An anionic: Sod -type terbium-MOF with extra-large cavities for effective anthocyanin extraction and methyl viologen detection

Article abstract of DOI:10.1039/c8cc02193g

An anionic sod-type zeolitic metal-organic framework [(CH₃)₂NH₂]₉{Tb₆(η⁶-TATAT)₄(H₂O)₁₂}·3Cl·DMA·7H₂O [1, H₆TATAT = 5,5′,5′′-(1,3,5-tr

Full text of DOI:10.1039/c8cc02193g

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Bai, W. Du, Z.
Zhu, Z. Yang, S. Zhu, J. Xu, Z. Xie and J. Fang, Chem. Commun., 2018, DOI: 10.1039/C8CC02193G.
This is an Accepted Manuscript, which has been through the
Volume 52 Number
1 4 January 2016 Pages 1–216
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Accepted Manuscripts are published online shortly after
Chemical Communications
www.rsc.org/chemcomm
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

Please do not adjust margins
ChemComm
Page 1 of 4
View Article Online
DOI: 10.1039/C8CC02193G
Journal Name
COMMUNICATION
Anionic sod-type Terbium-MOF with Extra-Large Cavities for
Effective Anthocyanin Extraction and Methyl Viologen Detection
Wei Du,a Zhifeng Zhu,a YueꢀLing Bai,*a,b Zhen Yang,a Shourong Zhu,a Jiaqiang Xu,*a Zhaoxiong
Xie,b and Jianhui Fanga
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
extraction, supercritical fluid extraction and macroporous adsorption
resin separation methods.12 The selective adsorption and separation by
anionic MOFs has never been used in this field.
An anionic sodꢀtype zeolitic metalꢀorganic framework
[(CH3)2NH2]9{Tb6(η6ꢀTATAT)4(H2O)12}·3Cl·DMA·7H2O
[1,
5,5',5"ꢀ(1,3,5ꢀtriazineꢀ2,4,6ꢀtriyltriimino)triꢀ1,3ꢀ
H6TATAT
=
Anthocyanins (ACNs), are a class of flavonoids, have a strong
antiꢀfree radical and antioxidant effects. Early studies have shown
that anthocyanins are the most effective antioxidants and the
strongest free radical scavengers found in natural fruits, and its antiꢀ
oxidant effect is up to 50 times that of Vitamin E (VE) and 20 times
that of Vitamin C (VC).13,14 Therefore, ACNs can be widely used in
health products, antiꢀaging cosmetics, as well as antiꢀtumor and antiꢀ
mutation drugs.15,16 In addition, anthocyanin is a kind of waterꢀ
soluble pigment, which can change color with the change of acidity
and alkalinity of aqueous solution, and exists in the neutral and
anionic state of quinone ketone in neutral and basic conditions,
respectively, under acidic condition, it can convert into the cationic
form of the mother nucleus of anthocyanin (Fig. S13).17,18 This is
conducive to change the existing form by adjusting the pH of the
solution, to achieve the purpose of separation and extraction by ionic
MOFs.
benzenedicarboxylic acid] has been synthesized by metalꢀligand
directed assembly of hexacarboxylic acid units and Tb3+ ions.
Compound 1 with extraꢀlarge cavities enables it to efficiently
extract the natural product anthocyanins from the blackberries
and can be released rapidly in NaCl aqueous solution. And, the
nature of anionic framework makes it very sensitive to detect the
cationic methyl viologen (MV2+) with a detection limit as low as 1
× 10ꢀ8 M.
Zeoliteꢀlike metalꢀorganic frameworks (ZMOFs) are a class of very
important microporous solidꢀstate crystalline materials, which have
always received considerable attention due to their notable commercial
significance and potential applications in gas storage, ion exchange,
catalysis, luminescence, sensing and detection of target molecules.1–3 As
an important branch of ZMOFs, the sodalite (sod) framework has
attracted increasing interest owing to its extraꢀlarge cavities, excellent
thermal and chemical stability, which allows it to maintain its structural
integrity in water (not common in MOFs)4 and to have high ion
exchange and adsorption capacities.5,6 So far, most of the research work
is focused on the neutral MOFs, and ionic MOFs are rarely noticed. In
fact, ionic MOFs have more unique advantages, such as selective
adsorption and identification of cationic or anionic molecules by hostꢀ
guest electronic interactions and/or guestꢀguest exchange interactions.7,8
Therefore, some ionic MOFs, especially the anionic MOFs, have
attracted the interest of researchers in recent years because the anionic
frameworks can effectively remove heavy metal ions and organic
cationic dyes in wastewater, and have very important practical value.9,10
Many natural products also exist in the form of cations, nonꢀtoxic and
harmless, and have important food value and medicinal value.11,12 At
present, most of the natural products are extracted by accelerated solvent
Herein, we use one predesigned hexacarboxylic acid ligand reaction
with Tb3+ ions to synthesize a sodꢀtype ZMOF with formula of
[(CH3)2NH2]9{Tb6(η6ꢀTATAT)4(H2O)12}·3Cl·DMA·7H2O.
This
compound is an anionic framework and has extraꢀlarge cavities of
2.52 nm. Currently, only four examples of anionic sodꢀtype ZMOF has
been reported.19–22 The result of natural product extraction showed that
the anionic framework 1 can effectively extract anthocyanin from
blackberries (BB) under acidic condition by guestꢀguest molecules
exchange, and its saturated adsorption capacity can reach as high as
417.5 mg / g. In addition, Tb3+ ions have unique green fluorescence, so
compound 1 could be used to sense some small molecules, especially
sensing cations. Methyl viologen (N,N′ꢀdimethylꢀ4,4′ꢀbipyridinium
dication, MV2+) as a herbicide has been widely used in modern
agriculture, which can cause serious food safety and environmental
pollution because of its high toxicity, nonꢀdegradation and no
effective antidote.23,24 So, detecting and removing it is particularly
important for human health. Anionic framework 1 can rapidly
adsorbs it in aqueous solution and shows a dramatic fluorescence
quenching effect with a detection limit as low as 1 × 10ꢀ8 M. Earlier
Choi et al. had reported that a polymer of PFBIꢀSO3ꢀ can effectively
detect MV2+, but its detection limit can only reach 1 × 10ꢀ5 M.25
aDepartment of Chemistry, Drug of Center, College of Science, Shanghai University,
Shanghai 200444, China. E-mail: yuelingbai@shu.edu.cn
bState Key Laboratory for Physical Chemistry of Solid Surfaces and Department of
Chemistry, College of Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, China.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 4
View Article Online
DOI: 10.1039/C8CC02193G
COMMUNICATION
Journal Name
Compound 1 was obtained from DMA/H2O mixed solution body centered cubic arrangement of truncated octahedron (TꢀOh)
containing H6TATAT, Tb(NO3)3·6H2O and trace amount of composed of eight TATAT6ꢀ ligands with cages diameter of 2.52 nm
concentrated nitric acid at 130 °C. The crystal structure of 1 was (Fig. 1), and edge expansion of truncated octahedrons results in a
determined by Singleꢀcrystal Xꢀray diffraction. The compound 1 very open 3D structure with extraꢀlarge cavities (31.0 × 31.0 × 31.0 Å)
crystallizes in the cubic space group Fm-3c with large volume of occupied by guest Clꢀ ions, disordered dimethylamine cations, DMA
165284.72 Å3. The framework of 1 is anionic which is balanced by and water molecules. The total accessible volume is 76.5% for 1
protonated [(CH3)2NH2]+ originating from the decomposition of calculated by the PLATON26 after removing all of the guest
DMA during the reaction. In the asymmetric unit, there exists 1/2 molecules from the cages.
Tb3+, 1/3 TATAT6ꢀ, one coordinated water and 1/4 Clꢀ guest
The powder Xꢀray diffraction (PXRD) pattern of the asꢀ
molecule. Tb3+ ion is coordinated to two water molecules and six synthesized compound matched well with the simulated one,
carboxyl oxygen atoms from four individual TATAT6ꢀ ligands to indicating that the polycrystalline sample is pure phase (Fig. S4).
form a slightly distorted TbO8 hendecahedron geometry, which can And the crystals of compound 1 are stable and insoluble in water and
be regarded as a Tb(O2C)4 unit (Fig. 1), while each independent common organic solvents (Fig. S5). In order to investigate the
TATAT6ꢀ ligand can link six Tb3+ ions by six carboxyl groups stabilities of their cages, the samples were activated by solventꢀ
through monodentate and bidentate chelating coordination modes, exchange with water and ethanol, respectively. The thermal
respectively. If the Tb(O2C)4 unit and the ligand are assumed to be gravimetric analysis of asꢀsynthesized, ethanol activated and water
fourꢀconnected and sixꢀconnected node, an extended threeꢀ soaked
1 were investigated under a nitrogen atmosphere,
dimensional (3D) framework formed through 4 + 6 assembly respectively. The curve of asꢀsynthesized 1 shows a gradual weight
strategy (Fig. 1). To date, most of the sodꢀZMOF networks reported loss process; no obvious platforms appeared in the range of
are obtained by the 2 + 4 or 4 + 4 synthetic strategies, whereas the 4 25~800 °C. While the waterꢀsoaked sample of 1 exhibits a rapid
+ 6 strategy is relatively rare, in fact, the 4 + 6 synthetic strategy weight loss process of 22.16
makes it easier to obtain a framework with extraꢀlarge cavities.
% between 25 and 140 °C,
corresponding to the removal of all protonated dimethylamine, Clꢀ
Further analysis of the topology of 1 shows three kinds of ions, guest solvent molecules and coordinated water (ca. 21.83%).
windows in the structure: a large closed hexagonal window formed An obvious plateau appears and the framework is stable to ~480 °C,
by one ligand and six {Tb(O2C)4} units with a size of ca. 19.4 × 19.4 then the frameworks begin to decompose rapidly. The curve of
Å; two small open rectangle window constructed by four {Tb(O2C)4} ethanolꢀactivated 1 is similar to the waterꢀsoaked sample and the
units and four ligands with sizes of ca.11.6 × 11.6 Å and 7.8 × 7.8 Å, framework can be also stable to ~480 °C (Fig. S7). This result
respectively, the edge of relatively larger rectangle is formed by two indicates the anionic frameworks of waterꢀsoaked and ethanolꢀ
carboxyl groups on two adjacent benzene ring from one ligand activated 1 can remain intact and have an excellent thermal stability.
connecting two Tb3+ ions, while two carboxyl groups on the same Unfortunately, the BET surface area failed to be calculated through
benzene ring from a ligand coordinated to two Tb3+ ions form the the N2 adsorption/desorption experiments, presumably because the
edge of the smaller rectangle (Fig. S3). This anionic sodꢀZMOF is a
cages were blocked by the free [(CH3)2NH2]+ cations and/or the
extraꢀlarge cavities in the frameworks lost their longꢀrange order
under high vacuum activation.27
To explore the accessibility of porosity of this anionic framework,
the cationic anthocyanin adsorption and release were investigated.
Cyanidin chloride (Cy·Cl) was chose as a model for experiments.
The asꢀsynthesized 1 (10 mg) was immersed in ethanol solution
containing Cy·Cl (8.0 mg/L) at room temperature. The adsorption
behavior of 1 toward Cy·Cl were recorded by UVꢀVis spectra as
shown in Fig. 2a. The decolorization rate can reach 50 % at 6 h, up
to 91% after 84 hours. The results reveal that 1 can adsorb cationic
Cy+ molecules into the cages by the guestꢀguest molecules exchange
of free [(CH3)2NH2]+ cations with Cy+ molecules.28 In general, the
adsorption capacity is closely related to the concentration of
solutions and increases with the increased concentration. An uptake
capacity of 373.4 mg / g was achieved at room temperature in 12 h
when adding 10 mg compound 1 into the 10 mL Cy·Cl solution (8.0
g/L). Considering its possible potential application for extraction of
natural product anthocyanins from the fruits, the Cy+ release from
dye Cy@1 was investigated and recorded by UVꢀVis spectra. As
shown in Fig. 2b, the Cy+ ions could release quickly in NaCl
aqueous/ethanol solution and reach a plateau within 60 min, and the
release percent is 67.69 % for Cy+ after 120 min. While the Cy+
molecules are barely released in the deionized water, revealing that
Na+ could effectively facilitate the release of Cy+ ions by ions
exchange. Compared to Cy+ adsorption rate, the release rate is
significantly faster, indicating Na+ ions are easier to enter cages by
ions exchange because of its smaller size. The high adsorption
Fig. 1 The coordination environment of Tb3+ ion and the coordination model of
TATAT6ꢀ ligand. The threeꢀdimensional structure of compound 1 and its anionic
sodꢀtype topology. Free guest molecules, water molecules and H atoms have
been omitted for clarify. Colour code: Tb, cyan; O, red; N, blue; C gray.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 3 of 4
View Article Online
DOI: 10.1039/C8CC02193G
Journal Name
COMMUNICATION
Fig. 2 (a) Time dependent UVꢀvis spectra of 8.0 mg/L cyanidin chloride
ethanol solution with 10 mg compound 1. (b) Time dependent UVꢀvis spectra
of 10 mg Cy+@1 in 10 mL water and NaCl aqueous/ethanol mixed solution,
respectively.
capacity and rapid release rate led us to continue to explore its
possible practical application in the extraction of natural product
anthocyanins (ACNs). ACNs are widely found in many common fruits,
flowers and vegetables and they are usually linked to one or more
glucose, galactose, rhamnose, xylose and glycosides in the form of
anthocyanin aglycone, of which cyanidinꢀ3ꢀglucoside (C3G) is the most
widely distributed and the most common in berries. Natural
Fig. 3 (a) Time dependent UVꢀvis spectra of 2 mL blackberry (BB) aqueous
solution with 10 mg compound 1. Inset: the color change of blackberries
solution at different pH. (b) The ESIꢀMS spectrum for the filtrate of the
natural anthocyanin release in NaCl aqueous solution. The simulated isotopic
anthocyanins have a typical characteristic, that is, the color of distributions of m/z = 88.1 for DMAꢀH+ and 472.2 for C3GꢀNa+, respectively.
anthocyanin aqueous solution will change with the pH changes and
accompanied by changes in state of the anthocyanins (Fig. S8 and 13).
performed with Materials Studio 7.0. The adsorption distribution
trend displays C3G+ ions are mainly adsorbed in the cavities, while
Na+ ions can be adsorbed in the cavities and on the surface of
compound 1 due to its small molecular size and high charge density
(Fig. S14ꢀ15). The energy distribution of 1 to adsorb C3G+ is in the
range of ꢀ260 ~ ꢀ150 kJ /mol and that is ꢀ1500 ~ ꢀ500 kJ /mol for
Na+ (Fig. S16), which indicates that the hostꢀguest electronic
interactions between the anionic framework 1 and Na+ ions is
stronger than that of C3G+ with 1, so Na+ ions can easily exchange
with C3G+ ions in release experiments. The results of the recycling
experiment show that the first two cycles of C3G+ can be well
adsorbed by the exchange of Na+ ions, but with the number of cycles
increasing, the exchange rate of C3G+ with Na+ ions gradually
decreases due to the strong hostꢀguest interaction between Na+ ions
and the framework, resulting in a gradual decrease of the adsorption
rate of C3G+ ions (Fig. S19). But anyway, this result shows that
compound 1 can effectively extract cationic anthocyanin from
natural products and the extracted product is very pure, indicating
that the anionic framework of 1 has a good potential application in
extracting cationic natural products. Furthermore, it is a very
effective and economically competitive extraction approach because
its method is simple and does not require expensive separation and
purification equipment, which should be developed into a new
technology for extracting natural products. It also opens up a novel
and attractive potential application for MOFs, which has never been
reported in previous studies about MOFs.
Blackberry is known as the "king of anthocyanins." Here, we use
blackberries as the sample to extract natural anthocyanins. A light
purple solution was obtained after soaking 0.5 g blackberries in
water for an hour, filtrated this solution and divided it into multiple
portions, and then adjust pH to 3, 5, 7, 8, 9 and 11, respectively, the
results show that the solution in different pH values show different
colors, pink in acidic condition and blue in alkaline condition,
indicating that natural anthocyanins in blackberries dissolved in
water (Fig. 3a, inset). In order to study the effect of anionic
framework 1 on the extraction of natural anthocyanins, 2 mL of the
filtrate was used and its pH was adjusted to about 5 with dilute
hydrochloric acid, making the anthocyanin presented in a cationic
state, the adsorption behaviors of 1 toward natural anthocyanin were
recorded by UVꢀVis spectra. As shown in Fig. 3a, the maximum
absorption peak of natural anthocyanins solution appears at 527 nm,
which is consistent with the theoretical value (500ꢀ550 nm). With the
increase of time, the absorbance decreased rapidly, and the crystal color
gradually deepened, indicating the compound 1 could rapidly adsorb the
cationic natural anthocyanins, and the adsorption rate in 24 hours can
reach as high as 94%. The maximum adsorption capacity is 417.5 mg
/ g, which was estimated by adding 10 mg compound 1 into 10 mL
saturated blackberries solution for 12 h at room temperature. This
high adsorption capacity and rapid adsorption behavior maybe result
from the effect of extraꢀlarge cavities and guest–guest ions exchange
in water solution. In order to investigate which type of anthocyanin
is adsorbed by compound 1, a release experiment was performed and
characterized by electrospray ionization mass spectrometry (ESIꢀ
MS). The release experiment was also performed in NaCl aqueous
solution. As shown in Fig. 3b, the two main ion peaks of the release
solution were observed at m/z = 88.1 and 472.2, respectively. The
peak of 88.1 corresponds to DMAꢀH+ solvent molecule in the
cationic mode of the ESI source, while another ion peak with a
weight 472.2 could be attributed to C3GꢀNa+. It should be noted that
the C3G cations were exchanged by the Na+ ions, which is
converted to a neutral state in a neutral aqueous solution. The
mechanisms of adsorption and exchange for Na+ and C3G+ ions are
Considering the strong fluorescence of Tb3+ ions and the anionic
nature of the framework, compound 1 should be more sensitive to
detect and sense some cations. MV2+ cation is a wellꢀknown electron
deficient, making it easily convert to colored cationic radicals (MV+·)
via the photoinduced electron transfer to quench fluorescence.29–31
Coupled with the strong toxicity and wide use in agriculture, simple and
quick detection and removal of MV2+ cations are of great importance
to food safety and the environment. Here, toxic MV2+ detective
experiments were studied to extend the application of 1. 10 mg
compound 1 was immersed into 10 mL MV2+ aqueous solution (8.0
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 4
View Article Online
DOI: 10.1039/C8CC02193G
COMMUNICATION
Journal Name
mg/L). The color of crystals 1 turned to yellow immediately and
transformed into a bright orange after 2 min, suggesting that the
anion framework 1 rapidly adsorbed MV2+ cations and optical
charge transfer led to the conversion of MV2+ to colored
MV+· cationic radical. The brilliant green fluorescence of 1 is
completely quenched after adsorbing methyl viologen under 365 nm
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
2
3
Q. Yang, Q. Xu and H.ꢀL. Jiang, Chem. Soc. Rev., 2017, 46, 4774–4808.
H. Zhang, J. Nai, L. Yu and X. W. (David) Lou, Joule, 2017, 1, 77–107.
W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and S. K.
Ghosh, Chem. Soc. Rev., 2017, 46, 3242–3285.
4
5
6
M. Eddaoudi, D. F. Sava, J. F. Eubank, K. Adil and V. Guillerm, Chem.
Soc. Rev., 2015, 44, 228–249.
B. Demir and M. G. Ahunbay, J. Phys. Chem. C, 2013, 117, 15647–
15658.
J.ꢀS. Qin, D.ꢀY. Du, W.ꢀL. Li, J.ꢀP. Zhang, S.ꢀL. Li, Z.ꢀM. Su, X.ꢀL.
Wang, Q. Xu, K.ꢀZ. Shao and Y.ꢀQ. Lan, Chem. Sci., 2012, 3, 2114.
Y. Han, S. Zhang, N. Shen, D. Li and X. Li, Mater. Lett., 2017, 188, 1–4.
A. V. Desai, B. Manna, A. Karmakar, A. Sahu and S. K. Ghosh, Angew.
Chemie Int. Ed., 2016, 55, 7811–7815.
7
8
9
X. S. Wang, J. Liang, L. Li, Z. J. Lin, P. P. Bag, S. Y. Gao, Y. B. Huang
and R. Cao, Inorg. Chem., 2016, 55, 2641–2649.
Fig. 4 The solidꢀstate emission spectra of the compound 1 and soaked
samples 1 in different concentrations of MV2+ aqueous solution, respectively.
10 P. Kumar, A. Pournara, K.ꢀH. Kim, V. Bansal, S. Rapti and M. J. Manos,
Prog. Mater. Sci., 2017, 86, 25–74.
11 S. Galadari, A. Rahman, S. Pallichankandy and F. Thayyullathil,
Phytomedicine, 2017, 34, 143–153.
12 S. Silva, E. M. Costa, C. Calhau, R. M. Morais and M. E. Pintado, Crit.
Rev. Food Sci. Nutr., 2017, 57, 3072–3083.
13 J. Paes, R. Dotta, G. F. Barbero and J. Martínez, J. Supercrit. Fluids,
2014, 95, 8–16.
14 S. Norberto, S. Silva, M. Meireles, A. Faria, M. Pintado and C. Calhau,
J. Funct. Foods, 2013, 5, 1518–1528.
UV light (Fig. S21). The quencherꢀconcentration dependence of the
fluorescence spectra of compound 1 were shown in Fig. 4. The asꢀ
synthesized 1 (20 mg) were soaked in 10 mL aqueous solutions
containing MV2+ with different concentrations (1 × 10ꢀ2, 10ꢀ3, 10ꢀ4,
10ꢀ5, 10ꢀ6, 10ꢀ7, 10ꢀ8 M) at room temperature for 10 min, respectively.
The solidꢀstate spectrum of compound 1 displayed strong emission
peaks at 489, 544, 583 and 621 nm under 346 nm excitation
wavelength, corresponding to the characteristic fluorescence peaks
of Tb3+ ion of 5D4→7FJ (J = 6 ~ 3) transitions. The noticeable
fluorescence quenching effect was found for the sample soaked in 1
× 10ꢀ8 M MV2+ aqueous solution, when the concentration of MV2+
was increased to 1 × 10ꢀ7 M, the fluorescence of soaked sample 1
was almost quenched completely. The powder Xꢀray diffraction
(PXRD) results of soaked sample can still keep the original
diffraction peaks unchanged (Fig. S22), indicating that 1 can keep its
framework intact after soaking in MV2+ solution. To our knowledge,
this is the most sensitive MOF reported for the detection of highly
toxic MV2+. The fast adsorption and coloration, and strong
fluorescence quenching effect make compound 1 a very sensitive
MV2+ sensor, which is extremely important for food safety and
environmental protection.
15 D. Hou, Curr. Mol. Med., 2003, 149–159.
16 M. Ding, R. Feng, S. Y. Wang, L. Bowman, Y. Lu, Y. Qian, V.
Castranova, B. H. Jiang and X. Shi, J. Biol. Chem., 2006, 281, 17359–
17368.
17 L. Cabrita, T. Fossen and Ø. M. Andersen, Food Chem., 2000, 68, 101–
107.
18 K. Torskangerpoll and Ø. M. Andersen, Food Chem., 2005, 89, 427–
440.
19 C. Kutzscher, D. JanssenꢀMüller, A. Notzon, U. Stoeck, V. Bon, I.
Senkovska, S. Kaskel, F. Glorius, O. M. Yaghi, A. McCoy, S. J.
McNicholas, G. N. Murshudov, N. S. Pannu, E. A. Potterton, H. R.
Powell, R. J. Read, A. Vagin and K. S. Wilson, CrystEngComm, 2017,
19, 2494–2499.
20 L. Sun, H. Xing, Z. Liang, J. Yu and R. Xu, Chem. Commun., 2013, 49,
11155.
21 D. F. Sava, V. C. Kravtsov, F. Nouar, L. Wojtas, J. F. Eubank and M.
Eddaoudi, J. Am. Chem. Soc., 2008, 130, 3768–3770.
22 Y. Liu, V. C. Kravtsov, R. Larsen and M. Eddaoudi, Chem. Commun.,
2006, 1488.
In summary, an anionic zeolitic MOF with sod topology has
been obtained through 4 + 6 strategy. This MOF presents extraꢀ
large cavities with a size of ca. 31.0 × 31.0 × 31.0 Å based on
fourꢀconnected {Tb(O2C)4} units and sixꢀconnected TATAT6ꢀ
ligands. The nature of the anionic framework allows compound
23 Y.ꢀY. Jia, Y.ꢀH. Zhang, J. Xu, R. Feng, M.ꢀS. Zhang and X.ꢀH. Bu,
Chem. Commun., 2015, 51, 17439–17442.
24 R. Betarbet, T. B. Sherer, G. Mackenzie, M. Garciaꢀosuna, A. V Panov
and J. T. Greenamyre, Nat. Neurosci., 2000, 3, 1301–1306.
25 H. W. Choi, Y. S. Kim, N. C. Yang and D. H. Suh, J. Appl. Polym. Sci.,
2004, 91, 900–904.
1
to rapidly and efficiently extract natural anthocyanins C3G
26 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7–13.
by guestꢀguest molecule exchange, indicating that
potential candidate for extracting cationic natural products with
notable economically competitive and fairly simple process. In
1
is a good 27 M. J. Dong, M. Zhao, S. Ou, C. Zou and C. De Wu, Angew. Chemie Int.
Ed., 2014, 53, 1575–1579.
28 Z. Zhu, Y.ꢀL. Bai, L. Zhang, D. Sun, J. Fang and S. Zhu, Chem.
Commun., 2014, 50, 14674–14677.
29 E. L. Clennan, Coord. Chem. Rev., 2004, 248, 477–492.
30 W. Shi, F. Xing, Y.ꢀL. Bai, M. Hu, Y. Zhao, M.ꢀX. Li and S. Zhu, ACS
Appl. Mater. Interfaces, 2015, 7, 14493–14500.
addition, the solidꢀstate emission experiments exhibit that
1 is a
sensitive chemical sensor which can detective the highly toxic
dication MV2+ at extremely low concentration of 1 × 10ꢀ8 M.
This work was supported by the National Natural Science
Foundation of China (21571126 and 21401127) and supported
by Shanghai Key Laboratory of High Temperature
Superconductors (No. 14DZ2260700).
31 M. Hu, F. Xing, Y. Zhao, Y.ꢀL. Bai, M.ꢀX. Li and S. Zhu, ACS Omega,
2017, 2, 1128–1133.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins