Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
RETRACTED ARTICLE: Development of a porous
bifunctional metal-organic framework for
cyanosilylation of aldehydes and ablation of
human laryngocarcinoma cells
Jie Zhou, Jun-Wei Xiong & Yu Zhao
To cite this article: Jie Zhou, Jun-Wei Xiong & Yu Zhao (2019) RETRACTED ARTICLE:
Development of a porous bifunctional metal-organic framework for cyanosilylation of aldehydes
and ablation of human laryngocarcinoma cells, Phosphorus, Sulfur, and Silicon and the Related
Elements, 194:8, 829-835, DOI: 10.1080/10426507.2018.1550643
To link to this article: https://doi.org/10.1080/10426507.2018.1550643
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
2019, VOL. 194, NO. 8, 829–835
https://doi.org/10.1080/10426507.2018.1550643
RETRACTED ARTICLE: Development of a porous bifunctional metal-organic
framework for cyanosilylation of aldehydes and ablation of human
laryngocarcinoma cells
Jie Zhoua, Jun-Wei Xiongb, and Yu Zhaoc
a
ENT Department, Chongqing Qianjiang National Hospital, Chongqing, China; bENT Department, Chongqing General Hospital, Chongqing,
China; cENT Department, Fuling Center Hospital of Chongqing City, Chongqing, China
ARTICLE HISTORY
This work presents the synthesis and properties study of a new dual-functional metal-organic
framework (MOF) with the chemical formula of [Cu7(nbpt)4(H2O)2(OH)4](DMF)5(H2O) (1,
DMF ¼ N,N-dimethylformamide) based on a Y-shaped tricarboxylic ligand 30 -nitro-[1,10 -biphenyl]3,40 ,5-tricarboxylic acid (H3nbpt). This compound has been characterized by elemental analysis, FTIR spectroscopy, thermogravimetric and X-ray diffraction analyses. The crystal structure analysis
reveals that compound 1 is composed of a {Cu7(OH)4}10þ secondary building unit that is connected by the nbpt3- ligands into a 3D framework with 1D nanosized channels running along the
b axis. Compound 1 was investigated for its heterogeneous catalytic activities towards the cyanosilylation of aldehydes under solvent-free conditions, which shows that it catalytic activities could
be greatly enhanced by removing the coordinated solvents, indicating that the exposed open
metal sites in the activated 1 (1a) is beneficial to the cyanosilylation reaction. In addition, the anticancer activates of 1 has been evaluated on four human laryngocarcinoma cells (TU212, Hep-2,
M4E and TU686) via the MTT assay.
Received 20 June 2018
Accepted 17 November 2018
KEYWORDS
Metal-organic framework;
nitro-tricarboxylic acid
ligand; solvothermal
reaction; cyanosilylation
reaction; anticancer activity
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GRAPHICAL ABSTRACT
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ABSTRACT
Introduction
The cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN), as a direct and efficient method for
the formation of C–C bonds in organic synthesis, has recently
received tremendous attention as cyanohydrins are key intermediates in the synthesis of biologically important compounds such as a-hydroxy acids, a-hydroxyl ketones and
a-amino acids.[1–3] The majority of these studies have revealed
that the reaction is catalyzed by homogeneous catalysts i.e.
metallic Lewis acids/bases, inorganic solid acids/bases, and
nonmetallic organic molecules, whose performance is still
limited with a large difficulty in separation and recyclable
use.[4] From an economic point of view, the strong industrial
preference for heterogeneous catalysts arises from their
inherent stability and ease of recovery, allowing for more efficient separation and recycling. Hence, the development of
efficient heterogeneous catalysts for cyanosilylation of carbonyl compounds with TMSCN is a very important subject in
current research, and several efficient catalysts have been
developed so far. However, from the point of green chemistry,
it is a pressing challenge to seek an efficient heterogeneous
catalyst under environmentally friendly conditions.[5, 6] Thus
there is a great need for the developing efficient and environmental friendly catalysts for cyanohydrin reaction.
Metal organic frameworks (MOFs) are exciting hybrid
materials with a plethora of potential applications including
gas storage, gas separation, catalysis, and drug delivery.[7–12]
They are crystalline nanoporous materials comprised of
ordered networks formed from organic electron donor
CONTACT Yu Zhao
yu_zhao666@126.com
ENT Department, Fuling Center Hospital of Chongqing City, Chongqing, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
ß 2018 Taylor & Francis Group, LLC
J. ZHOU ET AL.
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Figure 1. (a) View of the coordination environments of Cu(II) ions in 1 (b) The coordination modes of the organic ligand. (c) The 3D framework of compound 1
with the 1D nano-sized channels. (d) The schematic representation of the simplified topological network for compound 1.
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linkers and metal cations or clusters, whose pore size and
surroundings could be designed and controlled via elaborately selection of the building blocks. In particular, MOFs
have been widely studied as size- and shape-selective heterogeneous catalysts due to their large pore size, high BET surface areas and diverse functionalizations.[13–15] For the
optimal catalytic activity, two types of strategies are used: (i)
introduction of organic groups to provide guest-accessible
functional organic sites and (ii) formation of coordinatively
unsaturated metal sites. If the metal is coordinatively saturated, the organic moiety incorporating functionality for
non-covalent interactions can bind the reactant(s) through
H-bonding, p–p stacking, as examples., leading to their activation. In another case, metal ions bound to one or more
solvent molecules can be heated to remove the solvent molecules exposing the metal ion to the reactants that can directly bind the metal ion and hence can be activated. Since
the first discovery by Fujita et al, many papers concerning
the MOFs-based catalysts for cyanosilylation have been
reported.[16–18] For instance, Kaskel and coworkers have
revealed that MIL-101-Cr is an efficient catalyst for the cyanosilylation of benzaldehyde after the removal of the coordinated water molecules.[17] On the other hand, coordination
chemistry has a great potential to offer a wide variety of
compounds with different geometry, redox reactivity and a
diversity of mechanisms related to DNA binding, some of
them unique to metals.[19] The usefulness of coordination
metal complexes in cancer chemotherapy has been demonstrated by Cisplatin and other platinum coordination compounds which are amongst the most successfully used
anticancer drugs.[20] As a result of an intense and continued
research on coordination complexes with antitumor activity,
compounds of different metals other than Pt are entering
clinical studies. Recent studies have shown that the Cu(II)based coordination compounds show promising results.[21]
For instance, Guo and co-works have successfully prepared
a lanthanide MOF which shows high cytotoxicity toward the
human lung cancer cell A549[22]; Mukherjee and coworkers
have reported that the have studied the cytotoxic activity of
the nanostructured MOFs on human colorectal carcinoma
cell lines, and found that some of them could significantly
lead to the cancer cell death.[23] Although there are many
MOFs have been shown to be capable of catalyzing cyanosilylation or inhibiting human cancer cells, none of them can
achieve the above mentioned two functions simultaneously.
In this study, a new dual-functional metal-organic framework with the chemical formula of [Cu7(nbpt)4(H2O)2
(OH)4](DMF)5(H2O) (1, DMF ¼ N,N-dimethylformamide)
based on a Y-shaped tricarboxylic ligand 30 -nitro-[1,10 biphenyl]-3,40 ,5-tricarboxylic acid (H3nbpt) has been
achieved under solvothermal conditions. This compound
has been characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric and X-ray diffraction analyses.
The crystal structure analysis reveals that compound 1 is
composed of a {Cu7(OH)4}10þ secondary building unit that
is connected by the nbpt3 ligands into a 3D framework
with 1D nanosized channels running along the b axis.
Compound 1 was investigated for its heterogeneous catalytic
activities towards the cyanosilylation of aldehydes under
solvent-free conditions, which shows that it catalytic activities could be greatly enhanced by removing the coordinated
solvents, indicating that the exposed open metal sites of in
the activated 1 (1a) is beneficial to the cyanosilylation reaction. In addition, the anticancer activates of 1 and 1a has
PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
Table 1. The results for the catalytic cyanosilylation of aldehydes in the presence of 1 and 1a.
blanka
15.45%
1 conversiona
55.13%
1a conversiona
99.32%
16.89%
67.57%
99.82%
11.56%
53.15%
99.32%
9.12%
44.85%
96.43%
6.82%
a
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Aldehyde
except that the four O atoms come from three carboxylic O
atoms. The Cu(II)-O bond distances range from 1.920(2) Å
to 2.197(3) Å, which locate in the normal range among the
Cu(II)-O bond distances of the reported Cu(II)-carboxylate
MOFs in the literature.[24–26] Cu1, Cu3, Cu4 and their symmetry-related ones are held together via four l3-OH groups
and the Cu2 atom to give rise to the {Cu7(OH)4}10þ cluster,
which serves as the secondary building unit in the formation
of the network of 1. In the {Cu7(OH)4}10þ cluster, As for
the nbpt3- ligands, they reveal the same five-connected
mode but with their carboxylic groups showing different
coordination modes which are shown in the Figure 1b. The
connection of the {Cu7(OH)4}10þ cluster with the nbpt3ligands generates a porous three-dimensional framework
with 1D rhombus channels running along the b axis. The
window size for the 1D channel is 10.4;8.2 Å2, which fills
with water occupied open metal sites and the uncoordinated
nitro-groups (Figure 1c). The l3-OH group forms H-bonding interaction with the carboxylic O atom and the donoracceptor distance is 2.165 Å (O1-H1O13, Figure S1). With
omitting the coordinated water molecules, PLATON analysis
revealed that the 3D framework was composed of voids of
978 Å3, which represent 40.1% per unit cell volume. TOPOS
software was used to simplify this framework. In this 3D
framework, the {Cu7(OH)4}10þ cluster could be treated as
12-connected node, and the nbpt3- ligands could be considered as 3-connected nodes, so the whole framework of 1
could be viewed as a llj-type 3,12-connected net with a
point symbol of {420.628.818}{43}4 (Figure 1d).
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Scheme 1. The cyanosilylation reaction in the presence of selected complexes.
18.34%
24.25%
Conversion determined by GC, and the NMR spectra for the products are
shown in the Figure S4.
been evaluated on four human laryngocarcinoma cells
(TU212, Hep-2, M4E and TU686) via the MTT assay.
831
PXRD and thermogravimetric analysis for compound 1
Results and discussion
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Crystal structure of compound 1
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Compound 1 was synthesized by reaction of
Cu(NO3)26H2O and H3nbpt in a mixed solvent of DMF
and H2O in the presence of HNO3. It should be noted that
only white deposition was obtained without the presence of
HNO3, indicating the HNO3 might be a pH regulator which
is very important for the crystallization. It has been shown
that the addition of HNO3 plays a vital role in the formation
of the MOF-505 series. Single crystal X-ray diffraction analysis revealed that compound 1 crystallizes in triclinic P-1
space group and features a three-dimensional framework
based on the {Cu7(OH)4}10þ secondary building unit. The
asymmetric unit of 1 is composed of four crystallographically independent Cu(II) ions, two nbpt3 ligand, two l3-OH
groups and two coordinated water molecules. As shown in
Figure 1a, the Cu1 atom is four-coordinated by four O
atoms from three carboxylic O atoms and one l3-OH group,
forming a distorted tetrahedral coordination environment;
The distorted octahedral coordination surrounding of Cu2 is
finished by four l3-OH groups and two carboxylic O atoms;
Cu3 shows a similar coordination surrounding with Cu2
expect the six O atoms come from three carboxylic O atoms,
two l3-OH groups and one coordinated water; Cu4 atom
show the similar four-coordinated surrounding with Cu1
The simulated and experimental PXRD patterns of 1 are
shown in Figure S 2a (Supplemental Materials). A good
match between the experimental and theoretical PXRD patterns was observed, which is the evidence for the phase purity and structural consistency of the bulky products for
crystalline 1. In addition, the thermal stability of 1 was also
analyzed on crystalline samples from 30-800 C under N2
atmosphere (Figure S2b). The TGA curve of 1 shows that it
has a weight loss of 19.4% in the temperature range of
30–210 C, which is consistent with the removal of two
coordinated H2O, five free DMF molecules and one lattice
H2O molecules (calcd 19.6%). After taking off the solvent
molecules, the framework of 1 can be stable up to 250 C,
after which the framework began to collapse. The permanent
porosity of the activated 1 (1a) was unambiguously established by its N2 sorption isotherm at 77 K. The activated
sample 1a was prepared by exchanging in dichloromethane
overnight and then activated under dynamic vacuum at
110 C for 6 h. The framework integrality has been characterized by PXRD measurement, which shows a good match
between the PXRD patterns of 1 and 1a, indicating that the
framework was maintained because the broadened peaks
positions remained (Figure S 2a). The full activation of the
framework has been confirmed via the TGA curve, which
reveals that there is no obvious weight loss before the temperature of 251 C. The N2 sorption isotherms of the
J. ZHOU ET AL.
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Scheme 2. Proposed mechanism for the cyanosilylation reaction of carbonyl compounds catalyzed by 1a.
Catalytic activity
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activated sample at 77 K revealed a completely reversible
type-I behavior, a characteristic of microporous materials
(Figure S 3). Based on the N2 adsorption data, the
Brunauer–Emmett–Teller (BET) surface area and Langmuir
surface area of 1a were calculated to be 821 m2g1 and
953 m2g1, respectively with a corresponding pore volume
of 0.36 cm3 g1. The pore size distribution centers around
8.36 Å (as determined using the Horvath–Kawazoe method),
which are basically similar to the results from the singlecrystal X-ray diffraction study (Figure S 3 inset).
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As is well-known, the cyanosilylation reaction is an effective
chemical method to obtain cyanohydrins. Complex 1 possesses 1D open channels and unsaturated metal sites after
the removal of coordinated water molecules, indicating its
potential properties as a heterogeneous catalyst. Therefore,
the cyanosilylation of aromatic aldehydes with different substituent groups were selected to test the catalytic ability of
1a (Scheme 1). Under N2 atmosphere, a solution of aldehyde
(0.5 mmol) and cyanotrimethylsilane (1 mmol) was added to
activated the samples of complex 1a (10 mg) at room temperature. After the reaction was stirred for 4 h, the mixtures
were separated by a centrifuge. The liquid part was utilized
to analyze the conversions by gas chromatograph-mass spectrometry and the results are summarized in Table 1. Using
1a as the catalyst, the conversion of benzaldehyde and its
derivatives can reach above 97–99% under the given conditions, while the yields are only about 45-67% for 1 under
the same conditions. The cyanosilylation yield of 1a is much
higher than that of many MOFs used for the cyanosilylation
study under similar conditions, which might be ascribed to
its large inner spaces and high density of exposed metal
Table 2. Growth inhibitory effects on TU212, Hep-2, M4E and TU686 cells.
IC50 (lM)
Compounds
TU212
Hep-2
M4E
TU686
Ligand
Cu(NO3)23H2O
1
Vinorebine
>100
>100
25
35
>100
>100
25
25
>100
>100
35
30
>100
>100
40
45
sites.[27–29] It is noteworthy that the catalytic activity of 1a is
higher than that of compound 1. This can be attributed to
more open metal sites of Cu2þ in 1a, which can effective
enhance the catalytic activity. The stability of compound 1a
was examined after the catalytic study by PXRD, which
reveals the same PXRD pattern as the as-synthesized phase,
indicating that the compound was stable (Figure S 2a). In
addition, the parallel experiment without a catalyst was also
done, and the conversion of benzaldehyde and its derivative
is below 20%. These results indicate that compound 1a can
be used as an efficient catalyst for the cyanosilylation reaction under mild conditions. To further explore whether the
activation of the carbonyl species occurs inside the pores or
on the surface of the solid catalyst, substrates of increasing
dimensions were tested, a significant size-selectivity effect is
observed with catalyst, when the substrate was 1-naphthaldehyde with dimensions 9.7 8.4 Å2, the conversion was
reduced to 24.25% for 1a.
Based on the experimental results and previously reported
results, a plausible reaction mechanism is proposed to illustrate the process of 1a catalyzed cyanosilylation reaction.[27–29] The labile water molecules in the channels of
compound 1 were removed by heating to expose the unsaturated metal sites previously. The aldehydes were activated
by the coordinatively unsaturated Cu centers to react with
TMSCN (Scheme 2). The products were replaced by
PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
C60H32Cu7N4O38
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
a/
b/
c/
Volume/Å3
Z
qcalcg/cm3
l/mm-1
F(000)
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I> ¼2r (I)]
Final R indexes [all data]
Largest diff. peak/hole/e Å3 CCDC
1861.67
293(2)
triclinic
P-1
11.8251(4)
13.6676(4)
17.527(3)
70.019(4)
90.137(4)
68.262(3)
2445.8(4)
1
1.264
1.565
927.0
43112
8583 [Rint ¼ 0.1379, Rsigma ¼ 0.1141]
8583/102/562
1.031
R1 ¼ 0.0571, wR2 ¼ 0.1305
R1 ¼ 0.1076, wR2 ¼ 0.1518
0.64/0.67 1878531
Antitumor activity
Synthesis of compound
[Cu7(nbpt)4(H2O)2(OH)4](DMF)5(H2O) (1)
A mixture of Cu(NO3)23H2O (0.2 mmol, 0.048 g), H3nbpt
(0.1 mmol, 0.033 g), DMF (4 mL), H2O (1 mL) and three
drops of concentrated nitric acid was sealed in a 20 mL glass
vial, and then the mixture was heated to 90 C and kept at
that temperature for 3 d. After cooling slowly to room temperature, colorless block crystals were isolated with 45%
yield based on H3nbpt ligand. Anal. Calcd. (%) for 1
C75H69Cu7N9O44: C, 40.12; H, 3.10; N, 5.61. Found: C,
39.91; N, 5.42; H, 3.14. IR (KBr, cm1): 3426(w), 2993(w),
1680(s), 1651(s), 1563(s), 1477(s), 1381(s), 1274(s), 1221(s),
1108(m), 1061(w), 942(w), 845(s), 782(m), 716(w), 672(m).
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aldehydes, and the catalysts were continued to activate the
aldehydes in the next catalytic cycle.
Elemental analyses (C, H and N) were determined with
Perkin-Elmer 240 elemental analyzer. Thermogravimetric
analysis was carried out on a NETSCHZ STA–449C thermoanalyzer with a heating rate of 10 C/min under a nitrogen
atmosphere. Infrared spectra were measured on a Nicolet
Magna 750 FT-IR spectrometer in the range of
400–4000 cm1 using the KBr pellets. Powder X-ray diffraction (PXRD) analyses were recorded on a Bruker AXS D8
advanced automated diffractometer with Cu-Ka radiation.
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Table 3. Crystal data and structure refinements for 1.
Empirical formula
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The cytotoxicity of the organic ligand H3nbpt and 1 and the
reference drug vinorebine were evaluated by MTT (3-(4,5Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
bromide)
assay method against four human laryngocarcinoma cells
(TU212, Hep-2, M4E and TU686). Compounds were dissolved in DMSO and blank samples containing the same
volume of DMSO were taken as controls to identify the
activity of solvent in this cytotoxicity experiment. The anticancer drug Vinorebine was used as a positive control to
assess the cytotoxicity of the test compounds. The results
were analyzed by means of cell inhibition expressed as IC50
values and they are shown in Table 2. The organic ligand
was inactive against all of these cell lines (IC50 > 100 lM).
At this concentration, it should exert high cytotoxicity
against these cells, so we concluded that it exerted no inhabitation selectivity towards these cell lines. However, after the
tumor cells were incubated in the presence of compound 1
for 72 h, the IC50 value ranged from 25 to 40 lM, some of
which were even lower than those of vinorebine, indicating
that compound 1 exhibited antitumor activity against all of
these cell lines in different degrees. It is to be noted that the
ligand and Cu(NO3)2 did not show any significant activity
on all the four cancer cells, which confirmed that the chelation of the ligand with the Cu(II) ion is the only responsible
factor for the observed cytotoxic properties of the
new compounds.
Experimental
Materials and instrumentation
All reagents and solvents employed in this work were commercially available and used without further purification.
X-ray crystallography
Single crystal X-ray crystal data of 1 was collected on a computer–controlled Oxford Xcalibu E diffractometer with
graphite–monochromated Mo–Ka radiation (k ¼ 0.71073 Å)
at room temperature. Absorption corrections were applied
using SADABS. The structures were solved by direct methods by the SHELXS-2014 package and refined by full–matrix
least–square methods on F2 by using the SHELXL-2014/6.
All non–hydrogen atoms were refined anisotropically and all
H atoms were generated in their ideal locations.
Crystallographic data and refinement details are summarized
in Table 3, and the selected bond distances and angles for
compound 1 are given in Table S 1 (Supplemental
Materials). The H-bond details are listed in the Table S2.
Antitumor activity
The anticancer activity of compound 1 was evaluated against
four human laryngocarcinoma cells (TU212, Hep-2, M4E
and TU686) via the MTT assay. The two cancer cells were
seeded in a 96-well plate in which cells density is 5000 cells
per test well, and cultured overnight at 37 C in a 5% CO2
incubator. The tested compounds were dispersed in DMSO
and diluted in the respective medium containing 1% fetal
bovine serum (FBS). After 24 h, the medium was replaced
with the respective medium with 1% FBS containing the
compound 1 at various concentrations. After 48 h, 10 lL of
MTT (5 mg/mL) in phosphate buffered saline (PBS) was
added to each well and incubated at 37 C for 4 h. The
medium with MTT was then flicked off, and the formed formazan crystals were dissolved in 100 lL of DMSO. The
J. ZHOU ET AL.
absorbance was then measured at 570 nm using a microplate reader.
[11]
Conclusion
In summary, a new porous Cu(II)-organic framework based
on a Y-shaped tricarboxylic ligand 30 -nitro-[1,10 -biphenyl]3,40 ,5-tricarboxylic acid (H3nbpt) has been synthesized under
solvothermal condition. Crystal structure analysis reveals
that compound 1 is composed of {Cu7(OH)4}10þ secondary
building unit that connected by the nbpt3 ligands into a
3D framework with 1D nanosized channels running along
the b axis. The activated 1 could be used as a dual-functional material for effective cyanosilylation of aldehydes
under solvent-free conditions and inhibition of human cancer cell growth.
[12]
[13]
[14]
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