Molecular Vise Approach to Create Metal-Binding Sites in MOFs and Detection of Biomarkers

Article abstract of DOI:10.1002/anie.201803201

We report a new approach to create metal-binding site in a series of metal–organic frameworks (MOFs), where tetratopic carboxylate linker, 4′,4′′,4′′′,4′′′′-methanetetrayltetrabiphenyl-4-carboxylic acid, is partially replaced by a tritopic carboxylate linker, tris(4-carboxybiphenyl)amine, in combination with monotopic linkers, formic acid, trifluoroacetic acid, benzoic acid, isonicotinic acid, 4-chlorobenzoic acid, and 4-nitrobenzoic acid, respectively. The distance between these paired-up linkers can be precisely controlled, ranging from 5.4 to 10.8 ?, where a variety of metals, Mg²⁺, Al³⁺, Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Cd²⁺ and Pb²⁺, can be placed in. The distribution of these metal-binding sites across a single crystal is visualized by 3D tomography of laser scanning confocal microscopy with a resolution of 10 nm. The binding affinity between the metal and its binding-site in MOF can be varied in a large range (observed binding constants, K_obs from 1.56×10² to 1.70×10⁴ L mol^?1), in aqueous solution. The fluorescence of these crystals can be used to detect biomarkers, such as cysteine, homocysteine and glutathione, with ultrahigh sensitivity and without the interference of urine, through the dissociation of metal ions from their binding sites.

Full text of DOI:10.1002/anie.201803201

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Accepted Article
Title: Molecular Vise Approach to Create Metal-Binding Sites in MOFs
and Detection of Biomarker
Authors: Yang Wang, Qi Liu, Qin Zhang, Bosi Peng, and Hexiang
Deng
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201803201
Angew. Chem. 10.1002/ange.201803201
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Molecular Vise Approach to Create Metal-Binding Sites in MOFs
and Detection of Biomarker
Yang Wang+, Qi Liu+, Qin Zhang, Bosi Peng, and Hexiang Deng*
Abstract: We report a new approach to create metal-binding site in
mation, SI). The original tetra-topic linker was partially replaced
by a pair of tri-topic linker, tris(4-carboxybiphenyl)amine (TBPA)
and a mono-topic linker, likened to the stationary jaw and sliding
jaw of the molecular vise, respectively, and form the
a series of metal-organic frameworks (MOFs), where tetra-topic
carboxylate
linker,
4’,4’’,4’’’,4’’’’-methanetetrayltetrabiphenyl-4-
carboxylic acid, is partially replaced by a tri-topic carboxylate linker,
tris(4-carboxybiphenyl)amine, in combination with mono-topic linkers, corresponding MV-MOF (MV-PCN-521-R, R represents the
formic acid, trifluoroacetic acid, benzoic acid, isonicotinic acid, 4-
chlorobenzoic acid, and 4-nitrobenzoic acid, respectively. The
mono-topic linker). Six different mono-topic linkers (formic acid,
FA; trifluoroacetic acid, TFA, benzoic acid, BA; isonicotinic acid,
distance between these paired-up linkers can be precisely controlled, IA; 4-chlorobenzoic acid, CBA, and 4-nitrobenzoic acid, NBA)
ranging from 5.4 to 10.8 Å, where a variety of metals, Mg2+, Al3+, Cr3+, with different functionality were used to form six MV-MOFs (MV-
Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+ and Pb2+, can be placed
in. The distribution of these metal-binding sites across a single
crystal is visualized by 3D tomography of laser scanning confocal
microscopy with a resolution of 10 nm. The binding affinity between
the metal and its binding-site in MOF can be varied in a large range
(observed binding constants, Kobs from 1.56 × 102 to 1.70 × 104 Lmol-
1), in aqueous solution. The fluorescence of these crystals can be
used to detect biomarkers, such as cysteine, homocysteine and
glutathione, with ultra-high sensitivity and without the interference of
urine, through the dissociation of metal ions from their binding sites.
PCN-521-FA, -TFA, -BA, -IA, -CBA, -NBA, respectively, Figure
1C), each of which provides a unique space and chemical
environment to bind with metal ions (Mg2+, Al3+, Cr3+, Mn2+, Fe3+,
Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+ and Pb2+). The distribution of
these metal-binding sites across a single crystal can be directly
visualized, for the first time, by super resolution laser scanning
confocal microscopy (SR-LSCM) with 10 nm accuracy.
Furthermore, we show that one of these MV-MOFs in nanoscale,
nano-MV-PCN-521-IA can bind with Cu2+ to quench the
fluorescence of its nanocrystals, and function as a switch-on
sensor to precisely detect the concentration of biomarkers, such
as L-cysteine (Cys) in urine, with extremely low detection limit of
22.5 nM.
Introduction of additional metal ions (metalation) into the pores
of metal-organic frameworks (MOFs) has been done through (1)
substitution of metal ions within, or addition to the multi-metallic
secondary building units (SBUs),1 and (2) chelation of metals
either directly to the organic strut of backbone or to a dangling
functionality.2 This metallation chemistry has led to
enhancement in capacity and selectivity of gases uptake, and
better catalytic performance, due to the specific interaction
between the metal-binding site and guest molecules. Herein, we
introduce a third metallation strategy, where metals are placed in
between a pair of rigid linkers precisely anchored in opposite
position within MOF crystal lattice like a vise (Figure 1A). One
end of the vise is stationary and unchanged; while the other end
can be altered to vary the distance between the two parts, thus
precisely control the metal-binding site. In this study, we
demonstrated this “molecular vise (MV) approach” in PCN-521,3
a MOF constructed from tetra-topic organic linkers (4’,4’’,4’’’,4’’’’-
methanetetrayltetrabiphenyl-4-carboxylic acid, MTBC) and octa-
topic second building units (SBUs, Figure S34, Supporting Infor-
Fine tuning of coordination environment for metals has been
a major theme in the development of coordination chemistry,
however, this usually accompanied with changes in the
geometry of ligands around the metal. In this study, when the tri-
topic and mono-topic linkers were introduced into MOF lattice in
pairs by MV approach, their relative position and geometry were
fixed. This unique construct allowed us to systematically vary the
coordination environment for metal without altering the geometry
of ligands. In this way, the binding affinity between the metal and
its binding-site in MOF can be varied with hundred-fold
difference in aqueous solution, which hasn’t been observed in
any previous studies.
In the typical synthesis of MV-MOFs, MV-PCN-521 for
example, MTBC, TBPA and mono-topic linkers with different
functional groups were mixed with ZrCl4 to form a clear solution
in N, N-diethylformamide at 120 °C . This solution was kept in
oven for 3 days to yield transparent octahedral shaped MV-
PCN-521 crystals with the size about 100 μm (Figure 2A,
Section S2, SI), when the ratio of TBPA/MTBC was less than 4:1
in the starting material. If more TBPA was used, another kind of
crystals with hexagonal prism shape emerged, representing a
new MOF with 2D structure in space group Cmca, here we
named WHU-105 (Figure S24 and Table S6, SI). Detailed phase
diagram for the synthesis of pure WHU-105 and MV-PCN-521
was illustrated in Figure S25 in SI. Powder X-ray diffraction
(PXRD) patterns of MV-PCN-521 revealed that the underlying
topology of the parent MOF, PCN-521, was preserved (Figure
S21, S22 and S27, SI). From the single crystal X-ray diffraction
(SC-XRD) experiments, both PCN-521 and MV-PCN-521
crystals synthesized in this study exhibited higher symmetry in
[*] Y. Wang+, Dr. Q. Liu+, Q. Zhang, B. Peng, and Prof. H. Deng
Key Laboratory of Biomedical Polymers-Ministry of Education, College
of Chemistry and Molecular Sciences, Wuhan University
Wuhan 430072 (PR China)
E-mail: hdeng@whu.edu.cn
Dr. Q. Liu, and Prof. H. Deng
UC Berkeley-Wuhan University Joint Innovative Center, The Institute of
Advanced Studies, Wuhan University
Wuhan 430072 (PR China)
[+] These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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Figure 1. (A) Illustration of MV-MOF created by molecular vise approach. (B) Organic linkers used to construct MV-PCN-521. (C) Different metal-binding sites
created by various mono-topic linkers.
space group I4/mmm in comparison to previous reports. A
slightly different unit cell was observed as the original tetra-topic
linker, MTBC, was partially replaced by a pair of tri-topic linker,
TBPA and mono-topic linker, BA, in MV-PCN-521-BA0.1 (0.1
here represents the molar ratio of TBPA in MOF crystal).
Specifically, longer c axis [41.459(3) Å] and shorter a axis
[20.3794(14) Å] were observed in this MV-MOF in comparison to
The co-existence of TBPA and MTBC linkers in MV-PCN-
521 crystals of both micrometer and nanometer sizes was
confirmed by the presence of TBPA signals (132.8 ppm) in 13C
SSNMR spectra (Figure S65 and S66, SI). The precise ratio of
tri-topic linker was determined by the 1H NMR of digested MV-
PCN-521 samples with the fingerprint chemical shift of 7.20-7.25
ppm. Integration of the peak intensities revealed that the
the parent PCN-521 structure [a = 21.0704(9) Å, c = 40.3672(17) presence of TBPA in MV-PCN-521-BA0.1 was 11% (Figure S67,
Å]. The replacement of MTBC by TBPA and mono-topic linkers
requires them to fit into the original tetrahedron geometry of
MTBC. There were two different angles between the phenyl
units of TBPA, 105.9° and 117.0°, revealing in the crystal
structure of MV-PCN-521-BA0.1, both fell well into the possible
bending range of tri-phenyl-amine type of organic linkers (105.5°
to 129.3°) according to crystal structures in Cambridge
Structural Database. The full coordination of all three carboxyl
groups of TBPA and that of mono-topic linker with Zr6O8 SBUs
was further demonstrated by 13C solid-state nuclear magnetic
resonance (SSNMR), where 168.0 ppm peak in the spectra of
the pure organic linkers was completely shifted to 171.0 ppm in
spectra of MV-PCN-521-BA0.1 (Figure S65 and S66, SI). The
opposition arrangement between mono-topic linker and tri-topic
linker was confirmed by the absence of residual electron density
around the coordinated water of SBU in the difference electron
density map of MV-PCN-521-BA0.1 (Figure S33, SI). Nano-
crystals of these MV-MOFs, termed as nano-MV-PCN-521-R
here (Section S2.2, SI), were also synthesized, by applying
vigorous stirring in the reaction solution, instead of stationary
placement. Different from MV-PCN-521 crystals with 100 μm
size, a larger portion of TBPA can be introduced into these
nano-crystals, without sacrificing phase purity.
SI). In contrast, more than 50% of TBPA can be introduced into
nano-MV-PCN-521 (Figure S68 to S71, SI). Structural simulation
of these nano-crystals showed that the integrity of the
frameworks can be maintained by replacing two out of four
MTBC linkers with TBPA linkers in one unit cell (Figure S37 to
S42, SI). Scanning electron microscopy (SEM) images revealed
that the shape of nano-MV-PCN-521 crystals changed from
octahedral to truncated cube (Figure 2I, S72 and S73, SI). It was
worth noting that the ratio of mono-topic linker to tri-topic TBPA
1
linker was determined to be always 1:1 by H NMR of digested
MV-PCN-521 samples, no matter how much of TBPA was
introduced into MV-MOF backbone (Table S1). This combined
with the unaltered underlying topology of the parent MOF in
crystallographic studies demonstrated the pair-up nature of
mono-topic linker and tri-topic linker in MV-MOF-PCN-521
crystals (Figure 1C, S29-S31, SI). This allowed us to simulate
the opposite arrangement of these linker pairs in MV-MOFs,
from which the distance between Nitrogen atom of TBPA and
the terminal functional group of the mono-topic linker was
determined (Figure 1C, and S36 to S48, SI).
The permanent porosity of these MV-MOFs was assessed
by N2 adsorption at 77 K. Type-I curves were observed in their
isotherms and the calculated Brunauer−Emmett−Teller (BET)
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Figure 2. 3D tomography of both MV-PCN-BA0.1 (A-F) and nano-MV-PCN-521-BA (G-L) by laser scanning confocal microscopy. (A) Bright field image, and (B)
LSCM image, scale bar 100 μm, (C) Model of octahedral crystal of MV-MOF, (D) 3D reconstitution of MV-MOF in100μm size, scale bar 20 μm. (E) One slice of (F)
consecutive LSCM sections of MV-MOF, scale bar 20 μm. (G) Bright field image, and (H) STED image, scale bar 1 μm. (I) SEM image, and (J) 3D reconstitution
of nano-MV-MOF, scale bar 500 nm. (K) One slice of (L) consecutive LSCM sections of nano-MV-MOF, scale bar 500 nm. Region of twin crystal and bubbles in
MV-MOF (E) was highlighted in red dashes.
surface areas were 4000, 3390, 3320 m2g-1 for MV-PCN-521-
BA0.1, MV-PCN-521-BA0.05 and PCN-521, respectively (Figure
S51 to S56, SI), where the surface areas of MV-MOFs were
higher than that of the parent MOF. Based on these
observations, partial linker replacement in MOF structure was
indeed an efficient way to increase inner surface, in good
accordance with previous studies.4 However, when too much
replacement occurred, as illustrated here by nano-MV-PCN-521
crystals with higher percentage (more than 50%) of TBPA,
slightly lower surface areas were observed, ranging from 1980
to 3090 m2g-1. These MV-PCN-521 exhibited high chemical
stability, evidenced by unaltered sharp peaks in their PXRD
patterns after immersion in water for 6 days (Figure S50, SI).
Thermalgravimetric analysis (TGA) of these MV-MOFs showed
no weight lose until 550 °C in air (Figure S78 to S81, SI).
light [λ=405 nm, d = λ/(2NA)],8 corresponding to 45 and 65 unit
cells along and perpendicular to [101] direction, respectively
(Figure 2E and 2F). 56 slices from top to bottom with equal
space were displayed in Figure S74, where metal-binding sites
distributed allover these slices. Due to the high resolution of
LCSM, we were able to observe every structural details of the
crystal such as tiny bubbles and small twin crystal regions within
the whole MV-MOF crystal (Figure 2E). Here, the sizes of the
bubble and twin crystal circled in red dashes were 15 and 7 μm,
respectively. More than three MV-PCN-521 crystals in 100 μm
sizes were examined, where similar phenomena could be
observed, since no perfect crystal exists (Figure S74 to S76, SI).
In comparison to crystals of 100 μm size, the distribution of
metal-binding sites in nano-MV-PCN-521 crystals was more
homogeneous, reflected on their LCSM and stimulated emission
depletion (STED) images (Figure 2H, 2J, 2L, 2K and S77). One
truncated cube crystal with the size of around 800 nm was
examined by 3D tomography with 10 slices, each of which
provides a fluorescence map of 10 nm resolution within the slice,
corresponding to 5 unit cells. Note that the resolution along the
excitation light was slightly sacrificed to guarantee the resolution
in the focal plane.
Introduction of multiple functional groups into MOF structure
has attracted a lot of attentions in recent MOF studies due to the
synergy of these components and the flexibility in tuning pore
environments without altering the target topology.5 One of the
remaining challenges was to decipher the spatial arrangement of
these functional components.6 Similarly, the distribution of TBPA
and mono-topic linkers in MV-PCN-521 was hard to determine
using XRD measurement due to both occupational and
displacement disorder. In this study, given the fluorescence of
TBPA linkers, we applied laser scanning confocal microscopy
(LSCM)7 to detect the distribution of TBPA linker throughout the
crystals of MV-MOFs (Figure 2). Green fluorescence was clearly
observed in all the MV-PCN-521 crystals examined under
excitation light of 405 nm, indicating the successful replacement
of TBPA with MTBC, while PCN-521 exhibits no fluorescence
under the same condition (Figure 2A, 2B and S74 to 76, SI).
The coordination between metals and metal-binding sites in
MV-MOF crystals can be directly visualized by the instantaneous
fluorescence quench of these crystals, once in contact with
aqueous solutions of metal salt (Figure 3A). This is triggered by
ligand-metal charge transfer (LMCT) between the tertiary amine
TBPA linker and the metal cations at the metal-binding site.9
These metals can be facilely removed from the metal-binding
sites in MV-MOFs, when stronger coordinating ligands was
added in, thus leading to the recovery of fluorescence. A large
variety of metals, Mg2+, Al3+, Zn2+, Cr3+, Mn2+, Fe3+, Co2+, Ni2+,
Cu2+, Ag+, Cd2+ and Pb2+, can be placed at the metal-binding
sites in these MV-MOFs created by molecular vise approach
(Figure S84 to S108, SI). Quantitative binding and dissociation
of metals were observed, regardless of the space and
functionalities within these metal binding sites. This was
evidenced in the peak shift of metals and N in the linkers in their
X-ray photoelectron spectroscopy (XPS) spectra (Figure 3B to
3E). Specifically, in the case of nano-MV-PCN-521-FA, Cu2+
The precise distribution of metal-binding site in MV-MOF
single crystal was mapped layer by layer using fluorescence of
TBPA linker through three-dimensional (3D) tomography. An
octahedral single crystal with the edge of 92 μm was examined
along [101] direction by 180 slices, from which
a 3D
reconstruction of the crystal was generated, in good accordance
with the 3D model (Figure 2C and 2D). The thickness of each
slice is about 90 nm, and the resolution within the slice is about
180 nm according to the limit by the wavelength of the incident
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Figure 3. (A) Association and dissociation of metals in MV-PCN-521-FA, and fluorescence quenching and recovery displayed in test papers composed of nano-
MV-PCN-521-FA. (B) N spectra and (C) Cu spectra in XPS analysis of nano-MV-PCN-521-FA, quenched by Cu2+ and recovered by cysteine. (D) N spectra and
(E) Cu spectra in XPS analysis of nano-MV-PCN-521-IA, quenched by Cu2+ and recovered by cysteine. (F) Fluorescence intensity decrease in MV-PCN-521-FA
versus the concentration of Mn+. (G) Fluorescence intensity decrease in MV-PCN-521-R versus the concentration of Cu2+
.
2p3/2 peak shifted by 2.7 eV once anchored in this metal-binding
site, while a shift of 2.6 eV was observed in that of nano-MV-
PCN-521-IA with a different functional group. The difference in
the shift of N 1s peak between these two nano-MV-MOFs was
larger, 1.7 eV in the spectrum of nano-MV-PCN-521-FA, and 0.3
eV in that of nano-MV-PCN-521-IA, which can be attributed to
better coordination of Cu2+ at the metal-binding sites in nano-
MV-PCN-521-FA crystals (Table S8 and S9, Figure S96 and
S108, SI). Although all kinds of metals can quench the
fluorescence to some extent, the differences in their binding
affinity was obvious (observed binding constants, Kobs varies
from 1.56 × 102 to 1.70 × 104, Figure 3F and 3G). The detailed
coordination behavior of different metals in different meta-
binding sites of MV-MOFs was described in Section S10 in SI.
extremely low detection limit, 22.5 nM and 46.4 nM, for L-
cysteine and glutathione, respectively. It is worth noting that the
detection of these thiol-molecules was not affected by the
presence of urine, making these papers suitable for direct and
quick test in physical examinations. They can be recycled for at
least four times without losing their performance (Figure S83, SI).
Given the excellent stability of these MV-MOFs in water, the
corresponding test papers are well-suited for transport and
storage in remote areas and countries lack of sophisticated
medical instruments.
Acknowledgements
Given the excellent affinity between Cu2+ and nano-MV-
PCN-521-IA, a test paper composed of nano-MV-PCN-521-IA
was prepared for the detection of biomarkers such as cysteine,
homocysteine and glutathione, which are important health
index.10 The fluorescence of the test paper was quenched by
Cu2+ prior to the test, and immediately “turned-on”, when a
solution of biomarkers was dripped on this test paper (Figure 3A
and S83, SI). The concentration of biomarkers can be directly
read from the intensity of the fluorescence in comparison to a
standard titration curve (Figure S125 and S128, SI), with
LSCM were performed in College of Life Science of Wuhan
University with the assistance of Prof. M. Tang. SSNMR were
collected at Wuhan Institute of Phys-ics and Mathematics
(WIPM), Chinese Academy of Sciences, with the assistance of
Prof. J. Xu. We thank Prof. J. Xu (WIPM), Prof. M. Tang, Prof. H.
Cong, Prof. F. Ke, C. Wang, X. Xu, C. Lei, X. Gong, X. Cai, H.
Dai, Q. Han, X. He and W. Yan (Wuhan University) for their
invaluable assistance and discussion. Financial support was
provided by the 1000 Talent Plan of China, National Natural
Science Fundation of China (21471118, 91545205, 91622103)
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