluoro-
fluorescence and colorimetric
genic CN probe (3) that contains a trifluoroacetylamino
chemosensors for CN moiety.14 In its spirolactone form in 8 : 2 MeOH–H2O, 3
2.1 C–C bond formation (Fig. 3) is nonfluorescent and colorless. However, addition of
cyanide results in formation of a tetrahedral adduct, which
2.1.1 Cyanohydrin forming reactions. Carbonyl com-
undergoes ring opening to form the fluorescent adduct 3-I. The
pounds are known to readily undergo reactions with CN to
results of analysis of a Job plot show that a 1 : 1 adduct is
form corresponding cyanohydrins. These types of processes,
generated. Moreover, the detection limit of 3 for cyanide is
which can be enhanced by intramolecular hydrogen bonding
2.66  108 M, and other anions including F, Cl, Br, I,
interactions, can serve as the basis for the design of CN
AcO, SCN, N3, ClO3, NO3, SO32, and H2PO4 induce only
sensors.12 For example, addition of CN (100 equiv.) to a
solution of acylguanidine containing aldehyde 1 (Fig. 1) in a negligible fluorescence change, demonstrating the excellent
selectivity of the probe.
buffered (pH = 7.0; HEPES, 100 mM) H2O–CH3CN (9 : 1, v/v)
Another fluorescence probe for cyanide detection that is
leads to a decrease in absorption at 320 nm and a simultaneous
based on a carbonyl addition reaction was developed by Jang
increase in the intensity of a new absorption band centered at
et al.15 The diketopyrrolopyrrole 4 (Fig. 4), which displays
290 nm, a change that is ascribed to formation of the cyano-
absorption at 442 nm and fluorescence emission at 512 nm,
hydrin 1-I. The large second-order rate constant for the reaction
was observed to exhibit a high sensitivity and selectivity for
of cyanide with 1 of 22.3 M1 s1 is a consequence of the strong
CN. Specifically, addition of cyanide to a CH2Cl2 solution of 4
polarization of the CQO group in the aldehyde moiety by tight
hydrogen bonding interactions. In addition, in the presence of promotes disappearance of the emission centered at 512 nm
and a color change from green to red. These optical changes
CN (300 equiv.), reaction of 1 brings about a more than 7-fold
were attributed to the formation of 4-I through nucleophilic
enhancement in the intensity of emission at 440 nm.
addition of cyanide to both of the electron-deficient carbonyl
Another aldehyde containing, intramolecular proton trans-
carbons in 4. Among various anions (e.g., F, Cl, Br, I,
fer (ESITP) based sensor for ratiometric detection of CN in
aqueous solution was developed by Goswami et al.13 The sensor
(2) contains a 2-(2 0 -hydroxyphenyl)benzothiazole moiety (Fig. 2)
and, as expected, it displays green emission at 521 nm. Addi-
tion of CN to 2 induces a sharp decrease in the intensity of
emission at 521 nm and a simultaneous increase in the
intensity of a band centered at 436 nm, with an iso-emissive
Fig. 3 The reaction of 3 with CN.

Fig. 1 Fluorescence turn-on induced by reaction of 1 with CN. Fig. 4 Reaction of 4 with CN.

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Fig. 7 The reaction of 7 with CN.

Fig. 5 Reaction of 5 with CN.

ClO4, NO3, H2PO4, HSO4, AcO, SCN and HS), only

cyanide induces the strong fluorescence and color changes of 4.
Using this probe, cyanide can be detected at a micromolar level.
2.1.2 Additions to the dicyano-vinyl group. The 1,1-dicyano-
vinyl group has also been employed as a selectively reactive
moiety in the design of CN probes, in which CN undergoes
conjugate addition to the 1,1-dicyano-vinyl group to produce a
stabilized anionic adduct. This process alters the absorption and
fluorescence emission properties of the sensor. Using this
Fig. 8 Reaction of 8 with CN and the structure of 9.
strategy, Li and coworkers devised the ratiometric colorimetric
chemodosimeter 5 (Fig. 5) for detection of CN in CH3CN
solutions.16 CN addition to the dicyano-vinyl group in 5 pro-
the indene moiety to form 7-I, in which conjugation between
duces 5-I, in which the conjugated electron network is lessened
the 2,2 0 -dipicolylamine and dicyanomethylidene groups no
and the intramolecular charge transfer (ICT) efficiency is
longer exists. Probe 7 exhibits a 103-fold increase in its fluores-
decreased resulting in a blue shift of the absorption peak from
cence intensity in the presence of CN, which corresponds to a
515 to 435 nm. The detection limit of this probe for cyanide was
detection limit of 2  107 M. Interestingly, addition of AgClO4
determined to be 1.1 mM. In addition, because of the intense
to 7-I leads to restoration of the color and a decrease in the
change in color occurring, cyanide can be easily detected by
fluorescence intensity.
using the naked eye. Moreover, 5 can be employed as a practical
2.1.3 Michael additions. Cyanide selective sensors have
colorimetric sensor in a ‘‘dip-stick’’ format.
been developed using a Michael addition strategy. For example,
Jang et al. devised the turn-on sensor 6 (Fig. 6), which
Kim et al. described the sensor 8 (Fig. 8), which contains an
contains a dicyano-vinyl group conjugated with a BODIPY
a,b-unsaturated carbonyl group that undergoes rapid reaction
fluorophore for detection of CN in 99% aqueous solutions.17
with cyanide.19 In CH3CN, 8 is nonfluorescent owing to an
In a 1% THF–H2O solution, 6 fluoresces only weakly. However,
electron transfer quenching effect arising from the presence of
upon addition of CN, a dramatic increase in the fluorescence
the conjugated diethylamino and unsaturated carbonyl groups.
intensity at 510 nm takes place as a consequence of CN
Reaction of 8 with cyanide produces the intermediate enol 8-II
addition promoted removal of the conjugation required for
via the fluorescent keto form 8-I, in which the intramolecular
ICT quenching from the BODIPY moiety.
PET process is blocked. Specifically, addition of cyanide
Torroba et al. described the results of studies which showed
(100 equiv.) to the sensor brings about a 1300-fold fluorescence
that dicyanomethylidene linked indene derivative 7 (Fig. 7) is a
intensity enhancement along with a simultaneous increase in
highly selective and sensitive fluorogenic probe for detection of
the intensity of the absorption peak at 260 nm and a decrease
CN.18 Addition of CN to water or HEPES buffer solutions
in the peak at 430 nm. The latter change corresponds to a clear
containing 7 results in the disappearance of visible light
color change from yellow to colorless that can be observed by
absorption and the appearance of yellow-green fluorescence.
using the naked eye. Probe 8 was found to have a detection
The optical changes are attributed to cyanide anion addition to
limit for cyanide of ca. 1.7 mM with a signal-to-noise ratio of 3.
Based on a design using the conjugate addition strategy, Lin
et al. devised the ratiometric fluorescent probe 9 (Fig. 8) for
cyanide detection.20 In CH3CN, the sensor, which is comprised
of a conjugated 7-diethylaminocoumarin-2-formylacrylonitrile
moiety, exhibits an absorption peak at 523 nm and two emis-
sion bands at 573 and 473 nm. Upon addition of CN, a new
absorption peak at 363 nm appears concurrent with a drastic
decrease in the absorption band at 523 nm. In addition, the
intensity of the emission band of 9 at 573 nm dramatically
Fig. 6 Reaction of 6 with CN. decreases and the emission band at 473 nm slightly increases

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Fig. 11 Reaction of 12 with CN.

Fig. 9 The reaction of 10 with F and CN.
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an iminium group. Based on this property, several probes

upon cyanide addition. The reaction taking place between the containing indolium or pyridinium moieties were developed
sensor (10 mM) and cyanide (50 mM) that promotes these optical for the sensing of CN. For example, Kim et al. devised the
changes is so rapid that it is complete within 1 min. The indole conjugated coumarin 12 (Fig. 11) as a KCN sensor.23 In
detection limit of 9 for CN was determined to be 328 nM. the absence of CN, 12, in which ICT occurs from the coumarin
A 1,10-binaphthyl scaffold was employed by Wang et al. as the N atom to the positively charged indole group, exhibits two
foundation for the development of the highly selective, colori- absorption bands centered at 398 nm and 610 nm in H2O–
metric, and fluorescent chemodosimeter 10 (Fig. 9) for relay CH3CN (5 : 95, v/v) solution. Addition of CN to a H2O–CH3CN
recognition of F and CN.21 In THF, 10 displays two fluorescence (5 : 95, v/v) solution of 12 induces a red shift of the absorption
bands at 480 nm and 360 nm, corresponding to intermolecular band of the probe at 398 nm to 409 nm, while the band at
excimer and monomer emission, respectively. Addition of F 610 nm completely disappears, causing a color change from
promotes a decrease in the intensity of the fluorescence peak at dark blue to yellow. Concurrently, an enhancement in the
360 nm and concurrent formation of a new fluorescence band at intensity of the fluorescence at 484 nm takes place. The optical
460 nm, which is ascribed to the formation of the monomeric changes are attributed to nucleophilic addition of the cyanide
coumarin derivative 10-I through lactonization of the intermedi- to 12 to form 12-I, in which conjugation between the indole and
ate phenolate anion. Meanwhile, the fluorescence peak at 480 nm coumarin groups and, consequently, ICT is disrupted.
shifts to 550 nm where it appears as a shoulder peak. When CN Another example of a probe that functions via addition to an
is added to a solution containing 10-I, a 2.5-fold enhancement of iminium group is the triazolopyridinium salt 13 developed by
the fluorescence bands at 460 nm and 550 nm occurs. The results Aprahamian et al. (Fig. 12) for fast, sensitive, and selective detection
of NMR and mass spectrometric analysis suggest that the fluores- of CN.24 In DMSO–H2O (99 : 1), 13 displays weak fluorescence
cence changes taking place are a consequence of addition of CN because of the presence of a p-OMe–phenyl group, which serves to
to binaphthyl–coumarin hybrid 10-I, which generates the cyano- transfer charge to the triazolopyridinium subunit. In the presence of
coumarin derivative 10-II. The CN detection limit using 10-I was 2 equiv. of NaCN, 13 undergoes cyanide addition to form 13-II, in
found to be 1.41 mM (36.7 ppb). which the charge transfer process is blocked. This process results in
The p-quinomethane derivatives 11a and 11b (Fig. 10), a 60-fold enhancement of the intensity of fluorescence at 504 nm.
described by Martı́nez-Máñez, are novel chromogenic sensors The detection limit of this probe was determined to be 0.2 ppm.
for CN in aqueous medium and HCN in the gas phase.22 Upon Utilizing the same general strategy, along with the aggregation-
addition of CN, solutions of these substances undergo a induced emission feature of the tetraphenylethylene (TPE) group,
change in color from pink to colorless owing to the occurrence Zhang designed the sensitive and selective fluorescence probe 14
of a conjugate addition reaction. Although 11b responds to (Fig. 13) to detect CN in aqueous solution.25 The positively-charged
CN more rapidly than does 11a, 11b unfortunately also
exhibits a chromogenic response to HS. The limits of detec-
tion of 11a and 11b were determined to be 265 and 300 ppb,
respectively. Furthermore, an aminated basic silica support
containing absorbed 11a can be used to detect HCN at a
concentration of as low as 2 ppm.
2.1.4 Indolium or pyridinium addition reactions. The elec-
trophilicity of sp2-carbon atoms toward CN can be enhanced
by installation of a positively charged nitrogen atom to create
Fig. 12 Reaction of 13 with NaCN.

Fig. 10 Reaction of 11a and 11b with CN. Fig. 13 Reaction of 14 with NaCN.

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indolium unit in the probe reacts with CN to afford 14-I, in

which aggregation takes place in association with the generation
of a fluorescence band. In the presence of 1 equiv. of CN, a
solution containing 14 undergoes a 300-fold enhancement in its
fluorescence intensity. The detection limit of this CN selective
probe, which does not respond to F, Cl, Br, I, SCN, SO42,
H2PO4, CH3COO, NO3, NO2, N3, EDTA, S2 or metal ions,
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was determined to be as low as 91 nM. The formation of

aggregates following cyanide addition was demonstrated by
Fig. 15 The mechanism of the fluorescence change of 18 induced by CN.
using both confocal laser scanning microscopy (CLSM) and
dynamic light scattering (DLS). Finally, CN can be detected
rapidly by employing a 14 containing paper test strip system. insensitive to F in that only the addition of CN induces a
red shift in the absorption band from 464 nm to 504 nm,
demonstrating that 17 is more applicable for CN sensing in an
2.2 Proton transfer based receptors
aqueous medium.
The benzimidazole unit has been used advantageously in the 4-Amino-3-hydroxynaphthalene-1-sulfonic acid (18) (Fig. 15),
design of probes to detect CN. The probes operate through was used by Zhang et al. in a proton transfer based approach for
deprotonation of the NH imidazole proton, which is made acidic selective recognition of CN.28 Owing to the electrostatic inter-
by incorporation of appropriate electron withdrawing groups. In action between NH3+ and SO3 groups and p–p stacking
these systems, deprotonation induced by CN generates a shift in between naphthalenes in the zwitterion under neutral condi-
the absorption and fluorescence emission bands by blocking ICT. tions, 18 self assembles in water to form the complex 18-I,
Probes 15 and 16 (Fig. 14), designed by Das et al.26 and which is strongly fluorescent at 452 nm. However, when 25
containing an anthraquinone conjugated imidazole moiety, equivalents of CN are added to an aqueous solution of this
detect CN with high selectivity. Addition of CN to 15 in sensor, deprotonation reactions take place that sequentially
CH3CN–HEPES buffer (1 : 1, v/v) causes an increase in the form 18-II and 18-III and result in disruption of the intra-
absorption peak at 474 nm and an accompanying decrease in molecular charge interactions. These processes lead to the
the peak at 393 nm. In the case of 16, a decrease in the disappearance of the fluorescence emission band at 452 nm.
absorbance peak at 390 nm and an increase in the band at By using fluorescence titration experiments, the detection limit
552 nm take place when CN is added. The CN induced of 18 for CN was evaluated to be 3.2  107 M.
absorption spectral changes are attributed to the formation of
the respective hydrogen bonded adducts, 15–CN and 16–CN.
The detection limits of these probes were determined to be 2.3 C–B bond forming reactions
0.06 ppm and 0.078 ppm, respectively. In addition, 15 was Another approach to the development of cyanide sensors relies
demonstrated to have the potential for being employed to on C–B forming reactions. One example of this strategy is found
detect CN adsorbed on surfaces of Pseudomonas putida cells. in Akkaya and co-workers’ design of the borondipyrrin dye 19
The closely related probe 17 (Fig. 14) based on the anthra[1,2-d]- (Fig. 16) to detect both cyanide and fluoride ions.29 In chloro-
imidazole-6,11-dione platform was developed for selective detection form, 19, bearing an oxalyl-tethered bis-pyrrole moiety bridged
of F and CN.27 Addition of F and CN to an acetonitrile–DMSO by two fluoroboronate chelating units, is bright orange. Upon
(95 : 5, v/v) solution of 17 promotes a red shift in the absorption addition of cyanide ions, the color of the solution immediately
bands by B120 nm and B81 nm, respectively. In a corresponding changes from orange to red, corresponding to a red-shift of the
manner, the color of 17 changes from light yellow to dark blue upon absorption peak to 520 nm. In contrast, addition of low con-
addition of F and from light yellow to red for CN. The color centrations of fluoride results in a sharp color change from
changes induced by F and CN are a consequence of intra- orange to purple, accompanied by a shift in the absorption
molecular charge transfer processes. Compared to the wavelength peak to 600 nm. Addition of excess amounts of F results in a
shift induced by CN, the one promoted by F is a result of gradual shift in the absorption peak to 520 nm concurrent with
deprotonation of NH in the benzimidazole moiety. Interest-
ingly, in 9 : 1 CH3CN–water (1% DMSO), the sensor is

Fig. 14 Structures of 15–17. Fig. 16 Reaction of 19 with CN.

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[4-(Me3N)-2,6-Me2-C6H2]+.31 This derivative can bind both fluoride

and cyanide anions in THF to afford the corresponding zwitter-
ionic fluoroborate (22-F) and cyanoborate species (22-CN). Titra-
tion experiments indicate the progressive quenching of the
emission band at 392 nm upon incremental addition of anions,
and the binding constants of 22 in THF for fluoride and cyanide
anions exceed 107 M1, which was attributed to the accessibility of
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the boron atom as well as the favorable inductive and Coulombic

effects imparted by the anilinium substituent. The probe 22 is
unstable in pure water, however, it showed selective binding
toward cyanide rather than fluoride in nitromethane–water.
Fig. 17 Reactions of 20 and 21 with CN. Gabbaı̈ and co-workers also reported a cationic cyclometa-
lated ruthenium(II) complex (23) (Fig. 18) which contains a
triaryl boron group. This cationic Ru(II) complex reacts with
a decrease in the intensity of the band at 600 nm. Thus, the fluoride and cyanide anions to afford the corresponding
color changes can be used to clearly distinguish fluoride and zwitterionic fluoroborate and cyanoborate species.32 The crystal
cyanide ions. The spectra changes occurring in this system are structures of this borane, which binds fluoride or cyanide
ascribed to selective detachment of the difluoroboron bridges anions in organic solvent to afford 23-F or 23-CN, have been
by substitution reactions with CN and F at boron. Moreover, determined. Either fluoride or cyanide binding to the boron
the different absorption shifts induced by CN and F are a center induces similar UV-vis spectral changes, where a 30 nm
consequence of the differential reactivity of the two anions with bathochromic shift of the metal-to-ligand charge transfer band
the two different boron centers in 19. from 550 nm to 580 nm was observed. The UV-vis titrations in
Cationic boranes are capable of undergoing efficient complexa- CHCl3–DMF (9 : 1, v/v) indicated that the binding constants of
tion with cyanide, owing to the favorable Coulombic receptor– 23 to F and CN are 1.1(0.1)  104 M1 and 3.0(1.0) 
CN attractions. Gabbaı̈ and co-workers used this property to 106 M1, which shows the higher affinity of 23 to CN than F.
design two turn-on fluorescence sensors, 20 and 21 (Fig. 17),
which can be used to detect CN in aqueous solution at ppb
2.4 Electron transfer reactions
concentrations.30 Both 20 and 21 are weakly fluorescent owing
to intramolecular electron-transfer from the excited fluorophore A single electron transfer (SET) driven reaction based strategy
to the phosphonium borane moiety. Addition of cyanide ions to for detection of cyanide has been reported, which features
these probes generates the corresponding boron adducts 20-I some advantages, such as a unique SOMO–LUMO electronic
and 21-I, in which the electron-deficiency of the phosphonium transition process, multidimensional signal outputs and
borane unit is lessened and electron transfer from the pendant potential application in practical electronic devices. Mukho-
fluorophore to the cationic borane is diminished. This process padhyay et al. reported a series of SET-based cyanide indicators
results in the observation that addition of cyanide to solutions of that are based on naphthalenediimide (NDI), perylenediimide
20 and 21 cause enhancements in the fluorescence efficiencies. (PDI) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) moieties
In H2O–MeOH (6 : 4, v/v), the detection limit of 21 for cyanide by employing their low-LUMO properties.33–35 Specifically,
ions is as low as 26 ppb. Moreover, 21 displays no response to addition of cyanide to the sensors 24a or 24b (Fig. 19) leads
other anions such as F, Cl, Br, I, NO3, H2PO4, SO42, and to formation of the corresponding air-stable radical anions
CH3CO2, when they are present at this low concentration. 24a-I or 24b-I, accompanied by an instantaneous change in
Gabbaı̈ et al. devised another cationic borane fluorescent color from colorless to dark brown for 24a and from orange to
sensor, 22 (Fig. 18), which bears a 9-thia-10-boraanthracene
moiety substituted at boron by the cationic anilinium group

Fig. 18 Reaction mechanisms of 22 and 23 with CN. Fig. 19 Reaction mechanisms of 24a and 24b with CN.

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Fig. 21 Mechanism for the fluorescence change of 26 induced by CN.

Fig. 20 Reaction mechanisms of 25a–c and TCNQ induced by CN.

photoinduced electron transfer (PET) from the excited coumarin
33 fluorophore to the central cobalt ion in the complex. When CN
turquoise-blue for 24b. In the presence of cyanide, these sensors
is added, the PET process is inhibited owing to the formed cyano
display a new set of absorption peaks at 470, 603, 701, 786, and
ligated complex having a higher energy LUMO level. The
1100 nm for 24a and 699, 761, 794, 952, and 1100 nm for 24b,
proposed formation of a 1 : 2 complex between 26 and CN
which are characteristic of the radical anions. The sensors can be
was supported by the results of high-resolution mass spectro-
regenerated by treatment with an oxidizing agent (NOBF4). By
metric analysis, which showed that the cyano-complexes have
using absorption titration experiments, 24a was shown to exhibit
binding constants of K1 Z 107 M1 and K2 = 4.0  105 M1.
sensitivities of 0.67 and 1.3 mM in THF and DMF, respectively,
Another cyanide sensor that relies on the formation of a
while a sensitivity of 0.2 mM in THF was determined for 24b by
cyano-ligated metal complex was developed by Guo et al. In this
monitoring fluorescence intensity changes. Furthermore, thin
study, the Cu(II)-based complex 27 (Fig. 22) bearing a rhodamine B
films of 24b on glass substrates, fabricated by utilizing the vapor
fluorophore was devised for CN detection.37 In 9 : 1 (v/v) CH3CN–
deposition technique, display a significant color change in the
Tris-HCl buffer solution (10 mM, pH 7.0), the Cu2+ hydrazide
presence of as low as 0.1 mM CN in petroleum-ether.
complex 27 is weakly fluorescent owing to Cu2+ promoted PET
Other probes (25a–c) based on the formation of radical
(photoinduced electron transfer) or EET (electronic energy trans-
cations of naphthalenediimide with CN under ambient condi-
fer) quenching of the rhodamine fluorophore. However, addition
tions have been reported (Fig. 20).34 In the presence of cyanide,
of cyanide to 27 results in formation of a cyano-ligated copper
the p–p* and ICT bands of 25a diminish with formation of new
complex, which is highly fluorescent owing to inhibition of the
bands at 494, 533, 678, 778, and 891 nm, which was attributed to
quenching of the rhodamine excited state. The observation that no
ET processes from 25a to 25a . The half-lives of 25a –25c 
change takes place in the absorption spectrum of 27 upon cyanide
were determined to be 18 h, 4.1 h and 1.3 h, suggesting that the
addition indicates that the integrity of the copper containing
stability of the radical anions are relative to intramolecular
complex is maintained. CN recognition employing 27 is complete
H-binding. Furthermore, compound 25a was found to be highly
in less than 5 min, and the detection limit is 1.4  107 M.
selective and sensitive for CN among different anions.
A much more chemically complex copper based cyanide
Similarly, TCNQ also displays high sensitivity and selectivity
sensor was developed by Tian et al.38 The probe, 28a (Fig. 23),
for cyanide, based on SET from cyanide to deep-lying LUMO
is comprised of an unsymmetrical dithienylethene moiety con-
orbitals of TCNQ to form a radical anion TCNQ .35 The TCNQ
taining a naphthalene group as a fluorophore and an imine
probe generates differentiable signal outputs that are readable
donor for Cu2+ complexation. Irradiation of 28a in CH3CN
by both UV-vis-NIR absorption and scattering-based spectro-
using 365 nm light results in the formation of a substance that
scopic methods such as Raman and hyper Rayleigh scattering.
has an absorption band centered at 607 nm. Concurrently,
Upon addition of cyanide in MeCN–H2O (9 : 1 v/v), TCNQ
the color of the solution changes from colorless to blue.
displayed a new set of absorption peaks at 480, 680, 740 and
These optical changes are proposed to be a consequence of
840 nm accompanied with a sharp decrease at 395 nm, suggest-
photoelectrocyclization of 28a to form 28b. Upon irradiation
ing the formation of the radical anion (TCNQ ). The intense
with visible light (550 nm), the color of the blue solution
840 nm NIR absorption peak implies that the sensor has the
changes to colorless and the absorption spectrum of the
potential for detecting cyanide anions in biological samples.

3. Probes based on metal complexes

3.1 Metal complexes as receptors
Several strategies that rely on the use of metal complexes have
been devised for the design of cyanide sensors. For example,
Hong et al. developed the Co(II)-salen based fluorescent sensor
26 (Fig. 21) for CN recognition.36 In CH3CN, the fluorescence
of 26 is inefficient owing to the participation of intramolecular Fig. 22 The mechanism of the fluorescence change of 27 induced by CN.

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Fig. 24 The structures of 29 and 29–Cu2+.

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solvents. Sensors based on metal ion displacement have been

found to be applicable for detecting CN in aqueous media. An
example of this type of probe is the novel NIR fluorescent CN
sensor 29–Cu2+ (Fig. 24) designed by Yoon and Park et al.,39 which
contains a polyamine substituted heptamethine cyanine dye in
the form of a copper complex. This probe selectively senses
cyanide in 20 mM HEPES buffer (pH 7.4, 0.5% CH3CN). Addition
of Cu2+ to a solution containing complex 29 causes a decrease in
Fig. 23 Proposed processes involved in sensing by 28a and 28b with the intensity of the absorption peak at 718 nm with concurrent
Cu2+, and complexes 28a–Cu2+ and 28b–Cu2+ with CN, and the
formation of a new peak at 743 nm. Adding CN to a solution
photochromic processes responding to light stimuli.
containing the formed 29–Cu2+ complex promotes a significant
fluorescence enhancement, caused by reaction of cyanide with
starting 28a is recovered. When Cu2+ is added to a solution the copper to form a stable [Cu(CN)x]n species. Using 0.5 mM of
containing 28a, a color change from colorless to yellow occurs 29–Cu2+, the detection limit for cyanide was determined to be
as a result of the formation of a copper–28a complex. The ring 5 mM with a signal-to-noise ratio of 3. Importantly, various other
closed isomer 28b–Cu2+ is generated by irradiation of a solution anions, such as F, Cl, Br, I, NO3, HSO4, HCO3,
of 28a–Cu2+ with 365 nm light. A corresponding color change CH3COO, Pi (phosphate), PPi (pyrophosphate), SCN and ClO4,
from yellow to blue occurs concurrently with a decrease in the do not promote a response of the probe. This sensor has also been
intensity of the absorption band at 354 nm and the formation used to visualize cyanide produced by P. aeruginosa in C. elegans.
of a new band at 584 nm. The color and absorption spectro- Zhu described the three closely related 2,2 0 -dipyridyl-
scopic changes can be reversed by irradiation of the solution aminoanthracene–Cu2+ probes 30–Cu2+, 31–Cu2+ and 32–Cu2+
using visible light. When CN is added to a solution containing (Fig. 25) for the detection of CN in MeOH–H2O (4 : 1, v/v).40
28a and Cu2+, the absorption band at 354 nm decreases owing The sensing mechanism followed by these probes involves CN
to the formation of the complex 28a–Cu2+–CN. Upon irradia- induced Cu2+ ion removal, which leads to strong fluorescence
tion with 365 nm light, the intensity of the absorption band of enhancements. The complex 31–Cu2+ was observed to have a
28a–Cu2+–CN at 350 nm decreases and a new band at 581 nm higher cyanide sensitivity and selectivity than 30–Cu2+ and
appears, accompanied by a color change from yellow to blue. 32–Cu2+. The respective detection limits of 30–Cu2+ and 31–Cu2+
These changes correspond to formation of the ring-closed were determined to be 3  107 M and 2  107 M. Finally, the
isomer 28b–Cu2+–CN. Upon irradiation with visible light, the fluorescence of 30 and 31 could be repeatedly switched off and on
color of the solution changes from blue to yellow and the by alternate addition of Cu2+ and CN, indicating the highly
original absorption spectrum is recovered. The fluorescence reversible nature of both probes.
intensity of 28a exhibits a more than 5-fold enhancement when Das devised the ‘‘turn-on’’ phosphorescence probe 33–Cu2+
1 equiv. of Cu2+ is added. This enhancement is attributed to two (Fig. 26), which is comprised of an Ir(III) complex coordinated
factors, including inhibition of excited state free rotor type with Cu2+, for detecting CN in HEPES–CH3CN (99.6 : 0.4, v/v;
CQN bond isomerization by complexation of 28a with Cu2+, and pH 7.6) buffer.41 Upon addition of CN to the complex, a turn-on
suppression of photoinduced electron transfer (PET) quenching. emission with a maximum at 583 nm takes place as a conse-
Addition of 3 equiv. of CN to 28a–Cu2+ causes a distinct increase quence of the removal of copper by formation of Cu(CN)n(n  2)
in the fluorescence intensity at 448 nm, indicating that the (n = 2 or 4). The complex, which has a detection limit as low as
complex 28a–Cu2+–CN is formed. The limit of detection for 0.38 ppm, can be used as an imaging reagent to detect CN in
CN by this sensor system was determined to be 22.5 nM and a live HeLa cells. Furthermore, 33–Cu2+ can also be used to
linear relationship between the fluorescence intensity and concen-
tration of CN was found to exist in the range 4.0–20.0 mM.

3.2 Metal ion displacement reactions

The development of fluorescence sensors for cyanide detection
that can be used in aqueous media is a much more significant
goal than developing sensors that only function in organic Fig. 25 Structures of 30–32.

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Fig. 26 Structure of 33–Cu2+.

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Fig. 29 Reaction of 37 with CN or F.

nucleophilic addition of CN to the aldehyde groups, which alters

the electronic nature of the phenanthroline ligand. Furthermore,
when CN is added to solutions containing 35 and 36, a color
change from orange-red to yellow occurs that can be seen by using
the naked eye. The results of photoluminescence titration experi-
ments show that the reactions between the sensors and CN in
CH3CN take place in two steps. The first involves addition to one
CHO group in the complex to form a 1 : 1 adduct and this is
Fig. 27 Mechanism for the fluorescence enhancement of 34–Cu2+
followed by a second addition to the other –CHO group. The
induced by CN.
detection limits of these probes fall in the sub-micromolar range.
Importantly, no noticeable emission enhancement takes place
when other anions including F, Cl, Br, I, H2PO4, HSO3,
determine the activity of hydroxynitrile lyase, which catalyzes the
OAc and HCO3 are added to CH3CN solutions of these probes.
decomposition of mandelonitrile to form HCN.
Gabbaı̈ et al. designed the triaryl borane containing cationic Ru(II)
Kim devised the coumarin-Cu(II) based probe 34–Cu2+ (Fig. 27)
complex 37 (Fig. 29) for detecting fluoride and cyanide anions.44
for detection of cyanide in aqueous solution.42 Among various
In organic solvents, 37 reacts with F and CN to form 37-I–F and
anions (F, Cl, Br, I, AcO, H2PO4, HSO4, NO3, ClO4,
37-I–CN, respectively, the structures of which have been demon-
HCO3, SCN, OH, CO32, HPO42, PO43, AMP, ADP and ATP),
strated by using X-ray crystallographic analysis. Addition of F and
only cyanide induces a fluorescence enhancement of 34–Cu2+.
CN to solutions of 37 results in a color change from deep purple to
The mechanistic basis for the operation of this probe was shown
nearly black. This change is associated with a 30 nm bathochromic
to be an addition reaction of cyanide, which promotes decom-
shift in the absorption maximum corresponding to the metal-to-
plexation of the Cu(II) ion from non-fluorescent 34–Cu2+, followed
ligand charge transfer band. The results of UV-vis titration experi-
by hydrolytic cleavage of the resulting free Schiff base moiety,
ments afforded the constants 1.1(0.1)  104 M1 for F binding
which forms the strongly fluorescent coumarinaldehyde 34-I. The
and 3.0(0.1)  106 M1 for CN binding to 37 in CHCl3–DMF
detection limit of 34–Cu2+ for cyanide was determined to be
(9 : 1, v/v). The addition of other anions including Cl, Br, I, or
108 M. In addition, the fluorescence enhancement of this sensor
NO3 does not cause changes in the UV-vis spectrum of 37.
occurs in the pH range of 6–10. Finally, the results of confocal
microscopy experiments demonstrate that this probe can be
employed to image cyanide in HepG2 cells. 4. Probes based on polymeric
3.3 Reactions of ligands with CN
frameworks
Two ruthenium complexes, 35 and 36 (Fig. 28), were designed The sensing material 38 (Fig. 30), comprised of functionalized
by Schmittel et al. to detect cyanide.43 In CH3CN, both 35 and polyfluorene CPs (conjugated polymers) containing pendanti-
36 exhibit weak emission at 732 nm upon excitation at 473 and midazole moieties, was developed by Salinas-Castillo et al. for
472 nm, respectively. Upon addition of CN (2 equiv.) to solutions cyanide detection.45 CP microspheres were derived from 38
of these sensors, the emission band at 732 nm disappears using a microemulsion and polymerization procedure. In aqu-
concurrently with the appearance of a new band at 624 nm for eous media, the blue fluorescence of the CP microspheres is
35 and at 614 nm for 36. These changes are a result of the quenched by Cu2+ as a result of metal ion binding to the

Fig. 28 Structures of 35 and 36. Fig. 30 Structure of 38.

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cyanide sensing.47 In the presence of cyanide, conjugate addi-

tion to the bis-cyanoalkene moiety results in destruction of the
conjugation of the polymer’s main chain, a process that
induces a change in optical properties that is reflected in both
the absorption and fluorescence spectra. Specifically, addition
of 20 equiv. of cyanide to a DMF solution of 40 promotes a
decrease in the intensity of the absorption band at 403 nm and
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simultaneous formation of a new band at 338 nm. The asso-

ciated color change from yellow-green to colorless can be
clearly observed by using the naked eye. In addition, the visible
change occurs concurrently with a decrease in the fluorescence
intensity at 597 nm and with no change in the emission band at
455 nm. The detection limit of this sensing system for CN was
determined to be 14 ppb.
Fig. 31 Schematic representation of the colorimetric and reversible
fluorometric response of the polymerized 39 vesicles for CN detection.
Reproduced from ref. 46 with permission from The Royal Society of 5. Probes based on nanoparticles
Chemistry.
The iridium(III) complex 41 (Fig. 33) for detecting cyanide using
upconversion nano-phosphors (UCNPs) was designed by Li
imidazole moieties. Injection of cyanide into the copper treated et al.48 The UCNPs display a small intensity ratio (I540/I800) of
sensor promotes recovery of the fluorescence of the CP micro- upconversion luminescence (UCL) at 540 and 800 nm because
spheres as a result of Cu2+ dissociation. The detection limit of of the existence of a FRET process. However, when cyanide
38–Cu2+ for cyanide was determined to be 18 mg L1. is added to a DMF–H2O (9 : 1, v/v) solution of the probe, the
Ring opening reactions of spiropyran groups embedded within I540/I800 ratio of the UCL intensities is enhanced, a phenomenon
a polydiacetylene (PDA) backbone can serve as the chemical basis that is attributed to the reaction of CN with the a,b-unsaturated
for polymeric cyanide sensors. For example, Zou et al. designed carbonyl moiety in the ligand. This reaction leads to an inter-
the sensing system 39-I, which is formed by polymerization of ruption of FRET quenching. Upon addition of CN to a solution
spiropyran linked diacetylene vesicles, 39 (Fig. 31).46 In a typical of oleic acid (OA)–41–UCNPs, the color changes from pink to
manner, the PDA is blue as a result of the existence of a maximum colorless, a change that does not take place when other anions
absorption band centered at 640 nm. Upon addition of 50 mM such as NO3, ClO4, F, Cl, Br, I, NO2, SO42 and AcO are
CN to an aqueous solution of 39-I, a color change from blue to added. Using the ratio I540/I800, the detection limit of the OA–41–
red occurs accompanied by an enhancement of fluorescence at UCNPs was determined to be as low as 0.18 mM. Finally,
550 nm. Finally, when 0.1 M aqueous HClO4 is added to the ratiometric UCL images can be generated for HeLa cells contain-
mixture of red colored PDA–CN vesicles, the fluorescence inten- ing cyanide.
sity decreases because of the formation of HCN and the resulting Kim and co-workers developed the novel organic–inorganic
removal of CN from the spiropyran units in 39-II. Thus, this sensor 42 (Fig. 34), which is based on bisindole anchored
sensing system is a reversible fluorometric probe for CN detec- mesoporous silica nanoparticles.49 In the presence of CN,
tion. By using simple UV-vis absorption and fluorescence mea- the sensor undergoes a remarkable color change from red to
surements, a low level of CN (up to 0.5 mM) can be determined by yellow in association with a decrease in the intensity of the
employing this PDA based probe.
Tong and Wang et al. developed the novel conjugated
polyfluorene 40 (Fig. 32), containing a dicyano-vinyl unit, for

Fig. 33 Proposed recognition mechanism and the FRET process of OA–

41–UCNPs towards CN. Reproduced from ref. 48 with permission from
Fig. 32 The fluorescence change of 40 induced by CN. The American Chemical Society.

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Fig. 34 Reaction of 42 with CN.

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absorption band at 492 nm and generation of a new band at

450 nm. The absorption change was suggested to be a conse-
quence of addition of CN to the methylidene–indoline moiety
in the sensor to form adduct 42-I. Other anions, such as F,
Cl, Br, I, AcO, H2PO4 and HSO4, do not promote
significant optical changes, indicating the good selectivity of Fig. 37 Schematic illustration of the UCNP-based color trigger system
this system to CN. By using fluorescence titration experi- toward CN. Reproduced from ref. 52 with permission from John Wiley
ments, the detection limit was estimated to be 3 mM. and Sons.
In another effort, Hong and Jun et al. developed a highly
specific fluorescent probe based on Cu2+–c-mpg-C3N4 (meso-
and recovery of the original fluorescence. By monitoring the
porous graphitic carbon(IV) nitride) (Fig. 35), for detection of
fluorescence changes occurring on tiny amounts of QD follow-
CN.50 The photoluminescence (PL) of c-mpg-C3N4 is quenched
ing sequential mixing and grinding of 2,2 0 -bpy with CuCl2 and
by Cu2+. Upon addition of CN to the copper complexed probe,
then with NaCN, as little as 800 ng (16 nmol) of pure NaCN can
the intensity of a PL emission band centered at 455 nm
be detected.
increases, suggesting that a [Cu(CN)n](2  n) species is formed
Yao et al. developed a hybrid material composed of an
leading to restoration of the original fluorescence efficiency of
iridium complex and UCNPs to detect cyanide anions selec-
the probe. In aqueous solution, the sensor displays an excellent
tively in pure water.52 The probe was fabricated by using the
selectivity toward CN over other anions, such as OH, Cl,
two steps displayed in Fig. 37. First, the amphiphilic block-
CH3COO, H2PO4, Br, SO42, N3, F, and I with a detec-
polymer poly(maleic anhydride-alt-1-octadecene)-polyethylene
tion limit of 80 nM. Furthermore, the probe can be utilized to
glycol (C18PMH-PEG) was coated onto the surface of hydro-
detect CN in human blood samples and serum proteins.
phobic oleic acid (OA)-coated NaYF4:20%Yb, 2%Ho UCNPs to
Mareque-Rivas and co-workers designed a naked-eye sensor
fabricate a hydrophilic nanostructure. This is followed by
for solid cyanide salts that takes advantage of mechanochemical
loading the CN-reactive iridium(III) complex, [(ppy)2Ir(dmpp)]PF6,
reactions in the solid-state (Fig. 36).51 Manual grinding of
43, onto the hydrophobic layer to form the hybrid upconversion
2,2 0 -bpy and CuCl2 on a CdSe quantum dot (QD) surface creates
material. The UCNPs display two emission bands at 530–560 nm
the [CuCl2(2,2 0 -bpy)] complex absorbed to the hydrophobic QD
and 630–670 nm under 980 nm excitation, and 43 has a significant
surface. This process leads to quenching of the QD fluores-
absorbance with a maximum at 530 nm. In the absence of CN,
cence. A subsequent ligand exchange reaction with cyanide to
the luminescent resonance energy transfer (LRET) process
form copper cyanide complexes promotes release of the QDs
quenches the green emission of the UCNPs. The added CN then
combines with 43 making the LRET process less efficient and, as a
result, green emission from the probe is restored. The detection
limit of the 43–UCNPs was estimated to be 37.6 mM.
Gupta et al. designed a catalytic signal amplification method
for the detection of CN in aqueous solution using [FeIII(biuret-
amide)]2 immobilized inside mesoporous silica nanoparticles
(Fe-MSNs) (Fig. 38).53 The detection mechanism of this probe
involves a sequence of processes. First, CN binding to catalase
reduces the catalytic activity of the enzyme, leading to incom-
Fig. 35 Scheme of a chemosensor for cyanide ions using Cu2+–c-mpg-
C3N4. Reproduced from ref. 50 with permission from The Royal Society of
plete disproportionation of H2O2. In a process catalyzed by
Chemistry. Fe-MSNs, residual H2O2 oxidizes 3,3 0 ,5,5 0 -tetramethylbenzidine
to generate a colorimetric signal. This method displays a linear
dependence of absorbance on cyanide in the concentration
range of 0–156 ppb with a limit of detection (LOD) of 23.4 ppb.
Finally, Li et al. described a simple chemodosimetric signal-
ing system for cyanide (Fig. 39), which is based on release of a
fluorescent polymer from coated gold nanoparticles (Au NPs).54
Au NPs efficiently quench the strong blue fluorescence of the
Fig. 36 CdSe QDs for cyanide detection. carbazole fluorophore in 44, which coats the nanoparticle

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sensor is further applied to detect cyanide in complex samples,

including red wine, coffee, juice, and soil.

6. Concluding remarks
In this review, a number of studies focusing on the develop-
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ment of new fluorescence and colorimetric sensors for cyanide

during the 2010–2013 time period are described. The probes
were categorized by either using their structural classifications
or the type of chemical process that leads to signal production.
As described above, considerable attention has focused on the
development of cyanide sensing systems and application of the
sensors to biologically and environmentally interesting pro-
Fig. 38 Cyanide detection assay of Fe-MSNs. Reproduced from ref. 53 blems. We believe this research area will become more active
with permission from The Royal Society of Chemistry. and significant in the future, owing to the extremely high
sensitivities and selectivities of the optical sensors for detecting
cyanide ions. As a result, these probes will gain growing
importance in monitoring cyanide in industrial wastes and
drinking water. Because several recent probes based on poly-
mers and nanoparticle scaffolds have been developed, it is
likely that solid systems will be constructed to serve as ‘‘dip-
in’’ sensors for the detection of CN by using the naked eye.
Moreover, developments made in devising cyanide sensors for
in vivo imaging will play an important role in elucidating the
mechanism of biological cyanogenesis. The designs of these
sensors will need to take into consideration some or all of the
important properties including high photostability, good solu-
bility in aqueous media, good cell permeability and low inter-
Fig. 39 Reaction of 44-coated Au NPs with CN.
ference from biological environments.

surface through interactions with the tethered imidazole

groups. Addition of CN in water causes release of the Au Acknowledgements
NPs and restoration of the fluorescence of 44 in conjunction J.Y. acknowledges a grant from the National Research Founda-
with a color change from deep brown to colorless. The change tion of Korea (NRF) funded by the Korean government (MSIP)
in fluorescence intensity as a function of CN concentration (No. 2012R1A3A2048814). X.C. would like to acknowledge sup-
displays good linearity in the range of 0 to 1.3  104 M with a port from the NSFC (21376117), the Project of Priority Academic
detection limit of 3  107 M. The probe is highly selective for Program Development of Jiangsu Higher Education Institu-
CN in contrast to other anions and can be applied to monitor tions (PAPD), and the Scientific Research Foundation for the
real water samples. Returned Overseas Chinese Scholars of State Education
There are some advantages of using luminescent molecular Ministry.
gold(I) clusters for solid-state cyanide sensing. They can be
easily synthesized and can exhibit phosphorescence of high
quantum yield in the solid state. By the reaction between Notes and references
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