Cu2+-selective turn-on fluorescence signaling based on metal-induced hydrolysis of pyrenecarbohydrazide

Article abstract of DOI:10.1016/j.tetlet.2017.06.038

We developed a simple Cu²⁺-selective turn-on fluorescence signaling probe based on the hydrolysis of 1-pyrenecarbohydrazide (1) to 1-pyrenecarboxylic acid. Probe 1 exhibited prominent fluorescence signaling of Cu²⁺ ions in a 10% aqueous Tris-buffered (pH 7.0) DMSO solution with a detection limit of 5.93?×?10^?8?M. Signaling with control compounds derived from pyreneacetic acid and pyrenebutyric acid showed that the fluorescence signal became less pronounced as the distance between the hydrazide functionality and the pyrene fluorophore increased. As a practical application, this probe was employed for the determination of Cu²⁺ in a simulated semiconductor wastewater.

Full text of DOI:10.1016/j.tetlet.2017.06.038

Accepted Manuscript
Cu2+-selective turn-on fluorescence signaling based on metal-induced hydroly-
sis of pyrenecarbohydrazide
Hyein Ryu, Ji Hye Baek, Myung Gil Choi, Jong Chan Lee, Suk-Kyu Chang
PII:
S0040-4039(17)30760-8
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.06.038
TETL 49030
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
6 April 2017
10 June 2017
13 June 2017
Please cite this article as: Ryu, H., Hye Baek, J., Gil Choi, M., Chan Lee, J., Chang, S-K., Cu2+-selective turn-on
fluorescence signaling based on metal-induced hydrolysis of pyrenecarbohydrazide, Tetrahedron Letters (2017),
doi: http://dx.doi.org/10.1016/j.tetlet.2017.06.038
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Cu2+-selective turn-on fluorescence signaling
based on metal-induced hydrolysis of
pyrenecarbohydrazide
Leave this area blank for abstract info.
Hyein Ryu, Ji Hye Baek, Myung Gil Choi, Jong Chan Lee, Suk-Kyu Chang*
Department of Chemistry, Chung-Ang University, Seoul 06974, Republic of Korea

1
Tetrahedron Letters
journal homepage: www.els evier.com
Cu2+-selective turn-on fluorescence signaling based on metal-induced hydrolysis of
pyrenecarbohydrazide
Hyein Ryu, Ji Hye Baek, Myung Gil Choi, Jong Chan Lee, Suk-Kyu Chang∗
Department of Chemistry, Chung-Ang University, Seoul 06974, Republic of Korea
ARTICLE INFO
ABSTRACT
Article history:
Received
We developed a simple Cu2+-selective turn-on fluorescence signaling probe based on the
hydrolysis of 1-pyrenecarbohydrazide (1) to 1-pyrenecarboxylic acid. Probe 1 exhibited
prominent fluorescence signaling of Cu2+ ions in a 10% aqueous Tris-buffered (pH 7.0) DMSO
solution with a detection limit of 5.93 × 10–8 M. Signaling with control compounds derived from
pyreneacetic acid and pyrenebutyric acid showed that the fluorescence signal became less
pronounced as the distance between the hydrazide functionality and the pyrene fluorophore
increased. As a practical application, this probe was employed for the determination of Cu2+ in a
simulated semiconductor wastewater.
Received in revised form
Accepted
Available online
Keywords:
Cu2+ ions
Fluorescence signaling
Hydrazide hydrolysis
Pyrenecarbohydrazide
Semiconductor wastewater
2017 Elsevier Ltd. All rights reserved.
The development of selective signaling and visualization systems
for biologically and environmentally important species has
attracted increasing research interest.1 In particular, selective and
sensitive metal ion signaling is important in chemical, biological,
environmental, and industrial applications.2 Copper, the third
most abundant transition metal ion in the body after iron and zinc,
is one of the most important metal ionic species in the human
body. It plays critical roles in several physiological processes,
such as a signal messenger in cell signaling, bone formation,
cellular respiration, connective tissue development, and a
catalytic cofactor in metalloenzymes.3 Further, because of its
high ductility, malleability, electrical and thermal conductivities,
and resistance to corrosion, copper has been one of the most
important metals in modern industrial activities.4 However,
copper causes serious diseases, such as Alzheimer's, Parkinson's,5
Menkes, and Wilson diseases,6 as well as Indian childhood
cirrhosis.7 Owing to its toxicity, the United States Environmental
Protection Agency (USEPA) has recommended a safe limit of 20
µM for Cu2+ in drinking water.8 For this reason, development of
selective and sensitive methods for convenient monitoring of
Cu2+ levels in environmental analytes is a critical challenge.
they tend to exhibit convenient, selective, and sensitive
colorimetric and fluorescence changes.12
In particular, fluorescence signaling is attractive owing to its
high sensitivity and specificity. However, most Cu2+-selective
fluorescence sensors show turn-off-type signaling behavior
resulting from fluorescence quenching by strongly interacting
Cu2+ ions.13 In contrast, well-designed reaction-based probes
utilizing specific Cu2+-assisted reactions commonly show more
desirable turn-on-type fluorescence signaling. For the
construction of Cu2+-selective reaction-based probes, Cu2+-
assisted hydrolysis, oxidation, and spirolactam ring-opening
processes have been employed.
The most successful approach for designing Cu2+ signaling
reaction-based probes is based on the spirolactam ring-opening
process of a variety of rhodamine hydrazide derivatives, building
on the pioneering research of Czarnik.14,15 Concurrently, Cu2+-
assisted hydrolysis reactions involving an acetate of 4,4-difluoro-
4-bora-3a,4a-diaza-s-indacene (BODIPY),16
a picolinate of
coumarin,17 and hydrazones of coumarin and hydroxyquinoline
have been successfully employed for the selective determination
and visualization of Cu2+ ions in various biological and
environmental samples.18 In particular, hydrolysis of 5-
(dimethylamino)naphthalene-1-sulfonyl hydrazide19 and D-
luciferin hydrazide20 was effectively utilized for the
determination of Cu2+ levels in simulated urine samples and
intratumoral imaging of Cu2+ ions, respectively. Cu2+-assisted
oxidative processes involving coupling reactions between 4-
aminoantipyrine and phenol21 or anilines,22 and oxidative
Quantitative Cu2+ determinations have been routinely carried
out using standard instrumental methods, such as atomic
absorption spectroscopy,9 inductively coupled plasma mass
spectrometry,10 and inductively coupled plasma atomic emission
spectrometry.11 However, such instrument-based determination
techniques require high costs and well-trained personnel and are
prone to operational difficulties. For this reason, a number of
optical probes have been developed for Cu2+ determination, and
———
∗ Corresponding author. Tel.: +82 2 820 5199; fax: +82 2 825 4736; E-mail: skchang@cau.ac.kr (S.-K. Chang)

2
Tetrahedron Letters
coupling reaction of azoaromatics23 and N-acylhydrazones24
have also been successfully developed.
Upon treatment with Cu2+, probes 1–3 revealed pronounced
fluorogenic signaling behaviors in 10% aqueous Tris-buffered
DMSO solution. However, owing to the different residual
fluorescence intensities of 1–3, the most pronounced signaling
contrast was observed for 1 (signal enhancement (I/Io): 130 (at
392 nm, for 1), 13.4 (at 378 nm, for 2), and 1.62 (at 378 nm, for
3). Therefore, Cu2+ signaling experiments were conducted with
probe 1, which exhibited the strongest fluorogenic signaling
behavior. UV–vis measurements, on the other hand, revealed no
significant changes in spectral properties of 1 on the addition of
Cu2+ or other tested metal ions (Figure S6, Supporting
Information).
However, the majority of the literature focuses mainly on the
determination and imaging of Cu2+ ions in biological samples.
Cu2+ determination using optical probes in environmentally
important analytes, such as tap water and wastewater, is
relatively less exploited. Herein, we report a fluorogenic Cu2+-
selective signaling probe based on Cu2+-induced hydrolysis of
pyrenecarbohydrazide to pyrenecarboxylic acid. This probe has a
simple structure and is easy to synthesize. The effect of spacer
length in the probe on the signaling was also elucidated using
control compounds with no, methylene, and trimethylene spacers
between pyrene and the hydrazide moiety. Finally, the designed
probe was used for the determination of Cu2+ concentrations in
simulated semiconductor wastewater.
Optimal signaling conditions were obtained by surveying the
profile of the fluorescence intensity changes as a function of pH
and solvent for probe 1 alone and in the presence of Cu2+ ions. As
shown in Figure S7 (Supporting Information), the most
pronounced off–on fluorescence signaling contrast was observed
in 10% aqueous Tris-buffered DMSO solution. In 10% aqueous
DMSO solution (Tris-buffered at pH 7.0, final concentration = 10
mM), hydrazide 1 exhibited very weak fluorescence. With the
addition of Cu2+ ions, probe 1 revealed marked navy-blue
emission under UV illumination. The fluorescence enhancement
(I/I0) at 392 nm generated by Cu2+ ions was 130-fold (Figure 1).
Other tested metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Mn2+,
Fe3+, Co2+, Ni2+, Ag+, Zn2+, Cd2+, Hg2+, Pb2+, and Al3+) did not
induce any significant changes in the fluorescence spectra, with a
relatively small range of fluorescence enhancement ratios (I/I0) at
392 nm between 1.03 (for Na+) and 1.82 (for Co2+).
The hydrazide-based probes were designed by combining a
pyrene moiety as a fluorophore and a fluorescence-quenching
hydrazide moiety as a signaling handle. To understand the Cu2+-
selective signaling behavior in the Cu2+-assisted hydrolysis of
hydrazide, a series of pyrene-hydrazides with various spacers
between the two subunits were prepared (Scheme 1). First, N-
hydroxysuccinimide (NHS)-activated esters were prepared by the
reaction of 1-pyrenecarboxylic acid, 1-pyreneacetic acid, or 1-
pyrenebutyric acid with oxalyl chloride and subsequent treatment
with NHS (dichloromethane, yield: 88.9% for 1, 92.4% for 2, and
92.9% for 3). Then, hydrazides 1–3 were synthesized readily by
reaction of the activated esters with hydrazine monohydrate
(THF, yield: 93.1% for 1, 90.5% for 2, and 94.8% for 3). It was
found that cleaner reactions with improved yields were obtained
using NHS-activated esters rather than the direct reaction
between activated acyl chloride and hydrazine. UV–vis and
fluorescence measurements suggest that probe 1 is stable under
the photoirradiation conditions (Figure S1, Supporting
Information) and in common organic solutions except for water
where considerable decreases of absorbance and fluorescence
were observed after 24 h storage (Figure S2, Supporting
Information).
150
20
2+
+ Cu
120
90
60
30
0
16
12
8
1
1
1
only,
4
+ common metal ion
0
350
400
450
Wavelength (nm)
500
550
Scheme 1. Preparation of Cu2+-selective pyrene-hydrazide probes 1–3.
Figure 1. Changes in fluorescence intensity (I/I0) of 1 at 392 nm in the
presence of representative metal ions (Mn+). Inset: fluorescence spectra of 1.
[1] = 5.0 × 10–6 M, [Cu2+] = [Mn+] = 5.0 × 10–5 M in a mixture of Tris-buffer
(pH 7.0, final concentration = 10 mM) and DMSO (1:9, v/v). λex = 340 nm.
To develop a probe for a specific metal ion in practical
samples, selective signaling of the target metal ion in the
presence of coexisting environmentally relevant metal ions is
critical. For this reason, the interference of other metal ions in
Cu2+ signaling was investigated (Figure 2 and Figure S8,
Supporting Information). The fluorescence intensity ratio
(I1+Cu(II)+metal/I1+Cu(II)) of probe 1 at 392 nm was virtually invariant
for most metal ions (from 0.97 (for Ni2+) to 1.01 (for Ba2+)). In
addition, Cu2+ signaling by probe 1 was not noticeably affected
by environmentally relevant pH conditions (pH 5.0–8.0) (Figure
S9, Supporting Information). This pH-dependency of Cu2+
signaling of probe 1 is primarily due to the unique fluorescence
property of 1-pyrenecarboxylic acid as inferred from the
observation that the pH profile of Cu2+ signaling of probe 1 is
similar to that of 1-pyrenecarboxylic acid (Figure S10,
Supporting Information). Specifically, under neutral pH
1-Pyrenecarboxylic acid-derived hydrazide 1 exhibited very
weak fluorescence emission owing to the PET quenching from
acylhydrazide NH2 to pyrene fluorophore.18 Suggested quenching
process could be confirmed by the observation that the
fluorescence emission of probe 1 enhanced under the acidic
conditions due to the revival of the PET-suppressed emission of
pyrene fluorophore by the protonation of acylhydrazide NH2
(Figure S3, Supporting Information). Meanwhile, increasing the
distance between the pyrene fluorophore and the quenching
hydrazide moiety in pyreneacetic acid-based and pyrenebutylic
acid-based hydrazides 2 and 3 noticeably increased the residual
fluorescence emission (Figures S4 and S5, Supporting
Information).25

3
conditions (pH 7.0 Tris buffer), probe 1 exhibited the greatest
Cu2+ signaling contrast (I1+Cu(II)/I1
at 392 nm = 130). In
only
addition, we confirmed that the structural variation of the probes
1–3 did not influence the Cu2+ signaling (Figure S11, Supporting
Information). From this wide pH tolerance, rapid signaling time,
and lack of interference from other metal ions, we deduced that
probe 1 might be useful for determination of Cu2+ ions in
environmentally relevant practical samples.
1
0.8
0.6
0.4
0.2
0
1
Figure 3. Partial H NMR spectra of 1 in the absence and presence of Cu2+
ions and 1-pyrenecarboxylic acid. [1] = [1-pyrenecarboxylic acid] = 0.01 M
in DMSO-d6. Because of the paramagnetic effect of Cu2+ ions, the middle
spectrum was obtained after simple purification of the signaling product by
passage through a short silica column.
To obtain the detection limit of probe 1 for Cu2+ determination,
changes of the fluorescence intensity of probe 1 at 392 nm in the
presence of varying concentrations of Cu2+ ions were analyzed.
Although Cu2+ signaling of probe 1 is based on the Cu2+-induced
catalytic hydrolysis of hydrazide moiety (Scheme 2), we could
obtain the quantitative results for Cu2+ determination after 20 min
of sample preparation, where saturated signalings were observed
(Figure S13, Supporting Information). As shown in Figure 4, the
fluorescence intensity at 392 nm increased linearly as a function
of [Cu2+] in the range of 0–1.0 × 10–5 M. From the Cu2+-
concentration-dependent fluorescence data, the detection limit of
1 for Cu2+ ions was calculated as 5.93 × 10–8 M (0.004 ppm) as
per IUPAC recommendation (3sbl/m, where sbl is the standard
deviation of the blank signal (number of measurements = 16) and
Figure 2. Changes in the fluorescence intensity ratio of 1 at 392 nm during
Cu2+ signaling in the presence of common metal ions (I1+Cu(II)+metal/I1+Cu(II)). [1]
= 5.0 × 10–6 M, [Cu2+] = [Mn+] = 5.0 × 10–5 M in a mixture of Tris-buffer (pH
7.0, final concentration = 10 mM) and DMSO (1:9, v/v). λex = 340 nm.
Cu2+-selective fluorescence signaling of 1 is due to Cu2+-
induced catalytic hydrolysis of the hydrazide moiety of the probe
to its carboxylic acid and hydrazine (Scheme 2).26,27 The
m
is the calibration sensitivity (Figure S14, Supporting
hydrolysis of probe 1 by Cu2+ was confirmed by H NMR and
1
Information).28
mass spectroscopy. The 1H NMR spectrum of the purified
signaling product was identical to that of 1-pyrenecarboxylic acid
(Figure 3). In addition, the mass spectrum revealed a diagnostic
peak at m/z = 245.1 consistent with transformation to the
suggested signaling product 1-pyrenecarboxylic acid (calcd for
[C17H9O2]–, m/z = 245.06). Also, from the observation of nearly
identical fluorescence spectra of a mixture of probe 1 and Cu2+
20
20
15
10
5
[Cu2+
]
16
12
8
ions (1
+
Cu2+) and fluorescent signaling product 1-
0
pyrenecarboxylic acid (Figure S12, Supporting Information), we
further confirmed that the Cu2+ signaling of probe 1 is due to the
hydrolysis of probe 1 to 1-pyrenecarboxylic acid.
0
10
20
30
40
50
[Cu2+] (µM)
4
Scheme 2. Cu2+ signaling by pyrenecarbohydrazide 1.
0
360
410
460
Wavelength (nm)
510
560
Figure 4. Fluorescence titration of 1 with Cu2+. [1] = 5.0 × 10–6 M, [Cu2+] =
0−5.0 × 10–5 M in a mixture of Tris-buffer (pH 7.0, final concentration = 10
mM) and DMSO (1:9, v/v). λex = 340 nm.
Copper is known to be one of the most important metals in
semiconductor-related industrial fields.29 As
a
practical
application of probe 1, determination of Cu2+ ions was conducted
in a simulated semiconductor wastewater (Figure 5). The
simulated semiconductor wastewater was prepared following the
literature.30 As shown in Figure 5, a satisfactory calibration curve
was obtained up to 5.0 × 10–6 M of Cu2+, and the detection limit
for Cu2+ in the simulated semiconductor wastewater was found to
be 6.93 × 10–8 M (0.005 ppm).28 In addition, we confirmed that
the probe could also be used to determine Cu2+ ions in tap water
samples (Figure S15, Supporting Information).

4
Tetrahedron Letters
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Figure 5. Concentration-dependent fluorescence signaling of Cu2+ by probe
1 in simulated semiconductor wastewater. [1] = 5.0 × 10–6 M, [Cu2+] = 0−5.0
× 10–6 M in a mixture of Tris-buffered (pH 7.0, final concentration = 10 mM)
wastewater and DMSO (1:9, v/v). λex = 340 nm. Error bars were obtained by
three measurements.
In summary, a simple Cu2+-selective fluorescence signaling
probe based on a hydrazide derivative of pyrene fluorophore was
investigated. The designed probe exhibited marked Cu2+-
selective turn-on fluorescence signaling behavior via Cu2+-
assisted hydrolysis of pyrenecarbohydrazide to pyrenecarboxylic
acid. Investigation of related model compounds suggested that
the fluorescence signal became less significant as the distance
between the hydrazide functionality and the pyrene fluorophore
increased. The limit of detection of the probe for Cu2+ signaling
was 5.93 × 10–8 M (0.004 ppm). Moreover, as a practical
application, Cu2+ signaling in simulated semiconductor
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Supplementary data
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5
Highlights:
•
•
•
•
Cu2+-selective fluorescence probe based on
pyrene fluorophore was developed.
Probe exhibited markedly selective signaling
via Cu2+-induced hydrazide hydrolysis.
Signal became less prominent with increased
distance between hydrazide and pyrene.
Probe could be useful for the determination of
Cu2+ in a simulated wastewater.