Rapid and specific luminescence sensing of Cu(II) ions with a porphyrinic metal-organic framework

Article abstract of DOI:10.1039/c7cc04250g

We herein present a porphyrinic metal-organic framework (MOF) as a highly sensitive fluorescent probe targeting Cu(ii) ions with a fast response. The well-isolated nature of porphyrin moieties within the framework greatly enable accessible recognition sites, which leads to an outstanding detection limit performance of 67 nM among MOF-based materials.

Full text of DOI:10.1039/c7cc04250g

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Reactivity differences of Sc
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Rapid and Specific Luminescent Sensing of Cu(II) Ion with
Porphyrinic Metal‐Organic Framework
a
a
a
a
a
Linnan Li, Sensen Shen, Ruoyun Lin, Yu Bai and Huwei Liu
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
We herein present a porphyrinic metal‐organic framework (MOF) and electrochemical methods6 have been devoted to the
as a highly sensitive fluorescent probe targeting Cu(II) ion with a detection of Cu(II) ion in aqueous solution. Nevertheless, these
fast response. The well‐isolated nature of porphyrin moieties methods are usually time‐consuming and/or need high‐priced
within the framework greatly enable accessible recognition sites, equipment while others require relatively complicated sample
which leads to an outstanding detection limit performance of 67 preparation, which limit their wide applications. More recently,
nM among MOF‐based materials.
with the advantages of simplicity, rapid response, good
selectivity and high sensitivity, tremendous efforts have been
Copper is one of ubiquitous metals that occurs naturally in rock,
soil, water, sediment, and air. It has made indispensable
contributions to sustaining and improving human society since
the dawn of civilization. Presently, copper is widely used in
electrical equipment, building construction, industrial
directed towards the design and construction of fluorescent
chemosensors for different analytes.7
To meet these demands for chemical sensors, a fascinating
hybrid material class, the metal‐organic frameworks (MOFs),
8
could be a promising solution. MOFs, which are crystalline
1
machinery, renewable energy and so forth. Moreover, as an
solids constructed by joining metal‐containing units with
organic linkers as indicated by the name. Given their regular
nanostructured pores, high surface area and flexible
functionalities, MOFs have been applied in a wide range of
essential element to all living organisms including human, trace
concentrations of cooper maintain the proper functioning of
organs and metabolic processes in vivo. However, too much
ingestion of cooper can lead to a set of adverse health effects
such as vomiting, diarrhea, stomach upset or even associated
with severer liver and kidney damage.2 Considering its
important role in various areas, excess copper released into
environment through multiple ways could affect surrounding
ecosystem and directly threaten our human health. On this
account, the World Health Organization (WHO) and U.S.
Environmental Protection Agency (EPA) has established the
limit of copper concentration in drinking water to be 2 ppm and
9
10
potential uses including for gas storage, separation, chemical
8
11
12
sensing, catalysis and biomedical applications. Especially,
through fine tuning the surface functionality and chemical
environment of pore channels, rational designed MOF materials
can serve as platforms for selectively probing small molecules
or different ionic species. While several research groups have
studied utilization of luminescent MOFs for the specific
detection of Cu(II) ion, MOF‐based sensors with excellent
sensitivity on the Cu(II) ion over other metal ions is still
1
.3 ppm.3 Hence, it is of great significance to develop an
13
challenging. In addition, porphyrin and related macrocycles
effective method that could provide simple, rapid, highly
sensitive and specific detection of Cu(II) ion in complex
environments.
can act as attractive bridging ligands in assembling MOFs
because of their rigid molecular structure, tunable peripheral
substituents, large physical dimensions, and an additional
In the past few years, several analytical techniques including
inductively coupled plasma atomic emission spectrometry (ICP‐
14
metalation site in the core. Considering the porphyrins are
inherent component in those MOFs, the multistep procedures
for the introduction of porphyrinic groups could be avoided.
And the well‐isolated nature of porphyrin moieties could also
effectively weaken the self‐aggregation and enable their
fluorescence response to the analytes. Compared with
hierarchically porous materials in which confined porphyrins
inside their pores, porphyrin‐based MOFs benefit stable
skeletons and abundant accessible recognition sites.1 As well
4
5
AES), inductively coupled plasma mass spectrometry (ICP‐MS)
a.
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic
Chemistry and Molecular Engineering of Ministry of Education, Institute of
Analytical Chemistry, College of Chemistry and Molecular Engineering, Peking
University, Beijing 100871, P. R. China. Email: hwliu@pku.edu.cn
Electronic Supplementary Information (ESI) available: Experimental details and
supplementary figures and tables. See DOI: 10.1039/x0xx00000x
5
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verified in recently research projects, the porous porphyrinic
MOFs have become one of the leading candidates for sensing
applications.16
Here, we report a fluorescent turn‐off chemosensor for Cu(II)
ion sensing based upon a porphyrinic MOF Zr
6 4 4
O (OH) (TCPP‐
2 3
H )
(termed MOF‐525). The material was facilely prepared
through a moderate solvothermal reaction between zirconium
precursor and meso‐tetra (4‐carboxyphenyl) porphyrin (TCPP)
as organic linker.17 Within the MOF framework, the macrocycles
of the TCPP units containing four nitrogens played the role of
potential recognition sites and signal reporter. After interacting
with Cu(II) ion, the electronic structure of the porphyrin plane
Fig. 1 (a) The PXRD patterns of as‐synthesized (red) and simulated MOF‐525 (black).
2
(b) The N adsorption‐desorption isotherms of MOF‐525.
was notably influenced, leading to the altered luminescent the frameworks and easily interact with recognition sites within
property of nanocrystals. Thus, a simple strategy with response the material, which fully facilitate the ions sensing function.
time of as short as 40 s is obtained using the MOF‐525 sensor Thermogravimetric analysis depicted in Fig. S6 shows that MOF‐
6 4 4
for Cu(II) ion detection (Scheme 1). This porphyrinic MOF 525 release the water from the dehydration of the Zr O (OH)
displays a highly selective and convenient sensing performance nodes in initial weight‐loss process. The followed dramatically
on Cu(II) ion over many other metal ions. Moreover, it exhibits weight‐loss corresponding to the decomposition of TCPP
a very low detection limitation (LOD) in reference to those ligands within the framework. The data indicate the MOF keeps
reported MOF‐based sensors. In this regard, the proposed thermally stable in the air up to around 400
technique is geared toward exploring the novel MOF‐based merely possessed exceptional chemical and thermal stability
Cu(II) ion sensing nanomaterials. due to the strong interaction between metal clusters and
℃. The material not
The powder X‐ray diffraction (PXRD) pattern of the activated porphyrin bridging ligands. Also, thanks to the unique structural
MOF‐525 sample is shown in Fig. 1a. The main diffraction peaks and electronic features of porphyrin moieties within the
can be observed at 4.5°, 6.4°, 7.9°, 9.1° 11.2° and 13.7° in the framework, it could hopefully embody different affinities to
experimental pattern of the sample. All of these peaks are metal ions and further provide potential recognition ability for
almost identical with the simulated PXRD pattern of previously specific ion in aqueous solution.18 Thus, the highly ordered,
reported MOF‐525 nanocrystals.17 Scanning electron permanent porous MOF could offer an ideal platform for
microscopic (SEM) image was taken to investigate the chemical sensing function.
morphology of the synthesized material. It can be observed in We investigated the spectroscopic properties of the MOF‐525
Fig. S5 that the MOF‐525 particle size of about 500 nm were sample. The UV‐visible spectra of the MOF‐525 sample in DMF
synthesized. The N
2
adsorption‐desorption isotherm of MOF‐ is shown in Fig. S7. A typical Soret peak at 430 nm and four Q
5
25 is shown in Fig. 1b. The Brunauer‐Emmett‐Teller (BET) bands located between 500 and 700 nm can be clearly
2
‐1
surface area of MOF is estimated to be 2236 m ∙g , which is observed. As expected, the spectrum is consistent with the UV‐
comparable with the values reported previously. The high N visible spectrum of free TCPP (Fig. S4a). The four Q bands
2
adsorption and surface area demonstrate the highly porous observed in the spectrum also confirm that the porphyrinic
structure of MOF‐525. Additionally, the pore size distribution of units in the MOF‐525 are free‐base TCPP instead of Zr(IV)
synthesized material reveals the adsorption average pore width porphyrin complexes.
and a uniform pore size of 1.9 nm. The pore size is in excellent The turn‐off fluorescence response of MOF‐525 with different
agreement with the cage size of MOF‐525 crystal structure.1
7c
concentration of Cu(II) ion at 25 °C is shown in Fig. 2a. It exhibits
The uniform pores of MOF allow the diffusion of analytes across a strong emission peak at 651 nm upon excitation at 512 nm,
which could be attributed to a typical S1→S0 state transiꢀon of
porphyrin. With the addition of Cu(II) ion into the suspension,
the fluorescence emission from MOF‐525 is instantly decayed
within 40 s. As expected, along with the Cu(II) ion increases from
‐
1
0
to 1.2 mg∙L , the fluorescence intensity gradually decreases.
‐
1
A high florescence quenching percentage is found at 1.2 mg∙L
(
about 18.9 μM) of Cu(II) ion, which quenches exceed 85% of
the initial fluorescence intensity.
Furthermore, the fluorescence quenching process could be
ꢀ
ꢁ
quantitatively described by the Stern‐Volmer equation, ꢀ
ꢂ
ꢃꢄꢅꢆꢇꢈ ꢉ 1 . Where I
0
and I represent the fluorescence
intensities of MOF‐525 suspension before and after the addition
of Cu(II) ion, respectively. [Q] is the molar concentration of
analyte, and KSV is the Stern‐Volmer quenching constant. The
Scheme 1 A simple strategy for rapid and specific luminescent sensing of Cu(II) ion
with porphyrinic MOF prepared by a facile solvothermal process.
2
Stern‐Volmer plot exhibits a good linear correlation (R = 0.99)
2
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‐1
‐1
Fig. 2 (a) The fluorescence emission spectra of MOF‐525 (6 mg∙L ) with Cu(II) ion of different concentrations from 0 to 1.2 mg∙L (excited and monitored at 512 and 651 nm,
respectively). (b) Linear relationship of the fluorescence intensity at 651 nm as a function of Cu(II) ion concentration.
‐
1
2+
2+
in the Cu(II) ion concentration range of 0.1‐1.2 mg∙L (Fig. 2b). Co and Pb haveobvious effects, while other metal ions show
The quenching constant of KSV is an important parameter to no significant changes on the fluorescence intensity. The
describe the fluorescence quenching efficiency, which is differential quenching effects of metal ions with MOF could
5
−1
quantified to be 4.5 × 10 M for Cu(II) ion. Then, the detection mainly be attributed to their electronic nature. Particularly, the
limit is calculated with respect to IUPAC recommendation alkali and alkaline‐earth metal ions having a closed‐shell
(
3σ/slope). The standard deviation σ is estimated by the electron configuration (also include some transition metal ions
fluorescence intensity of blank MOF‐525 suspension in the with filled d shells like Zn2 and Cd ), display essentially no
absence of Cu(II) ion (Fig. S8) and the slope value is calculated quenching effects. While some HTM ions like Cu(II) ion, having
using a calibration curve for fluorescence intensity against Cu(II) empty orbits due to the unsaturated electronic states could lead
ion concentration (Fig. S9). Remarkably, the LOD based on MOF‐ to energy/charge transfer process with porphyrin units. The
+
2+
5
25 for Cu(II) ion is able to reach 67 nM, which is far below the experimental results show the superior sensing ability to metal
limit of copper in drinking water that required by WHO and U.S. ions of MOF‐525 and the best selectivity toward Cu(II) ion
EPA standards. The value is also below mostly previously among all these potentially interfering metallic cations. This
reported MOF‐based sensors for Cu(II) ion as listed in Table S1. difference could be reasonably explained by much stronger
19
To study the potentials of the MOF‐525 fluorescent probe for affinity of Cu(II) ion to porphyrin core within MOF‐525.
specific Cu(II) ion detection, we tested the fluorescence To further explore the possible quenching mechanism, the
variations of MOF‐525 in the presence of equivalent various fluorescence lifetime decay of the MOF‐525 suspension was
+
+
2+
3+
+
2+
3+
possible coexistent cations (Li , Na , Mg , Al , K , Ca , Cr , measured both in the presence and absence of Cu(II) ion at 25
2
+
3+
2+
2+
2+
2+
2+
2+
2+
Mn , Fe , Co , Ni , Zn , Sr , Cd , Ba and Pb ). For °C. As shown in Fig. 4, the curve could be well fitted by single
‐
1
different metal ions ([M]=1.0 mg
, some heavy transition metal (HTM) ions such as Cu , Mn , porphyrin complex (τ=2.72 ns) decays faster than the free case
τ=5.00 ns) suggesting that the fluorescence quenching may
·L ), as demonstrated in Fig. exponential lifetime decay. The excited state of the Cu(II)‐
2
+
2+
3
(
occur through dynamic mechanism. After interaction with the
paramagnetic Cu(II) ion, it may led to the decreased electron
density at the porphyrin core and a similar trend was also
observed in other metal‐porphyrin complex.20 As reveled in
spectroscopic study, the porphyrin center cannot be metalated
with Zr(IV) during the synthesis of MOF. Thus the obtained
material is expected to provide accessible recognition sites for
the desired metals. In this scenario, the porphyrin moiety act as
a signaling fluorophore and ion receptor, revealing its versatile
sensing nature for Cu(II) ion.21 Besides, the porphyrin moieties
6 4 4
are well‐isolated by Zr (OH) O clusters which can effectively
restrain π‐π interactions between free‐base TCPP molecules
and diminish the aggregation‐induced quenching effect.
The easily constructed sensory material was also applied for
determining the concentration of Cu(II) ion in practical water
samples to demonstrate its potential applications. As shown in
Table S2, for mineral and tap water, there was no Cu(II) ion
Fig. 3 Comparison of the fluorescence intensity of MOF‐525 with different metal ions
‐
1
(1.0 mg∙L ).
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Fig. 4 The fluorescence lifetime of MOF‐525 in the absence (black) and presence
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Cu(II) ion. As a fluorescent “turn‐off” sensor, MOF‐525
manifests strong fluorescence quenching response to trace
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