Porous GdIII-Organic Framework as a Dual-Functional Material for Cyanosilylation of Aldehydes and Ablation of Human Liver Cancer Cells

Article abstract of DOI:10.1002/zaac.201800467

Metal-organic frameworks (MOFs) have gained great attention in recent years because they could behave as multifunctional materials which combine the advances of porous solids and coordination complexes. With the aim of constructing multifunctional MOFs, i

Full text of DOI:10.1002/zaac.201800467

Journal of Inorganic and General Chemistry
Zeitschrift für anorganische und allgemeine Chemie
III
DOI: 10.1002/zaac.201800467
ARTICLE
Porous Gd -Organic Framework as a Dual-Functional Material
for Cyanosilylation of Aldehydes and Ablation of Human Liver
Cancer Cells
Dong Han,[a] Xiu-Li Yan,[a] and Jian Liu*[a]
Abstract. Metal-organic frameworks (MOFs) have gained great atten-
tion in recent years because they could behave as multifunctional mate-
rials which combine the advances of porous solids and coordination
analysis reveals that compound 1 is composed of 1D helical chain
secondary building units that connect by the bpt ligands into a 3D
framework with 1D nanosized channels running along the b axis. In
3
–
complexes. With the aim of constructing multifunctional MOFs, in view of its high porosity and accessible open metal sites, the activated
this study, we choose a Y-shaped tricarboxylic ligand biphenyl-3,4Ј,5- 1 (1a) was studied for the cyanosilylation of aldehydes under solvent-
III
tricarboxylic acid (H
3
bpt) to react with Gd ions to afford a new dual-
free conditions. The catalytic activity of 1a is much higher than that
of compound 1, indicating that the exposed open metal sites of 1a is
functional lanthanide-organic framework with the chemical formula of
Gd (bpt) (H O) ]·(DMF) (H O) (1) (DMF N,N-dimethyl- beneficial to the cyanosilylation reaction. In connection to these, the
[
2
2
2
2
2
2
6
=
formamide) under solvothermal condition. The title complex was
characterized by means of elemental analysis, FT-IR spectroscopy,
different cytotoxicities of 1 and 1a were also evaluated on four human
liver cancer cells (SMMC-7721, Bel-7402, MHCC97 and Hep3B) by
thermogravimetric and X-ray diffraction analyses. Crystal structure the MTT assay.
1
Introduction
separation, energy conversion, contamination enrichment, and
In particular, MOFs have been widely studied as
size- and shape-selective heterogeneous catalysts due to their
so on.[
7–10]
As an important raw material, cyanohydrins have been
widely used as versatile building blocks for pharmaceuticals,
large pore size, high BET surface areas and diverse function-
[1]
agrochemicals, and fine chemicals. Generally, the addition
of cyanide to carbonyl compounds is one of the most useful
approaches for the preparation of cyanohydrins and has fre-
quently been at the forefront of synthetic chemistry.[ Trimeth-
ylsilyl cyanide (TMSCN) is one of the most useful and safe
cyanating reagents for nucleophilic addition to carbonyl com-
pounds to give cyanohydrin trimethylsilyl ethers.[ Hence, the
development of efficient catalysts for cyanosilylation of carb-
onyl compounds with TMSCN is a very important subject in
current research, and several efficient catalysts have been de-
veloped so far. During the past few decades, a lot of organic
catalysts have been developed for the cyanosilylation of carb-
onyl compounds with TMSCN, but these catalysts suffer from
[11–15]
alizations.
The removal of the coordinated solvents on
the metal ion/cluster could generate the coordinatively unsatu-
rated sites, which can be used as the activators in many organic
reactions similar to the Lewis acid catalysts. Since the first
discovery by Fujita et al., lots of papers concerning the MOFs-
2]
[
16–18]
based catalysts for cyanosilylation have been reported.
For instance, Kaskel and co-workers have revealed that MIL-
01-Cr is an efficient catalyst for the cyanosilylation of benzal-
3]
1
dehyde after the removal of the coordinated water mol-
ecules.[
17]
On the other hand, MOFs have also show great promise in
the field of biomedicine because it has been reported that
MOFs can interact with DNA through noncovalent interac-
tions, including intercalation and groove binding for large mol-
some drawbacks such as tedious separation and recycle prob-
lems, which restrict their practical applications.[
4–6]
Thus there
[
19–22]
ecules and slot external electrostatic binding for cations.
is a great need for the developing efficient and environmental
friendly catalysts for cyanohydrin reaction.
As an emerging class of crystalline material that composed
of metal modes and organic connectors, metal-organic frame-
works (MOFs) have gained great interests for their wide range
of potential applications as functional materials in gas storage/
For instance, Guo and co-works have successfully prepared a
lanthanide MOF, which shows high cytotoxicity toward the
human lung cancer cell A549; Mukherjee and co-works 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. Although there are many MOFs have
been shown to be capable of catalyzing cyanosilylation or in-
hibiting human cancer cells, none of them can achieve the
above mentioned two functions simultaneously.
*
Dr. J. Liu
E-Mail: jian_liu666@163.com
[a] Department of Anesthesiology
Shanxian Central Hospital (Affiliated Lake West Hospital of Jining
Medical College)
Shanxian, Shangdong, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201800467 or from the au-
thor.
In this study, a new dual-functional lanthanide metal-organic
framework with the chemical formula [Gd (bpt) (H O) ]·
2
2
2
2
(DMF) (H O) (1) (DMF = N,N-dimethylformamide) based on
2
2
6
Z. Anorg. Allg. Chem. 2019, 645, 422–427
422
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Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
a Y-shaped tricarboxylic ligand biphenyl-3,4Ј,5-tricarboxylic Table 1. Crystal data and structure refinements for [Gd
2
(bpt)
2
(H
2
O)
2
]·
(
2 2 6
DMF) (H O) (1).
acid (H bpt) was synthesized under solvothermal condition.
3
The title compound was characterized by elemental analysis,
1
FT-IR spectroscopy, thermogravimetric and X-ray diffraction
analyses. Crystal structure analysis reveals that compound 1 is
Empirical formula
Formula weight
C
30 2 14
H18Gd O
916.94
composed of 1D helical secondary building unit that connect Temperature/K
288.0(3)
3
–
Crystal system
Space group
a /Å
b /Å
c /Å
orthorhombic
P2
by the bpt ligands into a 3D framework with 1D nanosized
channels running along the b axis. Furthermore, the activated
1 1
2 2
28.3269(2)
14.3386(6)
14.9223(2)
90
90
90
6061.0(3)
4
1.005
2.205
16648
1
(1a) shows excellent heterogeneous catalytic activities
towards the cyanosilylation of aldehydes under solvent-free
conditions. The catalytic activity of 1a is much higher than α /°
β /°
γ /°
Volume /Å
that of compound 1, indicating that the exposed open metal
sites in 1a is beneficial to the cyanosilylation reaction. In ad-
3
dition, the anticancer activates of 1 were evaluated on four
human liver cancer cells (SMMC-7721, Bel-7402, MHCC97 ρcalcd. /g·cm
Z
–
3
–
1
μ /mm
Reflections collected
and Hep3B) by the MTT assay.
Independent reflections
10036 [Rint = 0.0362, Rsigma
.0658]
=
0
2
Experimental Section
Data/restraints/parameters
Goodness-of-fit on F
10036/139/421
1.063
2
2
.1 Materials and Instrumentation
Final R indexes [I Ն 2σ (I)]
Final R indexes [all data]
Largest diff. peak/hole /e·Å
R
1
= 0.0539, wR
= 0.0582, wR
2
= 0.1582
= 0.1641
R
1
2
–
3
All reagents and solvents employed in this work were commercially
available and used without further purification. Elemental analyses (C,
H and N) were determined with Perkin–Elmer 240 elemental analyzer.
Thermogravimetric analysis was carried out with a NETSCHZ STA–
2.51/–2.27
0.145(13)
Flack parameter
–1
2.4 Catalytic Test for Cyanosylation Reaction
449C thermo-analyzer with a heating rate of 1 K·min in a nitrogen
atmosphere. Infrared spectra were measured with a Nicolet Magna 750
FT-IR spectrometer in the range of 400–4000 cm–1 using the KBr pel-
lets. Powder X-ray diffraction (PXRD) analyses were recorded with a
Bruker AXS D8 advanced automated diffractometer with Cu-K radia-
α
tion.
A suspension of an aromatic aldehyde (1.0 mmol), trimethylsilyl cyan-
ide (TMSCN, 2.0 mmol) and catalyst (2.5 mol%, compounds 1 or 1a)
was placed in a Schlenk tube in an nitrogen atmosphere. Afterwards,
the mixture was stirred at 50 °C under solvent-free conditions until
disappearance of the aldehydes (0.25–4 h, checked by GC-MS). The
catalyst was removed by centrifugation and filtered quickly with ethyl
acetate. The conversion of aldehydes was determined by gas
chromatography (GC, Agilent 7890A) analysis.
2
.2 Synthesis of [Gd (bpt) (H O) ]·(DMF) (H O) (1)
2 2 2 2 2 2 6
A mixture of Gd
2
O
3
(0.05 mmol, 0.018 g), H
O (1 mL) and three drops of concentrated nitric acid
was sealed in a 20 mL glass vial. Subsequently, the mixture was heated
to 90 °C and kept at that temperature for 3 d. After cooling slowly to The anticancer activity of compounds 1, 1a, and the drug Vinorebine
room temperature, colorless block crystals were isolated with 45%
was evaluated against four human liver cancer cells (SMMC-7721,
yield based on Gd
22: calcd. C 36.92; H 3.79; N Bel-7402, MHCC97 and Hep3B) via the MTT assay. The two cancer
.39%; found: C 36.91; N 3.42; H 2.74%. IR (KBr): ν˜ = 3438 (w),
cell lines were seeded in a 96-well plate, in which the cells density is
5000 cells per test well, and cultured overnight at 37 °C in a 5% CO
3
bpt (0.2 mmol, 0.058 g),
DMF (4 mL), H
2
2.5 MTT Assay
2 3 2 2
O . C36H44Gd N O
2
2
1
978 (w), 1691 (s), 1624 (s), 1587 (s), 1476 (s), 1392 (s), 1276 (s),
221 (s), 1108 (m), 1061 (w), 942 (w), 845 (s), 782 (m), 716 (w), 672
2
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
(m), 578 (w) cm .
1
% FBS containing the compound 1 at various concentrations. After
2
.3 X-ray Crystallography
48 h, 10 μL 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 μL of DMSO. The absorbance was measured at
Single crystal X-ray crystal data of 1 was collected with a computer-
controlled Oxford Xcalibu E diffractometer with graphite-monochro-
mated Mo-K radiation (λ = 0.71073 Å) at room temperature. Absorp-
α
tion corrections were applied using SADABS. The structures were
solved by direct methods by the SHELXS-2014 package and refined
570 nm with a microplate reader. The percentage of cell inhibition was
determined using the formula, %inhibition = [mean OD of untreated
cells (control)/mean OD of treated cells (control)]ϫ100 and a graph
was plotted with the percentage of cell inhibition vs. concentration.
From this, the IC50 value was calculated.
2
by full-matrix least-square methods on F by using the SHELXL-2014/
6. All non-hydrogen atoms were refined anisotropically and all
hydrogen atoms were generated in their ideal locations. Crystallo-
graphic data and refinement details are summarized in Table 1. The Crystallographic data (excluding structure factors) for the structure in
selected bond lengths and angles for compound 1 are given in Table this paper have been deposited with the Cambridge Crystallographic
S1 (Supporting Information). The hydrogen bond details are listed in Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
the Table S2 (Supporting Information).
Copies of the data can be obtained free of charge on quoting the de-
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ARTICLE
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III
pository number CCDC-1876617 (Fax: +44-1223-336-033; E-Mail: the SHAPE software. The Gd –O bond lengths range from
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
2
.258(5) Å to 2.414(5) Å, which locate in the normal range
III
III
among the Gd –O bond lengths of the reported Gd -carb-
Supporting Information (see footnote on the first page of this article):
Additional structural figures, PXRD patterns, TGA curves, N2 sorption
isotherm, NMR data and the table for the selected bond lengths and
angles.
[9]
oxylate MOFs in the literature. Gd1 and Gd2 atoms are held
together by the carboxylic groups of the bpt3– ligand to afford
a dinuclear unit with the Gd1–Gd2 separation of 5.906(3) Å,
which is further extended into a 1D right-handed helical sec-
3–
ondary building unit chain via the bpt ligand along the b axis
3
Results and Discussion
3–
(Figure 1b). As for the bpt ligand, they reveal two different
coordination modes: one binds with five Gd ions using its three
3
.1 Crystal Structure of Compound 1
1
1
1
1
carboxylic groups showing the μ -η :η , μ -η :η , and
2
2
1
1
Compound 1 was synthesized by reaction of Gd O and μ -η :η fashion; the other one connects with six different Gd
2
3
1
H bpt in a mixed solvent of DMF and H O with the presence ions using its three carboxylic groups showing the same μ -
3
2
2
1
1
of HNO . It should be noted that only white deposition was η :η pattern. The connection of the 1D helical SBUs with the
obtained without the presence of HNO , indicating the HNO3 bpt ligands generates a porous three-dimensional framework
3
3
–
3
might act as a pH regulator which is very important for the with 1D rhombus channels running along the b axis. The win-
formation of the water soluble Gd3 ions in the reaction pro- dow size for the 1D channel is 11.3ϫ8.6 Å , which fills with
+
2
cess. Single crystal X-ray diffraction analysis revealed that water occupied open metal sites (Figure 1c).
compound 1 crystallizes in orthorhombic P2 2 2 space group
The coordination water molecule forms hydrogen bonding
1
1
and features a 3D framework based on the 1D helical chain interaction with the carboxylic O atom and the donor-acceptor
secondary building unit. The asymmetric unit of 1 is composed distance is 1.891 Å (O13–H13···O2, Figure S1, Supporting In-
III
3–
of two crystallographically independent Gd ion, two bpt
formation). With omitting the coordinated water molecules,
ligands, and two coordinated water molecules. As shown in PLATON analysis revealed that the 3D framework is com-
3
Figure 1a, both Gd1 and Gd2 atoms show the similar seven- posed of voids of 3928.8 Å , which represent 64.8% per unit
coordinated surroundings that are finished by seven O atoms cell volume. TOPOS software was used to simplify this frame-
(
eight carboxylic O atoms for Gd1, two water O atoms, and work. In this 3D framework, the two Gd ions could be treated
five carboxylic O atoms for Gd2).
as 5 and 6-connected node, and the one and two half bpt3–
III
The coordination arrangement of the two Gd ions could ligands could be considered as 5, 6 and 6-connected
be best described as a pentagonal bipyramid as calculated with nodes, so the whole framework of 1 could be viewed as a
Figure 1. (a) View of the coordination environments of GdIII ions in 1. (b) The 1D helical SBUs and the coordination modes of the organic
ligand. (c) The 3D framework of compound 1. (d) The schematic representation of the simplified topological network for compound 1.
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5
{
,5,6,6,6-connected net with
4 5.6 5}{4 8.6 7}{4 9.6 5.8}{4 9.6} (Figure 1d).
a
point symbol of 3.3 Catalytic Activity
∧
∧
∧
∧
∧
∧
∧
To evaluate the catalytic activity of compounds 1 and 1a,
we used the cyanosilylation of carbonyl compounds catalyzed
by Lewis acids as a test reaction (Scheme 1). The reaction of
carbonyls with trimethylsilyl cyanide (TMSCN) in the pres-
ence of a catalyst produces the corresponding cyanohydrin tri-
methylsilyl ethers, which are industrially valuable and impor-
tant intermediates. The cyanosilylation was carried out in the
presence of 1a with a 1:2 molar ratio of the selected carbonyls
and TMSCN at room temperature in a nitrogen atmosphere.
The conversions were calculated based on GC and the results
are summarized in Table 2. Using compound 1 as the catalyst,
the conversion of benzaldehyde and its derivatives can reach
above 58.85–78.57% in 2 h. Using 1a as the catalysts, the
conversion of benzaldehyde and its derivatives can reach
above 95–99% under the same conditions.
3
.2 PXRD and Thermogravimetric Analysis for Compound 1
The simulated and experimental PXRD patterns of 1 are
shown in Figure S2a (Supporting Information). Their peak po-
sitions are in good agreement with each other, indicating the
phase purity of the products. In addition, the thermal stability
of 1 was also analyzed on crystalline samples from 30–800 °C
in a nitrogen atmosphere (Figure S2b). The TGA curve of 1
shows that it experienced a three-step weight loss process. The
first weight loss of 9.18% (calcd. 9.24%) occurred in the tem-
perature range of 53–100 °C, which can be attributed to the
departure of the free water molecules. The second weight loss
of 15.32% (calcd. 15.57%) occurred in the temperature range
of 130–180 °C that corresponds to the loss of the coordinated
water and lattice DMF molecules. After taking off the solvent
molecules, the framework of 1 is stable up to 300 °C, which
was also confirmed by the powder X-ray diffraction of the
activated samples (Figure S2a). Upon heating above 300 °C,
the skeleton of 1 begins to collapse with the third weight loss.
The permanent porosity of the activated 1 (1a) was unam-
biguously established by its N sorption isotherm at 77 K. The
2
activated sample 1a was prepared by exchanging the solvent
and it was characterized by PXRD measurement, indicating
that the framework was maintained because the broadened
peaks positions remained (Figure S2a). The N2 adsorption
Scheme 1. The cyanosilylation reaction in the presence of selected
complexes.
The cyanosilylation yield of 1a is much higher than that of
study at 77 K of 1 reveals type I nitrogen adsorption isotherm many MOFs used for the cyanosilylation study under the sim-
3
–1
with the maximum uptake capacity of 316 cm ·g , suggesting ilar conditions, which might be ascribed to its large inner
that 1a mainly contain microporous cavities (Figure S3, Sup- spaces and high density of exposed metal sites.[
porting Information). The calculated Brunauer–Emmett–Teller worthy that the catalytic activity of 1a is higher than that of
BET) and Langmuir surface areas of 1a are 985 and compound 1. This can be attributed to more open metal sites
23–26]
It is note-
(
1
2
–1
3+
124 m ·g , respectively. Using the Horvath–Kawazoe (HK) of Gd in 1a, which can effective enhance the catalytic ac-
method on the N sorption isotherms, pore size distribution tivity. The stability of compound 1a was examined after the
2
was estimated, which reveals a pore size location of 8.6 Å, and catalytic study by PXRD, which reveals the same PXRD
thus is basically identical to the results from the single-crystal pattern as the as-synthesized phase, indicating that the com-
X-ray diffraction study.
pound was stable. In addition, the parallel experiment without
Table 2. The results for the catalytic cyanosilylation of aldehydes in the presence of 1 and 1a.
Aldehyde
Blank /% a)
1 conversion /% a)
1a conversion /% a)
1
1
1
2.36
6.59
3.22
76.13
99.32
78.57
69.15
58.85
99.58
99.47
95.43
1
6
0.36
.82
18.34
24.25
a) Conversion determined by GC; the NMR spectra for the products are shown in Figure S4 (Supporting Information).
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Table 3. Growth inhibitory effects on SMMC-7721, Bel-7402, MHCC97, and Hep3B cells.
Compound
IC50 /μM
SMMC-7721
Bel-7402
MHCC97
Hep3B
1
1
Ͼ100
25
Ͼ100
25
Ͼ100
35
Ͼ100
40
a
H
3
bpt
Gd(NO
Vinorebine
Ͼ100
Ͼ100
35
Ͼ100
Ͼ100
25
Ͼ100
Ͼ100
30
Ͼ100
Ͼ100
45
3 3 2
) ·6H O
catalyst was also done, the conversion of benzaldehyde and its 7721, Bel-7402, MHCC97, and Hep3B) and by MTT (3-(4,5-
derivative is below 20%. These results indicate that compound dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay
1a can be used as efficient catalysts for the cyanosilylation method. Compounds were dissolved in DMSO and blank sam-
reaction under mild conditions. To further explore whether the ples containing the same volume of DMSO were taken as con-
activation of the carbonyl species occurs inside the pores or trols to identify the activity of solvent in this cytotoxicity ex-
on the surface of the solid catalyst, substrates of increasing periment. The reference drug Vinorebine was used as a posi-
dimensions were tested, a significant size-selectivity effect is tive control to assess the cytotoxicity of the test compounds.
observed with catalyst, when the substrate was 1-naph- The results were analyzed by means of cell inhibition ex-
2
thaldehyde with dimensions 9.7ϫ8.4 Å , the conversion was pressed as IC50 values and they are summarized in Table 3. It
reduced to 24.25% for 1a.
is obvious that compound 1 is inactive against all of these cell
Based on the experimental results and previously reported lines (IC50 Ͼ 100 μM). At this concentration, it should exert
results, a plausible reaction mechanism is proposed to illustrate high cytotoxicity against these cells, so we concluded that it
the process of 1’ catalyzed cyanosilylation reaction.[23,24] The exerted no inhabitation selectivity towards these cell lines.
labile water molecules in the channels of compound 1 were However, after the tumor cells were incubated in the presence
removed by heating to expose the unsaturated metal sites pre- of compound 1a for 72 h, the IC50 value ranged from 25 to
viously. The aldehydes were activated by the coordinatively 40 μM, some of which were even lower than those of Vinoreb-
unsaturated central Ga atoms to react with TMSCN ine, indicating that compound 1a exhibited antitumor activity
(Scheme 2). The products were replaced by aldehydes, and the against all of these cell lines in different degrees. It is to be
catalysts were continued to activate the aldehydes in the next noted that the ligand and Gd(NO ) ·6H O did not show any
3
3
2
catalytic cycle.
significant activity on all the four cancer cells (IC50 = above
00–900 μM), which confirmed that the chelation of the ligand
7
III
with the open Gd sites is the only responsible factor for the
observed cytotoxic properties of complex 1a. The better cyto-
toxic activity of 1a than that of complex 1 may be attributed to
the extended planar structure induced by the π–π* conjugation
resulting from the removal of the coordinated water molecules
III
on the Gd sites, which make them interact with the DNA
more easily and finally leads to the cell death.
4
Conclusions
III
A new porous Gd -organic framework based on a Y-shaped
tricarboxylic ligand biphenyl-3,4Ј,5-tricarboxylic acid (H bpt)
3
was synthesized under solvothermal condition. Crystal struc-
ture analysis reveals that compound 1 is composed of 1D heli-
cal chain secondary building unit that connects by the bpt3–
ligands into a 3D framework with 1D nanosized channels. The
activated 1 could be used as a dual-functional material for ef-
fective cyanosilylation of aldehydes under solvent-free condi-
tions and inhibition of human cancer cell growth. These find-
ings clearly indicate that the MOFs may behave as multifunc-
tional materials by choosing suitable building blocks. The in-
formation obtained from our study would be helpful to under-
stand the mechanism of cyanosylation reaction in MOFs as
Scheme 2. Proposed mechanism for the cyanosilylation reaction of
carbonyl compounds catalyzed by 1a.
3.4 Antitumor Activity
III
well as the interactions of ligand bridged Gd complexes with
The interesting structural features and the obviously dif- DNA and should be useful in the development of better materi-
ferent of complexes 1 and 1a encouraged us to test their cyto- als for substrate-dependent cyanosylation reaction and new
toxicity against a panel of human liver cancer cells (SMMC- therapeutic agents for certain diseases.
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Keywords: dIII compound; Biphenyl-3,4Ј,5-tricarboxylic
acid; Solvothermal reaction; Cyanosilylation reaction;
Gadolinium; MTT assay
5
[
[
2
6
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