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Dansyl-containing boronate hydrogel film as fluorescent chemosensor of
copper ions in water{
Ryuhei Nishiyabu, Hiroyasu Kobayashi and Yuji Kubo*
Received 20th March 2012, Accepted 12th May 2012
DOI: 10.1039/c2ra20516e
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A new type of boronate hydrogel with covalently bound dansyldiethylenetriamine as an indicator has
been developed; the gel networks are based on boronate esterification of poly(vinylalcohol) with
benzene-1,4-diboronic acid. In this approach, phenylboronic acid-appended
N-dansyldiethylenetriamine 1 was newly synthesized to be incorporated into the gel matrix. The
resulting gel film showed an absorption band at 336 nm and fluorescence at 511 nm when excited at
340 nm in water. The fluorescence measurements indicated that at neutral conditions using a HEPES
buffer, the gel film was selectively quenched after immersion in an aqueous solution of Cu2+ for
30 min. The response had minimal interference from other metal ions such as Na+, K+, Mg2+, Ca2+,
Fe3+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Al3+, and Pb2+, which was noteworthy because
dansyldiethylenetriamine alone responds to Hg2+ and Ni2+ in addition to Cu2+ in water. The
reversible sensing capability was also evaluated by rinsing the film with an aqueous solution of
ethylenediaminetetraacetic acid (EDTA). The gel was found to be a reusable and free-standing film
capable of visually detecting Cu2+, providing a simple and expedient tool for on-site monitoring of
Cu2+ in environmental applications such as water analysis.

Introduction containing Hg2+, due to their similar chemical behavior to

Cu2+.7,8 Further, solution-based sensors are inconvenient for not
Chemosensors capable of fluorometrically detecting transition only real-time and real-space measurements but also repetitive
metal ions in water1 have been recognized as powerful sensing use. In this context, solid surface-supported fluorescent sensors
tools for applications in environmental and biological fields. are of growing interest for Cu2+ detection. For instance, Cu2+-
Accordingly, numerous efforts have been devoted to the design binding ligands and dansyl reporters were immobilized on silica
and development of selective fluorescent sensors in the dis- nanoparticles.11 Dansyl reporters have also been applicable to
ciplinary areas of supramolecular chemistry and analytical polymer-based12 as well as film-based13 fluorescent chemosen-
chemistry.2 Dansyl fluorophore (5-dimethylamino-1-naphthale- sors for Cu2+.
nesulfonate) is one of the most useful candidates for designing In an alternative approach, the use of boronate hydrogels14
the desired chemosensors, and it is characterized by a charge has attracted our attention for film fabrication. Although it is
transfer excited state that exhibits solvatochromism and high well-known that the addition of borate as a cross-linking agent
emission quantum yields.3 The synthetic availability of the leads to the formation of a three-dimensional polyvinyl alcohol
sulfonic acid group, together with its optical properties, led to (PVA) network,15,16 to the best of our knowledge, gel indicators
the development of fluorescent sensors for the detection of not based on the PVA–borate network have been as yet unknown,
only cations4–8 but also anions9 in water. In particular, Cu2+ is a possibly because PVA–borate gels are dissolved in water (vide
significant metal pollutant due to its widespread use, such as in infra). We realized that the employment of suitable boronic acid-
plating technology.10 The use of the dansyl moiety has been a appended cross-linkers and fluorophores would allow the
feasible approach for highly sensitive Cu2+ sensing by monitor- fabrication of PVA-based gel films that provide not only a
ing changes in fluorescence.5–8 However, a major drawback of
preferable microenvironment for the detection of the analyte in
dansyl-based systems is that they often suffer from cross-
water but also immobilize the working units. Subsequent systems
sensitivity toward other ions, particularly potential competitors
have potential as portable devices that would be user-friendly
detection tools. As a proof-of-concept study, we report here a
Department of Applied Chemistry, Graduate School of Urban
Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami- new type of reusable gel film that is composed of a covalently
ohsawa, Hachioji, Tokyo, 192-0397, Japan. E-mail: [email protected]; attached dansyl indicator in a PVA–boronate matrix.
Fax: +81-42-677-3134; Tel: +81-42-677-3134 Importantly, the film was highly selective toward copper ion-
{ Electronic supplementary information (ESI) available: NMR and FAB
mass spectra of compound 1 and experimental details. See DOI: 10.1039/ induced fluorescence response in water, with minimal inter-
c2ra20516e ference from competitive metal ions such as Hg2+.

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 View Article Online

Results and discussion

Synthesis of boronic acid-appended N-dansyldiethylenetriamine
To fabricate fluorescent boronate gels, it is required that the
synthetic connection of phenylboronic acid into the dansyl
indicator skeleton does not interfere with the metal ion binding
and optical properties. With this in mind, we decided to use
N-dansyldiethylenetriamine 26,17 because of the easy connection
of phenylboronic acid at the terminal amine moiety of 2; the
reductive amination of 2 with MIDI (N-methyliminodiacetic
acid)-protected formylphenylboronic acid in the presence of
NaBH4 afforded 1 after purification, in 18% yield. The assign-
ment of the new compound 1 was carried out using several
spectroscopic data (see ESI,{ Fig. S1–4). The optical properties
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came from UV-vis and fluorescence measurements; 1 shows an

absorption band at 329 nm (e = 4.4 6 103 M21 cm21) in 2% Fig. 1 Phase diagram of the PVA–DBA system in DMSO (1.5 mL) at
DMSO aqueous solution (5.0 mM HEPES, pH = 7.0), which is room temperature; ($) sol, (#) gel.
consistent with that of 2. This suggests that the incorporation of
phenylboronic acid into 2 causes no perturbation toward dansyl 1.2 6 1022 M. Under these conditions, excess amounts of free
fluorophore. Indeed, when excited at 340 nm in 2% DMSO hydroxyl groups of PVA remained to participate in boronate
aqueous solution (5.0 mM HEPES, pH = 7.0), an orange esterification with 1.
emission was observed with a fluorescence maximum at 545 nm The DMSO gel could be transferred to the corresponding
and a quantum yield of 0.02 against a quinine sulphate (W = hydrogel by immersing it in water (see experimental section). The
0.546 in 0.5 M H2SO4 aqueous solution).18 obtained hydrogels were stable in water and their characteriza-
tion was based on the FT-IR analysis. When the xerogel was
Formation of boronate–PVA gel measured by the KBr method, a characteristic intense peak
assigned to the boronate ester formation between PVA and DBA
We initially explored suitable cross-linkers for stable boronate
was observed at 664 cm21, together with a peak corresponding to
gels in water. It is known that PVA–borate systems form
the B–O stretch at 1304 cm21 (Fig. 2).20 This result confirmed
homogeneous gels.15,16 Thus, when the phase diagram reported
that the gel formation was driven by benzene diboronate-diol
in the paper16 is considered, dansyl-containing PVA–borate gel
was prepared from PVA (M.W. = 146 000–186 000, 6.4 6 1021
M19), borax (9.4 6 1022 M), and 1 (1.3 6 1024 M) (see ESI,{
Fig. S5). The resulting fluorescent gel was found to dissolve in
water within 90 min. To prepare stable boronate gels in water,
we studied how benzene-1,4-diboronic acid (DBA) with a
hydrophobic character would behave as a cross-linking agent
in the PVA matrix. For this preparation, DBA was initially
allowed to react with PVA in DMSO to provide an organogel
because of its low solubility in water. Fig. 1 shows the phase
diagram of the boronate–PVA gel in DMSO. 1.5 mL samples
were prepared by mixing various amounts of PVA and DBA.
For a solution containing a low concentration of PVA (,0.1 M),
the sol phase was characterized even at a relatively high
concentration of DBA. In contrast, when the PVA concentration
became adequate to ensure intermolecular cross-linking through
boronate esterification with DBA, gelation occurred. After Fig. 2 FT-IR spectrum of xerogel produced by PVA and DBA. A
several trials to obtain suitable gels to this end, we employed characteristic intense peak at 664 cm21 (*) was assignable to the boronate
the following conditions: PVA = 4.0 6 1021 M19 and DBA = esters.

Scheme 1 Synthesis of boronic acid-appended N-dansyldiethylenetriamine 1.

6556 | RSC Adv., 2012, 2, 6555–6561 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

cross-linking in PVA. The gel is stable in water and pH stability

tests indicated that the gel never decomposes between pH 1 and
11 (see ESI,{ Fig. S6).

Fabrication of boronate gel films with dansyl moieties

Taking the phase diagram of the PVA–DBA system into account
(Fig. 1), the target boronate gels with indicators were fabricated
as follows. A DMSO solution (0.15 mL) of indicator 1 (6.7 6
1024 M) and DBA (6.0 6 1022 M) at 25 uC was added to a
DMSO solution (0.60 mL) of PVA (5.0 6 1021 M19). The
resulting solution containing PVA (4.0 6 1021 M19), DBA
(1.26 1022 M), and 1 (1.3 6 1024 M) was cast into a slab at
room temperature to immediately afford DMSO gel films with a
molar cross-linking ratio of DBA to the PVA monomer unit of
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0.12. After aging for 24 h at room temperature, the film was Fig. 4 Change in fluorescence spectra of gel film (30 6 10 6 1 mm, 1 =
again immersed in DMSO, and then in solvents of increasing 1.25 6 1025 M) after immersion in Cu2+ in HEPES aqueous solution
water ratio to obtain the desired fluorescent hydrogel. The film (5 mM, pH = 7.0, 3.0 mL) for 30 min: lex = 340 nm. Inset: fluorescent
intensity changes at 511 nm plotted as a function of incremental amounts
was a swollen gel with dimensions of 30 6 10 6 1 mm
of Cu2+.
(Fig. 3a).21 The content of the indicator that was immobilized in
the PVA matrix was estimated via UV-vis measurement, and the
absorbance of the gel film suggested that (3.8 ¡ 0.3) 6 1028 mol DMSO aqueous solution (5.0 mM HEPES, pH = 7.0), possibly
of the indicator was incorporated into the boronate gel. A due to the hydrophobic microenvironment of the gel matrix.22
plausible structure is shown in Fig. 3b. The morphological These optical properties enabled us to detect green emission from
analysis of the xerogel was performed by field-emission scanning the film upon irradiation with UV light. We thus investigated
electron microscopy (FE-SEM), which suggested the formation how Cu2+ would induce a change in the fluorescence spectra of
of a fibrous network structure (Fig. 3c). the gel film. The boronate film was immersed in a HEPES
aqueous solution (5 mM, pH = 7.0) containing various amounts
Chemosensor capability of boronate hydrogel film of Cu2+. The resulting solution was shaken at 125 rpm for
30 min. As shown in Fig. 4, the fluorescence of the gel was
The boronate film exhibited fluorescence at 511 nm when excited significantly quenched upon addition of incremental amounts of
at 340 nm in a HEPES aqueous solution; the emission maxima Cu2+. A non-linear curve fitting procedure (Fig. 4, inset) was
was blue shifted by 34 nm and the fluorescence quantum yield carried out under the assumption of a 1 : 1 stoichiometric
increased significantly (W = 0.37) in comparison with dye 1 in 2% complex formation between the dansyldiethylenetriamine moiety
and Cu2+,6 and we reproduced the fluorescence titration data
wherein the association constant of the film with Cu2+ was
estimated to be (3.74 ¡ 1.02) 6 106 M21. For practical
applicability, the detection limit was estimated to be 8.83 6 1027
M (883 nM) from the fluorescence profile in Fig. 4.
The time dependency for Cu2+-induced fluorescence quench-
ing was also examined. The gel film was immersed in a HEPES
aqueous solution of Cu2+ (1.25 6 1025 M), being almost
consistent with the amount of dansyl moiety incorporated into
the gel. After shaking (125 rpm) the resulting solution, the
emission intensity was recorded at different times (Fig. 5a). A
good linear relation between ln[(I0 2 Ilim)/(Ilim 2 I)] versus time
was obtained to estimate the first-order rate constant, 8.7 6
1022 min21. This means that the quenching of fluorescence is
almost saturated (#90%) for 30 min (Fig. 5b and 5c).
Next, we investigated the selectivity of the gel toward other
metal ions in water. Aqueous solutions (3 mL) of metal ions
(1.25 6 1025 M) such as Na+, K+, Mg2+, Ca2+, Fe3+, Co2+,
Ni2+, Zn2+, Cd2+, Hg2+, Al3+ and Pb2+ were prepared in water.
The gel film was immersed into each solution. After shaking the
resulting solution (125 rpm) for 30 min, the fluorescence was
Fig. 3 (a) Photograph of the boronate hydrogel film with dansyl measured. As shown in Fig. 6, the film exhibited a remarkable
moieties; (b) proposed structure of the indicator hydrogel wherein OH- selectivity toward Cu2+. Other metal ions induced no fluores-
inserted sp3-hybridized tetrahedral boronate esters would be partly cence quenching of the film. Although it is known that
produced; (c) FE-SEM image of the xerogel. dansyloligoamines respond to not only Cu2+ but also Hg2+ in

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Fig. 5 (a) Time dependency for the Cu2+-induced fluorescent response of the gel film. (Inset: corresponding plot of ln[(I0 2 Ilim)/(Ilim 2 I)] versus time
for fluorescence quenching at 511 nm after immersion in a HEPES aqueous solution of Cu2+ (1.25 6 1025 M).) Photograph of gel films under UV light
(365 nm) after being immersed in HEPES aqueous solution (5 mM, pH = 7.0, 3.0 mL) for 30 min: (b) copper ion-free conditions; (c) in the presence of
Cu2+ (1.25 6 1025 M).

water,7 dansyl-containing boronate hydrogel films respond to

only Cu2+ in water.
To obtain further evidence regarding selectivity, competitive
experiments were carried out by adding Cu2+ (1.25 6 1025 M) to
the buffered solution in the presence of excess amounts of other
metal ions (1.25 6 1024 M). As shown in Fig. 7, there is almost
no fluorescence quenching of the films in the presence of
competitive metal ions, with the exception of 10 equiv. Ni2+,
which causes a 17% decrease in the emission. This can be
explained on the basis of energy transfer from dansyl to Ni2+,
which should be attributed to quenching.6 In contrast, the
addition of a relatively low amount of Cu2+ (1.25 6 1025 M) to
the solutions containing each metal ion other than Fe3+ 23
quenched the emission to 30% of its initial value. As a result,
although its selectivity toward Cu2+ slightly decreased in the case
Fig. 6 Fluorescence intensity changes in film gels after immersion in of Ni2+ and Fe3+, the film is still most responsive to Cu2+. Thus,
aqueous solutions of Na+, K+, Mg2+, Ca2+, Fe3+, Co2+, Ni2+, Cu2+, co-existent ions of Hg2+ (Fig. 7) have some or a negligible
Zn2+, Cd2+, Hg2+, Al3+ and Pb2+, respectively. [Mn+] = 1.25 6 1025 M, interference effect on Cu2+-sensing in the boronate gel film.
lex = 340 nm, lem = 511 nm. The fluorescence quenching could be recovered by simple
rinsing of the film with an aqueous solution of ethylenediami-
netetraacetic acid (EDTA). We investigated the reversible
sensing capability by alternatively exposing the film to 3 mL of
an aqueous solution (5 mM HEPES buffer, pH = 7.0) containing
Cu2+ (1.25 6 1025 M) and EDTA (1.25 6 1025 M). As shown
in Fig. 8, when the film was immersed in EDTA solution with
shaking at 125 rpm for 30 min at room temperature,
approximately 85% of emission could be restored as a result of
a competitive binding phenomenon between the film and EDTA
toward Cu2+. The reversible fluorescence switch was obtained
after alternating treatment with Cu2+ and EDTA, although the
fluorescence intensity of the film decreased gradually over
several cycles. Compared to homogeneous solution-based
chemosensors, the reversibility of the film has significant merits
for practical use as an indicator.
Fig. 7 Competitive experiments for fluorescence quenching of film. The
red bars represent the emission intensity of the film in the presence of Conclusion
other metal ions (1.25 6 1024 M). The blue bars represent the emission
intensity of the film that occurs upon addition of Cu2+ (1.25 6 1025 M) We prepared for the first time a PVA–boronate hydrogel via
in the presence of other metal ions (1.25 6 1024 M). boronate esterification between DBA and PVA. The incorporation

6558 | RSC Adv., 2012, 2, 6555–6561 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

where 3-nitrobenzyl alcohol was used as a matrix. Field-emission

scanning electron microscopy (FE-SEM) was performed using a
JEOL JSM-7500F (acceleration voltage of 5 kV). For FE-SEM
measurement, xerogel of the boronate ester gel was prepared by
a freeze-drying method and was coated with Au on an EIKO IB3
ION COATER. Infrared spectra were recorded on a JASCO FT-
IR-5300 spectrometer using a KBr pellet technique. Elemental
analysis was performed on a Yanaco CHNcoder MT-5 analyzer.
Absorption and fluorescence spectra were measured on a
Shimadzu UV-3100PC and a JASCO FP-6300 spectrophot-
ometer, respectively. For UV-vis absorption measurement, the
dansyl-functionalized boronate gel was put into a 1 cm 6 1 cm
cell filled with water. For fluorescence emission measurements,
the films were put into a cell filled with the solution at an angle of
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45u with respect to the incident light using a quartz glass plate
(42 mm 6 13 mm). The slit size for excitation and emission was
Fig. 8 Fluorescence intensity change in the gel film upon alternating 5 nm. Fluorescence quantum yields of dye 1 and dansyl-
treatment by aqueous solutions of Cu2+ (1.25 6 1025 M) and EDTA
functionalized boronate gel were determined using quinine
(1.25 6 1025 M): lex = 340 nm, lem = 511 nm.
sulphate (W = 0.546 in 0.5 M H2SO4 aqueous solution) with
340 nm excitation at 25 uC as a reference.18
of dansyldiethylenetriamine into the gel matrix using 1 allowed
us to develop an emissive film through casting into a slab,
exhibiting highly selective fluorescence quenching toward Cu2+ Synthesis of 3-[({(N-dansylamino)ethylamino}ethylamino)
over other metal ions tested in aqueous HEPES solution (pH = methyl]phenylboronic acid (1) (Scheme 1). To m-formylphenyl-
7.0). This result is worthwhile for developing chemosensors boronic acid MIDA ester (0.34 g, 1.3 mmol) in dry ethanol
because dansyloligoamines significantly respond to Hg2+ as well (250 mL) containing molecular sieves 3 Å, was added
as Cu2+ in a solution. In addition, the reusability of the sensing N-dansyldiethylenetriamine (0.44 g, 1.3 mmol) dissolved in dry
suggests that the film has potential as a simple and expedient ethanol (100 mL) under a N2 atmosphere at room temperature.
tool for on-site monitoring of Cu2+ in environmental applica- The mixture was stirred for 40 h at room temperature. After
tions such as water analysis. We believe that the ready binding checking the progress of the reaction by TLC, a dry ethanol
of functional phenylboronic acids into the PVA matrix would solution (130 mL) of NaBH4 (0.099 g, 2.6 mmol) was added to
lead to the preparation of a variety of indicator gels; for the solution and the mixture was further stirred at room
instance, two different indicators could be incorporated into the temperature for 1 h. After filtration, the solution was evaporated
gel matrix through boronate esterification wherein a synergistic in vacuo. The resulting residue was partitioned between CH2Cl2
effect between the indicators would provide advanced chemo- (100 mL) and saturated saline (100 mL), the water phase being
sensor systems. Further research in this regard is currently extracted with CH2Cl2 (100 mL 6 2). The organic phase was
under way in our laboratory. dried over anhydrous Na2SO4 and filtered. The material
obtained was chromatographed on silica gel (Silica gel 60
silanized) using a gradient of CH3OH (0–1.5% v/v)) in CHCl3 as
Experimental section
an eluent. In this way, 111 mg of 1 was obtained in 18% yield.
Materials UV-vis: lmax = 341 nm (e = 4.5 6 103 M21 cm21) in DMSO and
lmax = 329 nm (e = 4.4 6 103 M21 cm21) in 5 mM HEPES
Unless otherwise indicated, reagents and solvents used for
buffer solution (pH 7.0, I = 0.01); fluorescence: lem = 519 nm
this study were commercially available and used as supplied
(W = 0.29, lex = 340 nm) in DMSO and lem = 545 nm (W = 0.02,
(Tokyo Kasei, Kanto Kagaku, Wako, Aldrich, and Merck).
lex = 340 nm) in 2% DMSO aqueous solution (5.0 mM HEPES,
N-Dansyldiethylenetriamine was synthesized according to the
pH = 7.0); 1H NMR (500 MHz, CD3OD) d 8.59 (d, 1H,
procedure in a previous paper.17 As for the buffer solution,
J = 8.5 Hz), 8.32 (d, 1H, J = 8.7 Hz), 8.22 (dd, 1H, J = 7.3,
HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid)
1.2 Hz), 7.74 (s, 1H), 7.68 (s, 1H), 7.60 (dd, 1H, J = 8.65, 7.6 Hz),
buffer solution (5 mM, pH = 7, I = 0.01) was used. The pH
7.59 (dd, 1H, J = 8.6, 7.35 Hz), 7.53 (d, 1H, J = 7.8 Hz), 7.44 (t,
and ionic strength were adjusted by the addition of aqueous
1H, J = 7.5 Hz), 7.28 (d, 1H, J = 7.6 Hz), 4.17 (s, 2H, CH2), 3.12
sodium hydroxide (1.0 M) and sodium chloride solution (1.0 M).
(t, 2H, CH2, J = 6.1 Hz), 3.04 (t, 2H, CH2, J = 5.75), 3.01 (t, 2H,
CH2, J = 5.9 Hz), 2.88 (m, 8H, CH2 and CH3); 13C NMR
Measurements
(125 MHz, CD3OD) d 153.42, 136.20, 135.96, 135.46, 133.02,
NMR spectra were recorded on a Bruker AVANCE-500 132.01, 131.60, 131.32, 130.90, 130.54, 129.50, 129.45, 124.39,
spectrometer using tetramethylsilane (TMS) as an internal 120.25, 116.63, 52.78, 46.07, 45.82, 45.50, 41.87; 11B NMR (160
standard (0 ppm) for 1H and 13C NMR analysis and BF3?OEt2 MHz, CD3OD) d 28.39; FAB-MS: m/z 741 ([M + 2(3-nitrobenzyl
as an external standard (0 ppm) for 11B NMR analysis. All alcohol) 2 2H2O + H]+); elemental analysis: anal. calcd for
spectra were recorded at 298 K. Fast atom bombardment (FAB) C23H31BN4O4S?1.6HCl: C 52.25; H 6.21; N 10.60%, found: C
mass spectra were obtained on a JEOL JMS-700 spectrometer 52.47; H 6.09; N 10.34%.

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Fabrication of dansyl-functionalized boronate hydrogel film was immersed in aqueous EDTA solution (1.25 6 1025 M
in 5 mM HEPES buffer (3 mL) at pH 7.0) for 30 min with
A DMSO solution (0.6 mL) of PVA (M.W. = 146 000y186 000,
shaking at 125 rpm at room temperature. The fluorescence
5.0 6 1021 M)19 was added to a DMSO solution (0.15 mL)
measurement was then carried out.
containing benzene-1,4-diboronic acid (6.0 6 1022 M) and 1
(6.7 6 1024 M) in a vial. The resulting solution was immediately
cast into a slab to afford DMSO gel films (approximately 48 6 Acknowledgements
16 6 2 mm) and aged for 24 h at room temperature. The film
This research was supported by a Grant-in-Aid for Scientific
was immersed in DMSO (5 mL) again, and then shaken at 100
Research from the Ministry of Education, Science, Sports and
rpm for 30 min. Similar procedures were carried out in solvents
Culture of Japan (Nos. 21550137, 23750167), the Yamada
of increasing water ratio (5 mL, DMSO : water = 50 : 50 ,
Science Foundation, and the JGC-S Scholarship Foundation.
25 : 75, 12.5 : 87.5 (v/v)) to obtain the desired fluorescent
hydrogel. The film was a swollen gel with dimensions of 30 6
10 6 1 mm. The amount of immobilized 1 in the PVA–boronate References
gel matrix was calculated based on the absorption intensity of 1 (a) Current examples, see: B. K. Kanungo, M. Baral, R. K. Bera and
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and D. Das, TrAC, Trends Anal. Chem., 2012, 32, 113–132.
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DIlim |(A{ A2 {4|K2 |S0 |M0 )
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