Analytical

Methods
View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

MINIREVIEW

Cite this: DOI: 10.1039/c6ay00135a

View Journal

Recent developments in rhodamine salicylidene

hydrazone chemosensors
Yang Yang,*ab Chao-Ying Gao,ab Jinglin Liua and Dewen Dong*b
Rhodamine spirocyclic chemosensors have attracted a lot of attention due to their simplicity, high
sensitivity, and real-time detection for various analytes. Among the dierent types of substituents,
salicylidene hydrazone is a well-known component due to its electron-donating ability and adjustable
coordination cavity, which has strong sensitivity to various metal ions. In this review, the uorescent and
colorimetric sensors are classied according to their recognition and sensing categories, including Cu2+

Received 15th January 2016

Accepted 27th February 2016

and Hg2+ sensors, other metal ions sensors (Zn2+, Fe3+, Pb2+, Cr6+, Al3+) , CN
and amino acid sensors.
Salicylidene modulation with electron-donating groups is a powerful approach for uorescence

DOI: 10.1039/c6ay00135a

detection of metal ions with a nanomolar range, and the indirect sensing strategy is a good idea for the

www.rsc.org/methods

sensitive detection of anions and other species.

1. Introduction
The development of highly selectivity and sensitivity chemosensors for various transition-metal ions and biochemical
anions has been extensively investigated in recent years.13 The
salicylidene Schi base is one of the easiest synthesizable chemosensors that exhibits strong coordination with various analytes such as Zn2+, Fe3+, Mg2+, Cu2+, Al3+ and Pt2+.49 Until now,

College of Chemistry and Chemical Engineering, Inner Mongolia University for the
Nationalities, Tongliao 028000, PR China. E-mail: yangyang-000@163.com

Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry,

Chinese Academy of Sciences, Changchun, 130022, PR China. E-mail: dwdong@ciac.
ac.cn

Yang Yang received his PhD

degree in 2013 under the supervision of Prof. Bin Li from
Changchun Institute of Optics,
Fine Mechanics and Physics of
the Chinese Academy of Sciences
(CIOMP of CAS). He became
a postdoctoral fellow in Prof.
Dewen Dongs laboratory at
Changchun Institute of Applied
Chemistry of CAS (20142016).
He is currently a lecturer in the
college of chemistry and chemical engineering of Inner Mongolia University for the Nationalities
(IMUN). His research interest is focused on the synthesis and
application of uorescent functional materials in environmental
and biological elds.

This journal is The Royal Society of Chemistry 2016

1 Basic
chemsensors.

Fig.

structure

of

rhodamine

salicylidene

hydrazone

many attempts have been reported based on salicylidene Schi

base chemosensors using substituted salicylaldehyde and
familiar compounds.1012
Rhodamine B is the cheapest dye in the rhodamine family,
which is employed for labelling pigments, uorescence

Chao-Ying Gao received her MS

in 2008 from Northeast Normal
University (NENU) and then she
became a lecturer in the college
of chemistry and chemical engineering of IMUN. She is
currently preparing her thesis
for a doctorate in Changchun
Institute of Applied Chemistry of
CAS. Her research interests are
mainly in the synthesis of uorescent metalorganic frameworks
and
coordination
compounds.

Anal. Methods

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Analytical Methods

Minireview

standards and chemosensors.13,14 Rhodamine spirocyclic chemosensors have attracted a lot of attention due to their
simplicity, high sensitivity, and real-time detection for various
analytes in vivo and in vitro.1518 The preferential binding sites
are spiro-carbonyl O, imide N and other N or O sites such as
ortho-phenol O. However, their selectivity properties to analytes
are strongly inuenced by the structure, substituents, solvent
and temperature.19 Hence a subtle change in the rhodamine
binding sites might aect the spirolactam ring-opening
process which could modify their selectivity and sensitivity
(Fig. 1).20

2. Detection of analytes based on

rhodamine salicylidene hydrazone
2.1

Sensors for detecting Cu2+

The copper ion is an essential trace element in biological

systems, and plays as a catalytic cofactor for a variety of metalloenzymes in the lifecycle.21 Therefore, a convenient and fast
method to detect Cu2+ existing in environmental and biological
resources is of considerable importance. However, it was not
until 2006 that Tong's group reported the rst salicylidene
rhodamine hydrazone chemsensor RhB-Sal (1) and applied it to
the detection of Cu2+ ions in neutral buered media.22 In their
study, the rhodamine chemsensor 1 displayed a reversible
absorption and uorescence enhancement response to Cu2+ via
a 1 : 1 binding mode. Furthermore, the sensitivity of 1 for Cu2+
can be lower than 25 nM in 50% (v/v) buered water/CH3CN by
the absorption spectra method and the 0.1 mM level for the
uorescence method under these conditions. Even in neutral
buered aqueous solutions, the uorescence method was
successful in sensing Cu2+ at a micromolar level.
Ma et al. have designed and synthesized a rhodamine-based
uorescent probe 2 for copper ions.23 Probe 2 exhibited high
sensitivity toward Cu2+ and about a 37-fold increase in uorescence emission intensity, which was observed upon the
addition of 10 equiv. of Cu2+ in 50% waterethanol buered at
pH 7.10. Besides, upon binding Cu2+, a remarkable color
change from colorless to pink was easily observed by the naked

Jinglin Liu received his Ph.D.

degree in 2006 under the guidance of Prof. Xu Bai and Prof.
Hengbin Zhang from Jilin
University. He began his independent research career at
NENU in 2007. He was
promoted to a full professor in
the college of chemistry and
chemical engineering of IMUN in
2012. His current research
interests involve combinatorial
chemistry and organic synthesis
methodology.

Anal. Methods

eye. The linear response range covered a concentration range of

Cu2+ from 8.0  10
7 to 1.0  10
4 mol L
1 and the detection
limit was 3.0  10
7 mol L
1. Except for Co2+, the probe
exhibited high selectivity for Cu2+ over a large number of
coexisting ions. It has been used for direct measurement of Cu2+
content in environmental and biological systems.
Tang's group designed a rhodamine B based derivative 3 as
a colorimetric and uorescent dual mode sensor for recognition
of Cu2+ in CH3CN/H2O (1 : 1, v/v, HEPES 10 mM, pH 7.0)
solution.24 Sensor 3 displayed highly selective, sensitive and
rapid recognition behavior toward Cu2+ among a range of biologically and environmentally important metal ions. The 1 : 1
binding stoichiometry of 3 and Cu2+ was proved by nonlinear
least-squares tting of titration proles and Job's plot; the
association constant and uorescence detection limit were
calculated to be 1.92  106 M
1 and 7.96  10
8 M, respectively.
The Cu2+ recognition process was reversible and showed little
interference from other coexisting metal ions.
Chen and co-workers synthesized a salicylidene rhodamine
chemosensor 4 through the reaction of rhodamine hydrazide
and salicylaldehyde receptor.25 It exhibited a reversible and
sensitive turn-on response of absorption and uorescence
toward Cu2+ in aqueous acetonitrile solution. An approximate
65 and 6-fold enhancement in the absorbance at 556 nm and
uorescence intensity at 573 nm were estimated when the
concentration of Cu2+ reached 10 mM. 4 displayed more sensitivity than the known compound RhB-Sal for Cu2+ (ca. 30 and
2-fold, respectively) under the same conditions. The competition experiments for Cu2+ mixed with common metal ions
exhibited no obvious change in absorption and emission except
for Cr3+ ion, which could induce uorescence quenching to
a certain extent.
Yang's group developed a colorimetric and uorescent
sensor 5 by the condensation reaction of rhodamine B hydrazide and 2,4-dihydroxybenzaldehyde, which showed reversible
and highly selective and sensitive recognition toward Cu2+ over
other examined metal ions.26 Upon addition of Cu2+, sensor 5
exhibited remarkably enhanced absorbance intensity and color
change from colorless to pink in a DMSO and MeCN aqueous

Dewen Dong received his PhD in

1999 from Changchun Institute
of Applied Chemistry of CAS,
and then he became a Lecturer
in Shizuoka University (1999
2001) and a postdoctoral fellow
in the University of Hull (2001
2003). He joined the faculty of
NENU as a full professor in 2003
and moved to Changchun Institute of Applied Chemistry of CAS
as a professor in 2006. His
research includes synthetic
chemistry
and
functional
organic/polymeric materials.

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Minireview

Analytical Methods

buer solution or pure MeCN, and showed signicant oon

uorescence accompanied by color changes from colorless to
orange in MeCN. In DMSO/TrisHCl buer (1 : 9, v/v, pH 7.0)
solutions, the quantication of Cu2+ by 5 was satisfactory in
a linear working range of 10300 mM, with an absorbance
detection limit of 3.42  10
6 M. The sensor 5 was also

Table 1

successfully applied to the determination of Cu2+ in water

samples.
Gupta and co-workers also synthesized the rhodaminederived Schi base 6 and investigated its sensing behavior by
UV-vis and uorescence spectroscopic techniques.27 The sensor
exhibited a highly selective and sensitive colorimetric response

The comparison of the uorescence probes for Cu2+ based on salicylidene

Structure

Media

Analyte

Detection
limit

Working
range

Association
constant

Detection
mode

Probe ref.

CH3CN/H2O,
TrisHCl, pH 7.0

Cu2+

25 nM, 0.1 mM

010 mM

6.91  104

Abs, FL

1 (ref. 22)

EtOH/water,
TrisHCl, pH 7.1

Cu2+

0.3 mM

0.8100 mM

FL

2 (ref. 23)

CH3CN/H2O,
HEPES, pH 7.0

Cu2+

7.96  10
8

010 mM

1.92  106

Abs, FL

3 (ref. 24)

CH3CN/TrisHCl,
pH 7.0

Cu2+

10 mM,
naked eye

020 mM

3.09  104

Abs, FL

4 (ref. 25)

DMSO/TrisHCl,
pH 7.0

Cu2+

3.42  10
6

10300 mM

2.83  104

Abs, FL

5 (ref. 26)

CH3OH/H2O

Cu2+, Al3+,
Fe3+

0.99  10
8

020 mM

1.1  106

Abs

6 (ref. 27)

CH3OH/HEPES,
pH 7.0

Cu2+, VO2+

10
6 to 10
5,
naked eye

080 mM

Abs

7 (ref. 28)

CH3CN/H2O

Cu2+, Hg2+

10
5

10100 mM

Abs, FL

8 (ref. 29)

CH3OH/HEPES,
pH 7.0

Cu2+

3.7  10
8

05 mM

Abs

9 (ref. 30)

CH3OH/HEPES,
pH 7.0

Cu2+

1.2  10
9

020 mM

Abs, FL

10 (ref. 30)

Dry CH3CN

Cu2+

0.49, 14.98 mM

020 mM

6.72  104,
4.23  104

Abs, FL

11 (ref. 31)

CH3CN/HEPES,
pH 7.04

Cu2+

0.20 mM

020 mM

3.7  104

Abs, FL

12 (ref. 32)

This journal is The Royal Society of Chemistry 2016

Anal. Methods

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Analytical Methods

Minireview

to Cu2+ and Al3+, and an oon uorescence response toward

Fe3+ in semi-aqueous media. The spectral changes obtained are
large enough in the visible region of the spectrum and thus
enable naked-eye detection. The 1 : 1 stoichiometric ratio
between probe and metal ions was proposed based on a Job's
plot, which was further conrmed by ESI mass analysis. Paper
strips were also used for the detection of Cu2+, Al3+ and Fe3+
ions.
Huo et al. synthesized a rhodamine-based colorimetric chemosensor by incorporating rhodamine hydrazide and 5-chlorosalicylaldehyde in ethanol. The sensor 7 exhibited specic
absorbance responses to Cu2+ and turned from colourless to
purple red, which allowed naked-eye detection of Cu2+ ions in
50% CH3OHH2O solution.28 The low detection threshold for
Cu2+ in UV-vis spectrum was 10
6 to 10
5 M and at this level the
color change was very obvious. In contrast, the selectivity
towards VO2+ was determined from changes in the emission
spectra in the nanomolar range. This represents the rst reported rhodamine-based sensor capable of detecting both Cu2+
and VO2+ using two dierent modes.
Yang and co-workers reported a rhodamine salicylidene
hydrazone derivative 8 by condensation of 3,5-dichlorosalicylaldehyde and rhodamine B hydrazide. The sensor 8 was
utilized as a colorimetric and reversible chemosensor for Cu2+
and Hg2+ in aqueous CH3CN media.29 Among the various metal
ions, the sensor 8 exhibited remarkably enhanced absorbance
intensity and color change for Cu2+, and showed signicant

Table 2

oon uorescence accompanied with red emission upon

binding with Hg2+. The absorbance and uorescence signals of
8 could be restored with addition of EDTA into solutions of 8Cu2+ and 8-Hg2+, indicating that the binding process is chemically reversible.
Huo's group synthesized two salicylidene-based rhodamine
derivatives 9 and 10.30 Because of their dierent salicylidene
groups, 9 exhibited particular selectivity towards Cu2+ with color
changes from colorless to yellow, which can be used as a UV-vis
chemosensor for Cu2+. Due to the strong intramolecular charge
transfer, 9 was very weakly uorescent and the 9-Cu2+ metal
complex remains non-uorescent. The absorbance intensity of
9 was linearly proportional to Cu2+ concentrations of 05 mmol L
1
with a detection limit of 3.7  10
8 M. Dierent from the
process of 9, the sensor 10 was strongly uorescent, which can
be used as a dual-channel colorimetric and uorescent
compound for Cu2+. The uorescence detection limit of 10 to
Cu2+ is 1.2  10
9 M, which was more sensitive than the UV-vis
behavior of 9. The cell experiments show the good cellmembrane permeability of compound 10, and it can thus be
used to mark Cu2+ within living cells.
A new rhodamine derivative 11 bearing an electron withdrawing group NO2 at the 5-position of the 2-hydroxyphenyl
moiety was synthesized by Chen et al.31 The sensor displayed
similar high selectivity for Cu2+ over coexisting metal ions
except that Fe3+ brought about some absorption interference
and Bi3+ led to a little uorescence interference. The detection

The comparison of the uorescence probes for Cu2+ from naphthaldehyde and rhodamine 6G

Structure

Anal. Methods

Media

Analyte

Detection
limit

Working
range

Association
constant

Detection
mode

Probe ref.

CH3CN/HEPES,
pH 7.04
CH3CN/H2O

Cu2+

0.2 mM

020 mM

5.0  104

Abs, FL

13 (ref. 32)

Cu

0.32 ppb

05 mM

5.4  10

Abs

13 (ref. 33)

CH3CN/HEPES,
pH 7.4

Cu2+

0.156 mM

04 mM

FL

15 (ref. 34)

CH3CN/HEPES,
pH 7.04

Cu2+

0.2 mM

020 mM

5.6  105

Abs, FL

14 (ref. 32)

CH3CN/HEPES,
pH 7.4

Cu2+

0200 mM

2.5  104

Abs, FL

16 (ref. 35)

EtOH/H2O, NaAcHAc,
pH 7.0

Cu2+

10 nM,
25 nM

05 mM

1  106

Abs, FL

17 (ref. 36)

CH3CN/H2O,
pH 7.0

Cu2+

5 mM,
naked eye

050 mM

4.877  104

Abs, FL

18 (ref. 37)

2+

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Minireview

limit for Cu2+ calculated from the uorescence titration data

was 0.49 mM. The sensitivity of 11 for Cu2+ in pure CH3CN is
higher than aqueous solutions. The sensor 11 was expected to
reversibly bind to Cu2+ in each medium, forming a 1 : 1 stoichiometric 12-Cu2+ complex with an association constant of
6.72  104 M
1 and 4.23  104 M
1, respectively (Table 1).
Wang and co-workers reported three rhodamine-salicylidene
derivative 12, rhodamine-naphthalene derivative 13 and
rhodamine-binaphthol derivative 14 as specic uorescent and
colorimetric chemosensors for Cu2+.32 These probes exhibited
selective oon type changes in both absorption and emission spectra toward Cu2+ ions compared to other metal ions.
The detection limits of 12, 13 and 14 toward Cu2+ were all 0.20
mM (12.7 ppb) by plotting the uorescence intensity at 571 nm
versus the concentration of Cu2+. The Job's plots indicated a 1 : 1
stoichiometry between 12, 13 or 14 and Cu2+. The association
constants were 3.7  104 M
1, 5.0  104 M
1 and 5.6  105 M
1
respectively, which suggested that the complex of 14-Cu2+ was
more stable than that of 12-Cu2+ and 13-Cu2+.
Wu's group reported a rhodamine-based 2-hydroxy-1-naphthaldehyde hydrazone chemosensor 13, which showed
a reversible, selective, and sensitive absorbance enhancement
response to Cu2+ in a buered CH3CNH2O media.33 The probe
13 had a linear response to increasing amounts of low Cu2+
concentration (between 5 and 50 nM), establishing that the
system has a limit of quantication down to 0.32 ppb. The
association constant of molecule 13 with Cu2+ was 5.4  105
M
1, and the stoichiometry for 13-Cu2+ was calculated to be 1 : 1
by the Job's plot method and assumed by the nonlinear tting
of the titration curve.
Yin and co-workers synthesized a sugar-rhodamine salicylidene uorescent sensor 15, and investigated its properties for
Cu2+ according to the Cu2+ triggered spirolactam ring-opening
mechanism.34 The introduction of a sugar residue into the salicylidene part, combined with the solvent eect, signicantly
improved its selectivity and sensitivity. The synthesized probe
15 exhibited high selectivity and excellent sensitivity to Cu2+ in
acetonitrile media. The detection limit was 0.15 mM, about 200
times lower than the recommended water quality standard of
Cu2+ ions in drinking water. The probe 15 could be simply,
rapidly, and satisfactorily used to detect the concentration of
Cu2+.
Yoon and co-workers reported a rhodamine-pyrene derivative 16 as a ratiometric and naked-eye sensor for the detection
of Cu2+ ion in neutral buered media.35 It displayed a highly
selective and ratiometric uorescence change and a colorimetric change upon the addition of Cu2+, utilizing the spirolactam (nonuorescent) to ring opened amide (uorescent)
process. The nonlinear tting of the titration curve and the data
of Job's plot from absorption spectra assumed a 1 : 1 stoichiometry for the 16-Cu2+ complex with an association constant of
2.5  104 M
1.
Tongs group designed another rhodamine chemosensor 17
using salicylaldehyde and rhodamine 6G hydrazine as copperchelating and signal-reporting groups.36 The sensor exhibited
selective absorbance enhancement to Cu2+ over other metal
ions at 529 nm, with a dynamic working range of 0.055.00 mM
This journal is The Royal Society of Chemistry 2016

Analytical Methods

and a detection limit of 10 nM. The linear working range using

17 for Cu2+ was 0.13.6 mM and the detection limit was 25 nM.
Both absorptiometric and uorometric methods were applied
for the detection of Cu2+ in three water samples.
A rhodamine 6G based 4-(diethylamino) salicylidene hydrazone chemosensor 18 was reported by Liu et al.37 The sensor
exhibited a high selectivity for Cu2+ and could serve as a good
selective naked-eye chemosensor for Cu2+ in CH3CN. The
association constant of 18 with Cu2+ ion was found to be 4.877
 104 M
1, and a 1 : 1 stoichiometric complexation was
conrmed by the Job's plot. Upon the addition of Cu2+, the
spirolactam ring of 18 was opened and the solution changed
from colorless to red. Strangely, an unexpected uorescence
quenching was observed upon the addition of 5 equiv. Cu2+,
which is contrary to the uorescence turn-on of most rhodamine based chemosensors (Table 2).

2.2

Sensors for detecting Hg2+

Hg2+ is one of the most severe environmental contaminants

because it can cause serious health problems, damaging the
central nervous and endocrine systems, leading to many
cognitive and motion disorders.38 There are many rhodamine
spirocyclic chemosensors that have been applied for sensing
Hg2+ in environmental and biological resources.3945 However,
rhodamine sensors modulated with a salicylidene structure for
real-time monitoring of Hg2+ in environmental samples are still
greatly needed.46,47
Yoon's group synthesized two rhodamine hydrazone derivatives 19 bearing a thiol group as selective uorescent and
colorimetric chemosensor to Hg2+.48 The ring-opening process
of spirolactam enables large uorescent enhancement and
colorimetric change upon the addition of Hg2+. The 2 : 1 stoichiometry between 19 and Hg2+ was conrmed by Job's plots. A
plot of the uorescent intensities of 19 versus the log concentration of Hg2+ exhibited a linear response in the range of 1 nM
to 1 mM, and the detection limit was 1 nM. The sensor 19 can be
employed for the in vivo imaging of nanomolar concentrations
of Hg2+.
Zhao et al. also reported that 13 can achieve double-channel
detection of Hg2+ and Mg2+ by dierent binding modes and can
detect Hg2+ through a visible color change.49 The detection limit
for the sensor was estimated to be 80 nM. The association
constant between 13 and Hg2+ was determined to be 1.0  105
M
1. Selective binding sites of the compound 13 to Hg2+ and
Mg2+ caused immediate and remarkable uorescence
enhancement at 589 nm and 523 nm. Furthermore, this probe
can indirectly detect glutathione and cysteine with good linear
relationships.
Jiang and co-workers found the sensor 13 exhibits extremely
high sensitivity (as low as 2 ppb) and selectivity to Hg2+ in
methanol solution.50 The association constant of 13 with Hg2+
was calculated to be 3.9  10
5 (R 0.9966) by using nonlinear
least-squares analysis. Further characterization conrmed
a 1 : 1 complex, which restores the ICT eect to show uorescence. The excellent biological value of 13 was demonstrated by
the uorescence imaging in living yeast and HeLa cells.

Anal. Methods

View Article Online

Analytical Methods
Table 3

The comparison of the uorescence sensors for Hg2+

Structure

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Minireview

Media

Analyte

Detection
limit

Working
range

Association
constant

Detection
mode

Probe ref.

CH3CN/H2O

Hg2+

1 nM

10
9 to 10
6

FL

19 (ref. 48)

CH3OH
CH3CN

Hg2+
Hg2+, Mg2+

2 ppb
80 nM

0300 mM
0100 mM

3.9  10
5
1  105

Abs, FL
FL

13 (ref. 49)
13 (ref. 50)

CH3OH

Hg2+

4 ppb

08  10
4

1  106

Abs, FL

20 (ref. 51)

CH3CN/H2O

Hg2+

15 nM

0200 mM

Abs, FL

21 (ref. 52)

Jiang et al. developed a highly sensitive and selective Hg2+

probe 20 by connecting a water soluble receptor group
(sulfonated b-naphthol) and rhodamine B together through
hydrazine hydrate.51 The results illustrated that 20 has excellent
sensitivity and selectivity abilities toward Hg2+ and reaches as
low as 4 ppb of detection limit in methanol. The 1 : 1 binding
stoichiometry was conrmed by the Job's plot method, and the
association constant for Hg2+ was estimated to be 4.6  106
M
1. These outstanding cell permeablility and compatibility
characteristics conrm that this kind of Hg2+ probe has great
potential in biological and pharmacological systems.
Ma and co-workers designed a novel functionalized SBA-15
nanosensor with salicylidene based rhodamine hydrazone as
the binding site for Hg2+.52 The sensor showed uorescence
enhancement selectivity as well as selective coloration toward
Hg2+. Covalently graed 21 onto the inner surface of SBA-15
makes the nanosensor easy to recover and recycle. Job's plot
indicated that 21 coordinated to Hg2+ in a 1 : 1 binding stoichiometry; the detection limit of 21 for Hg2+ is about 1.5 
10
8 M. The addition of S2
led to both color and uorescence
fading, indicating the reversibility of the binding between 21
and Hg2+. Using Hg2+ and S2
as chemical inputs and the
uorescence intensity signal as output, 21-SBA-15 can be
utilized as an INHIBIT logic gate at the nanoscale level
(Table 3).

2.3

Sensors for detecting other metal ions

Zheng et al. have found that the old chemsensor RhB-Sal (1)
could be used for the selective and sensitive detection of CrO42

in acidic conditions.53 Based on the special oxidation reaction
with potassium dichromate to produce a highly uorescent
rhodamine B, the uorescence enhancement at 591 nm was
linearly well related to the concentration of CrO42
from 1.0 
10
8 to 3.0  10
7 M (0.4212.6 ng mL
1) with a detection limit
of 1.5  10
9 M (0.063 ng mL
1). The proposed method could

Anal. Methods

act as a simple naked-eye probe for selective detection of Cr6+,

and be explored to indicate Cr6+ from Cr2O72
and CrO42

anions.
Guchhait and Kar et al. developed a novel turn-on uorescent chemosensor based on a rhodaminedihydroxybenzaldehyde conjugate.54 The sensor 22 displayed an excellent
selectivity and high sensitivity toward Al3+ with remarkably
enhanced uorescent intensity by a chelation-enhanced uorescence (CHEF) process and also shows a clear color change
from colorless to deep magenta. Job's plot and TOF-MS analysis
conrmed the 1 : 1 binding stoichiometry between 22 and Al3+
ions, and the association constant calculated from the absorption titration result was found to be 2.56  103 M
1. Under UV
light illumination, one can visually detect even 2  10
8 M Al3+
in aqueous-acetonitrile buer solution without the aid of any
sophisticated instruments.
Tong et al. found that 4-N,N-diethylamino-salicylidene
rhodamine hydrazone 23 exhibited selective and ratiometric
uorescent response toward Zn2+ over other metal ions in
aqueous ethanol.55 Upon the addition of Zn2+, there was an
obvious color change of the uorescence from dark cyan to
greenish yellow which could be monitored easily by the naked
eye. An association constant of log Ka 5.22 was calculated for
the 1 : 1 metal-to-ligand complex according to the absorption
spectral titration data. The 23-Zn2+ complex showed its reversibility in the presence of EDTA.
Li et al. synthesized a colorimetric and uorescence turn on
chemosensor 24 for the detection of Pb2+ ions.56 The sensor
displayed a highly selective uorescence enhancement (about
550 fold) and colorimetric change from colorless to pink in the
presence of Pb2+ in chloroformTHF (7 : 3). The absorbance at
557 nm was saturated aer 2 equiv. of Pb2+ was added. The
uorescence intensity at 577 nm increased continuously with
the Pb2+ concentration in the range of 10
6 to 10
5 mol L
1. The
binding stoichiometry between 24 and Pb2+ was estimated to be
1 : 1 by Job's plot. The reversibility of the sensor was further

This journal is The Royal Society of Chemistry 2016

View Article Online

Minireview

Analytical Methods

Table 4 The comparison of the salicylidene probes for other metal ions

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Structure

Media

Analyte

Detection
limit

Working
range

Association
constant

Detection
mode

Probe ref.

H2SO4 buer

CrO42

1.5 nM

03 mM

FL

1 (ref. 53)

EtOH/H2O, HEPES,
pH 7.0

Zn2+

0.05 mM

010 mM

1.66  105

Abs, FL

22 (ref. 54)

CH3CN/H2O, HEPES,
pH 7.2

Al3+

20 nM

0100 mM

2.56  103

FL

23 (ref. 55)

CHCl3/THF

Pb2+

010 mM

Abs, FL

24 (ref. 56)

EtOH/H2O

Fe3+

6.93 mM

050 mM

2  104

FL

25 (ref. 57)

micromolar concentration range, was reasonably estimated to

be 6.93  10
6 M. Furthermore, aer treatment with EDTA, the
color and uorescent emission intensity changed back, indicating that 25 can be classied as a reversible chemosensor for
Fe3+ (Table 4).

conrmed by EDTA experiments. Sensor 24 could be used

potentially for the detection Pb2+ in the environment.
Chen et al. have designed and synthesized a new targetable
uorescent probe 25 by linking a conjugated naphthalene
chromophore to a rhodamine platform and a lipophilic triphenylphosphonium cation.57 The probe could sensitively and
selectively detect mitochondrial Fe3+ in living cells. It exhibited
a pseudo-large Stokes shi on the basis of the FRET mechanism
and excellent selectivity for Fe3+ excluding the interference of
other metal ions, especially Cr3+. The stability constant of the
25-Fe3+ complex was calculated to be 2.0  104 M
1. The
detection limit of 25 responded to Fe3+ linearly in the

Table 5

Structure

2.4

Detection of CN
and amino acids

Many well-designed rhodamine hydrazone cation chemosensors could be successfully developed as anionic chemosensors by utilizing the indirect method. Using the ensemble
salicylidene rhodamine hydrazone RhB-Sal and Cu2+ ions, Li's

The comparison of the metal complex sensors for CN
and amino acids
Media

Analyte

Detection limit

Working range

Detection mode

Probe ref.

CH3CN/H2O, TrisHCl,
pH 7.0

CN

ClO

Histidine,
protease
Cysteine

0.013 ppm
0.81 mM

0.17 mM
070 mM
05 mg mL

Abs
Abs
Abs

26 (ref. 58)
26 (ref. 59)
26 (ref. 60)

0.14 mM

028 mM

Abs, FL

27 (ref. 61)

CH3CN/H2O

CN

0.72 nM

010 mM

Abs, FL

28 (ref. 62)

THFCH2Cl2 solid state

UV

Abs

29 (ref. 63)

EtOH/H2O, TrisHCl,
pH 7.1

This journal is The Royal Society of Chemistry 2016

Anal. Methods

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Analytical Methods

group designed an indirect anionic chemosensor for

cyanide.58 Upon the addition of trace CN
, the magenta color
faded to colorless immediately, with a detection limit as low
as 0.013 ppm, much lower than the maximum contaminant
level for cyanide in drinking water (0.2 ppm). Later they
developed the rhodamine chemosensor 1 as a new type of
probe for the detection of ClO
based on the oxidation
property of hypochlorites and dierent coordinating properties of Cu+ and Cu2+.59 Upon the addition of trace ClO
, the
colorless solution turned magenta to report the concentration of the present hypochlorite ions, with the detection limit
as low as 8.1  10
7 M in real water samples. They also
proposed an indirect approach to utilize sensitive colorimetric sensor 26-BSA to detec sensitivelyt a-amino acids.60 As
the hydrolysis of bovine serum albumin (BSA) with the aid of
trypsin produces a-amino acids, the complex of 26-BSA could
act as a label-free, sensitive, selective sensor toward trypsin.
The detection process could be visually observed by the
naked eye.
Using the chemosensing ensemble method, Yang et al.
developed a uorescent chemosensing ensemble 27 for the
detection of cysteine based on the uorescence inner lter
eect.61 Upon adding cysteine to the above solution, the
complexation of Cu2+ and cysteine led to the dissociation of 27,
which thus decreases the uorescence inner lter eect of the
solution, and leading to the uorescence increase of the chemosensing system. The uorescence increase is linear with
cysteine concentration up to 10.0 mM, with a detection limit of
1.4  10
7 M.
Hu and co-workers reported a selective and sensitive method
to detect aqueous CN
based on a rhodamine B hydrazide and
2-tertbutyldimethyl silyloxy benzaldehyde conjugate (RTSB)
and Fe3+ derivative.62 RTSB displayed highly selectivity and
sensitivity to Fe3+ with uorescence emission enhancement at
581 nm accompanied by a color change from colorless to pink.
In response to CN
, the system 28 provides a remarkable
uorescence intensity change, blue shi and also a clear color
change from pink to colorless. The background anions show
small or no interference with the detection of CN
. The detection limit of the system for CN
was around 7.2  10
8 M.
Treatment of 28 with CN
aorded a similar NMR spectrum
with that of RTSB alone, which indicated that addition of CN

prompted the dissociation of 28 and the release of free probe
RTSB.
Recently, Tong and Tang et al. developed a new photochromic system based on rhodamine B salicylidene hydrazone
metal complex 29.63 The molecules showed absorption turnon and uorescence turn-o response upon UV irradiation
both in solution and in solid matrix. UV light promoted the
isomerization of the salicylaldehyde hydrazone moiety from the
enol-form to the keto-form, and subsequently induced the spirolactam ring-opening in the rhodamine B part and caused the
photochromic reaction. Owing to the good fatigue resistance,
and the tunable lifetime of the ring-open state, 29 was applied
in photo printing and UV strength measurement in the solid
state (Table 5).

Anal. Methods

Minireview

3.

Conclusions

In this review, we have covered the development and applications of rhodamine salicylidene hydrazone chemosensors based
on spiroring-opening of the xanthene platform. Considering the
uorophores and structureactivity of the salicylidene group,
most of them display strong selectivity and sensitivity to Cu2+ in
neutral buered aqueous solution. From the type of substituents on the salicylidene group, we found that the electrondonating groups have superior uorescence detection limits to
the electron-withdrawing substituent, in the order of CH3 >
OCH3 > H > NO2. The detection limits based on the absorbance intensity are similar: OCH3 > H > F > Cl > OH > NO2.
However, for both ligands and complexes, the presence of an
electron-withdrawing substituent, compared with no substituent on the salicylidene ring, will greatly improve its emission
band or absorption band enhancements and binding capacities. It is noteworthy that the structural modulation of salicylidene is a very powerful approach for other cations, and
application of the indirect sensing strategy is a good idea for the
sensitive detection of anions and other species.
Rhodamine salicylidene hydrazone probes play a major role
in pure organic solvent and aqueous organic media, the
combination of rhodamine probes with SiO2 or Fe3O4 nanomaterials and ber polymers, pave a fast and ecient way to the
detection and separation of heavy metal ions in the environment. Furthermore, the design and implementation of hydrophilic groups in rhodamine derivatives develops their sensing
abilities in biological imaging and drug delivery. In short, the
development of high selectivity, sensitivity, photostability and
good biocompatibility rhodamine probes will be of great
importance for the environmental and life sciences.

Acknowledgements
The authors gratefully thank the nancial supports of the
National Natural Science Foundation of China (21172211,
21542006, 21362020), the Natural Science Foundation of Inner
Mongolia Autonomous Region, China (2014BS0205) and the
Scientic Research Foundation of Inner Mongolia University for
the Nationalities (NMD1311, NMDGP1403).

References
1 J. Chan, S. C. Dodani and C. J. Chang, Nat. Chem., 2012, 4,
973984.
2 M. E. Moragues, R. Martnez-Manez and F. Sancenon, Chem.
Soc. Rev., 2011, 40, 25932643.
3 J. Du, M. Hu, J. Fan and X. Peng, Chem. Soc. Rev., 2012, 41,
45114535.
4 E. J. Song, H. Kim, I. H. Hwang, K. B. Kim, A. R. Kim, I. Noh
and C. Kim, Sens. Actuators, B, 2014, 195, 3643.
5 M. Shellaiah, Y.-H. Wu and H.-C. Lin, Analyst, 2013, 138,
29312942.
6 L. Wang, H. Li and D. Cao, Sens. Actuators, B, 2013, 181, 749
755.

This journal is The Royal Society of Chemistry 2016

View Article Online

Published on 22 March 2016. Downloaded by Indian Institute of Technology New Delhi on 26/03/2016 09:09:56.

Minireview

7 S. Kim, J. Y. Noh, K. Y. Kim, J. H. Kim, H. K. Kang, S.-W. Nam,

S. H. Kim, S. Park, C. Kim and J. Kim, Inorg. Chem., 2012, 51,
35973602.
8 Y. Ma, H. Liu, S. Liu and R. Yang, Analyst, 2012, 137, 2313
2317.
9 S. M. Borisov, R. Saf, R. Fischer and I. Klimant, Inorg. Chem.,
2013, 52, 12061216.
10 A. K. Mandal, M. Suresh, P. Das, E. Suresh, M. Baidya,
S. K. Ghosh and A. Das, Org. Lett., 2012, 14, 29802983.
11 Y. W. Choi, G. J. Park, Y. J. Na, H. Y. Jo, S. A. Lee, G. R. You
and C. Kim, Sens. Actuators, B, 2014, 194, 343352.
12 P. S. Hariharan and S. P. Anthony, Spectrochim. Acta, Part A,
2015, 136, 16581665.
13 M. Beija, C. A. M. Afonso and J. M. G. Martinho, Chem. Soc.
Rev., 2009, 38, 24102433.
14 V. Dujols, F. Ford and A. W. Czarnik, J. Am. Chem. Soc., 1997,
119, 73867387.
15 J. F. Zhang, Y. Zhou, J. Yoon, Y. Kim, S. J. Kim and J. S. Kim,
Org. Lett., 2010, 12, 38523855.
16 D. T. Quang and J. S. Kim, Chem. Rev., 2010, 110, 62806301.
17 Y. Yang, Q. Zhao, W. Feng and F. Li, Chem. Rev., 2013, 113,
192270.
18 H. N. Kim, M. H. Lee, H. J. Kim, J. S. Kim and J. Yoon, Chem.
Soc. Rev., 2008, 37, 14651472.
19 X. Chen, T. Pradhan, F. Wang, J. S. Kim and J. Yoon, Chem.
Rev., 2012, 112, 19101956.
20 H. Zheng, X.-Q. Zhan, Q.-N. Bian and X.-J. Zhang, Chem.
Commun., 2013, 49, 429447.
21 R. Uauy, M. Olivares and M. Gonzalez, Am. J. Clin. Nutr.,
1998, 67, 952S959S.
22 Y. Xiang, A. Tong, P. Jin and Y. Ju, Org. Lett., 2006, 8, 2863
2866.
23 J. Xu, Y. Hou, Q. Ma, X. Wu, S. Feng, J. Zhang and Y. Shen,
Spectrochim. Acta, Part A, 2014, 124, 416422.
24 L. Tang, J. Guo and N. Wang, Bull. Korean Chem. Soc., 2013,
34, 159163.
25 R. Tang, K. Lei, K. Chen, H. Zhao and J. Chen, J. Fluoresc.,
2011, 21, 141148.
26 Z. Xu, L. Zhang, R. Guo, T. Xiang, C. Wu, Z. Zheng and
F. Yang, Sens. Actuators, B, 2011, 156, 546552.
27 V. K. Gupta, N. Mergu and L. K. Kumawat, Sens. Actuators, B,
2016, 223, 101113.
28 F.-J. Huo, J. Su, Y.-Q. Sun, C.-X. Yin, H.-B. Tong and Z.-X. Nie,
Dyes Pigm., 2010, 86, 5055.
29 Y. Yang, C. Gao, B. Li, L. Xu and L. Duan, Sens. Actuators, B,
2014, 199, 121126.
30 W. Gao, Y. Yang, F. Huo, C. Yin, M. Xu, Y. Zhang, J. Chao,
S. Jin and S. Zhang, Sens. Actuators, B, 2014, 193, 294300.
31 K. Dai, B. Xu and J. Chen, J. Fluoresc., 2014, 24, 11291136.
32 M. Dong, T.-H. Ma, A.-J. Zhang, Y.-M. Dong, Y.-W. Wang and
Y. Peng, Dyes Pigm., 2010, 87, 164172.
33 G. H. Wu, D. X. Wang, D. Y. Wu, Y. Gao and Z. Q. Wang, J.
Chem. Sci., 2009, 121, 543548.
34 J. Yin, X. Ma, G. Wei, D. Wei and Y. Du, Sens. Actuators, B,
2013, 177, 213217.
35 Y. Zhou, F. Wang, Y. Kim, S.-J. Kim and J. Yoon, Org. Lett.,
2009, 11, 44424445.

This journal is The Royal Society of Chemistry 2016

Analytical Methods

36 Y. Xiang, Z. Li, X. Chen and A. Tong, Talanta, 2008, 74, 1148

1153.
37 Y. Wang, H. Wu, J. Sun, X. Liu, J. Luo and M. Chen, J.
Fluoresc., 2012, 22, 799805.
38 R. K. Zalups and L. H. Lash, Toxicol. Appl. Pharmacol., 2006,
214, 8897.
39 M. J. Culzoni, A. M. de la Pena, A. Machuca, H. C. Goicoechea
and R. Babiano, Anal. Methods, 2013, 5, 3049.
40 Z. Yang, L. Hao, B. Yin, M. She, M. Obst, A. Kappler and J. Li,
Org. Lett., 2013, 15, 43344337.
41 V. K. Bhardwaj, H. Sharma, N. Kaur and N. Singh, New J.
Chem., 2013, 37, 41924198.
42 Y. Chen and S. Mu, Sens. Actuators, B, 2014, 192, 275282.
43 K. Ghosh, T. Sarkar and A. Majumdar, Asian J. Org. Chem.,
2013, 2, 157163.
44 Y.-J. Gong, X.-B. Zhang, Z. Chen, Y. Yuan, Z. Jin, L. Mei,
J. Zhang, W. Tan, G.-L. Shen and R.-Q. Yu, Analyst, 2012,
137, 932938.
45 R. Han, X. Yang, D. Zhang, M. Fan, Y. Ye and Y. Zhao, New J.
Chem., 2012, 36, 19611965.
46 H. Y. Lee, K. M. K. Swamy, J. Y. Jung, G. Kim and J. Yoon,
Sens. Actuators, B, 2013, 182, 530537.
47 S. Tong, L. Zhang, L. Bing and L. Yi, Sens. Actuators, B, 2014,
203, 157164.
48 H. N. Kim, S.-W. Nam, K. M. K. Swamy, Y. Jin, X. Chen,
Y. Kim, S.-J. Kim, S. Park and J. Yoon, Analyst, 2011, 136,
13391343.
49 Y. Zhao, B. Zheng, J. Du, D. Xiao and L. Yang, Talanta, 2011,
85, 21942201.
50 L. Jiang, L. Wang, B. Zhang, G. Yin and R.-Y. Wang, Eur. J.
Inorg. Chem., 2010, 44384443.
51 L. Jiang, L. Wang, B. Zhang, G. Yin and R.-Y. Wang, Open J.
Inorg. Chem., 2011, 1, 1622.
52 Z. Dong, X. Tian, Y. Chen, J. Hou and J. Ma, RSC Adv., 2013, 3,
22272233.
53 A. F. Zheng, J. Chen, G. Wu, G. Wu, Y. G. Zhang and H. Wei,
Spectrochim. Acta, Part A, 2009, 74, 265270.
54 A. Dhara, A. Jana, N. Guchhait, P. Ghosh and S. K. Kar, New J.
Chem., 2014, 38, 16271634.
55 N. Li, W. Tang, Y. Xiang, A. Tong, P. Jin and Y. Ju,
Luminescence, 2010, 25, 445451.
56 L.-Q. Li and L.-P. Meng, Spectrochim. Acta, Part A, 2014, 122,
772775.
57 W. Chen, W. Gong, Z. Ye, Y. Lin and G. Ning, Dalton Trans.,
2013, 42, 1009310096.
58 X. Lou, L. Qiang, J. Qin and Z. Li, ACS Appl. Mater. Interfaces,
2009, 1, 25292535.
59 X. Lou, Y. Zhang, Q. Li, J. Qin and Z. Li, Chem. Commun.,
2011, 47, 31893191.
60 X. Lou, L. Zhang, J. Qin and Z. Li, Langmuir, 2010, 26, 1566
1569.
61 X.-F. Yang, P. Liu, L. Wang and M. Zhao, J. Fluoresc., 2008,
18, 453459.
62 Z.-Q. Hu, M. Du, L.-F. Zhang, F.-Y. Guo, M.-D. Liu and M. Li,
Sens. Actuators, B, 2014, 192, 439443.
63 K. Li, Y. Xiang, X. Wang, J. Li, R. Hu, A. Tong and B. Z. Tang,
J. Am. Chem. Soc., 2014, 136, 16431649.

Anal. Methods