Size, Shape and Porosity Control of Medi-MOF-1 via Growth

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Size, Shape and Porosity Control of Medi-MOF-1 via Growth Modulation under Microwave Heating Xiaodong Feng, Faheem Muhammad, Fuxing Sun, Yuyang Tian, and Guangshan Zhu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01442 • Publication Date (Web): 12 Dec 2018 Downloaded from http://pubs.acs.org on December 20, 2018

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Crystal Growth & Design

Size, Shape and Porosity Control of Medi-MOF-1 via Growth Modulation under Microwave Heating Xiaodong Feng,† Faheem Muhammad,† Fuxing Sun,‡ Yuyang Tian,*,† and Guangshan Zhu,†

† Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China ‡ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

KEYWORDS: Nanosized metal-organic frameworks, Growth modulation, Microwave method.

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ABSTRACT: It has been widely recognized that nanosized metal-organic frameworks (nanoMOFs) possess prominent advantages over bulky MOFs in both chemical and physical aspects, while the synthesis of nano-MOFs with well-tuned crystal sizes and shapes still remain a challenge. Herein, with the aid of microwave heating and growth modulation, we successfully synthesized the nanosized counterpart of medi-MOF-1. Cubic-shaped, nanosized medi-MOF-1 with the length of 200 nm has been achieved by adding a certain amount of capping ligands which cause the competitive coordination interactions during the crystal growth process. It is found that the crystal sizes and morphology were controlled by changing the concentration of the capping ligand. Furthermore, hierarchical porosity was introduced to nanosized medi-MOF-1 due to the existence of defects. It is believed that the nanosized counterpart of medi-MOF-1 would have remarkable potential applications in gas storage as well as the medical and pharmaceutical fields.

INTRODUCTION Metal−organic frameworks (MOFs) are assembled by ordered interconnections of inorganic nodes with rigid multi-topic organic linkers [1]. Due to their crystalline and intrinsic porous structures, MOFs possess high surface areas and unique pore-size distribution [2, 3]. Therefore, they are widely applied in the areas of gas storage, separation, sensing, catalysis and biomedical applications [4-7]. Furthermore, the structures and properties of MOFs can be deliberately fabricated and tuned by the different combination of inorganic metal ions/clusters and organic linkers. They are rapidly emerged as important multifunctional materials over the past decades for the applications of optical, electronic and magnetic devices [8-10]. Recently, MOFs have attracted wide attention as advanced materials for biomedicine to achieve the purpose of intravenous drug delivery, drug release and imaging agents, thanks to their high absorption


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capacity, active sites that binding targeting molecules and optical properties [11-15]. Regards to all the biomedical applications, bulky MOFs were restricted due to the rejection of the largesized species of the body's immune system. Therefore, synthesis of nanosized MOFs (nanoMOFs) is highly demanded for biomedical applications. Moreover, the nano-MOFs with an ideal size range have become new burgeoning materials which offered significant altered properties and reactivity compared with traditional bulky porous MOFs. Nanoscale counterparts not only have the advantages of MOFs in catalysis and sensor but also have plenty of prominent chemical and physical properties that could be applied in drug delivery and NMR imaging [15-18] etc. The nano-MOFs have elevated external surface, thus diminish the mass transfer limits and increase the activity of catalysts as well as the response time in sensor applications. In addition, the nanoMOFs have been demonstrated to exhibit increased plasma circulation times and can even be transported to the lymphatic system [19]. Researches on nano-MOFs as delivery vehicles, imaging contrast agents, molecular therapeutics and other chemotherapeutics have been widely reported. For example, He et al. have demonstrated the use of nano-MOFs for the delivery of cisplatin to enhance therapeutic efficacy by silencing multiple drug-resistant genes.[20] Zhuang et al. have developed ZIF-8 nanospheres incorporated with fluorescein dye and the anticancer drug camptothecin for drug delivery [21]. Tamames-Tabar et al. investigated the cytotoxicity of fourteen nanoscaled MOFs with different compositions in different cell lines [22]. Cunha et al. prepared porous biocompatible MOFs for caffeine delivery [23]. Indeed, an emerging field for drug delivery is highlighted that miniaturizing and controlling the crystal size and morphology of MOFs are key features to strengthen their contribution to the developing subject. Besides the size control, another concern on MOFs for biomedical application is the biocompatibility, biodegradability and toxicity. Many metals and ligands of MOFs are toxic and


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unavailable for clinical management. As medical materials, the components of MOFs and their metabolite should be biologically friendly. Therefore, chemists have devoted to developing biomolecules as linkers of biologically active MOFs for biological applications. Increasing the number of natural molecules such as amino acids, peptides, nucleobases, and carbohydrates were applied in forming extended porous coordination frameworks [24-27]. In 2012, our group reported the synthesis of a biocompatible MOF, medi-MOF-1 from the combination of curcumin [28], which is a natural extract from turmeric, zedoariae, mustard, curry and other plant rhizomas [29-30] as ligand and the less toxic zinc as a metal node. Zinc is a light metal and is widely recognized biologically acceptable. Meanwhile, curcumin is a natural phenolic antioxidant with a variety of pharmacological functions such as cholagogue, anti-infection, anti-virus, antibacterial, anticancer, anti-HIV, anticoagulant blood and atherosclerosis and so on [31-34]. For the first time, we introduced a functional natural extract to MOF structures. However, many efforts have been applied to synthesize the nanosized medi-MOF-1, but until now, no successful preparation of nanosized medi-MOF-1 has been reported.

Several approaches have been applied for the synthesis of nano-MOFs, including water-in-oil microemulsions, surfactant mediated hydrothermal syntheses, microwave-assisted, and modulation method, etc. [35-39]. However, the precise control over the size and shape still remains a huge challenge to be achieved. Herein, we reported the synthesis of medi-MOF-1 with the size of 200 nm through a combined route of microwave heating and modulation method. The results showed the size and shape were obviously changed with the modified synthetic procedure. Cubic-shaped, nanosized medi-MOF-1 with the length of 200 nm has been achieved. Notably, a hierarchical morphology caused by defects was observed, which would be potentially


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applied for diverse functions. The synthetic route reported in this work provides an efficient way to control the sizes, shapes and porosity of MOF materials.

EXPERIMENTAL SECTION Materials: Curcumin (Sinopharm Chemical reagent Co.Ltd, AR), Zinc acetate dihydrate (Zn(OAc)2·2H2O, AR), N,N’-dimethylformamide (Tianjin Tiantai Chemical Research Institute, AR), and absolute ethanol (Beijing Chemical Company, AR) were used as received without any further purification. 2-Methoxy-4-methylphenol (L1, Aladdin, >98.0%, GC), 4-Ethylguaiacol (L2, Aladdin, 99.0%), Isoeugenol (L3, Aladdin, >97.0%) were chosen as the capping ligands. Synthesis of medi-MOF-1 by microwave heating: Curcumin (30 mg, 0.0815 mmol) and Zn(OAc)2·2H2O (10 mg, 0.045 mmol) was dissolved in the mixture of N,N’-dimethylformamide (4.0 mL) and absolute ethanol (1.0 mL). Then the reaction mixtures were sealed and placed in microwave reactors and heated to 100°C, 13°C, 150°C and 180°C within 5 min respectively. The reactions were kept at different temperatures for 5 min and the resulting solids were obtained. For other batches of the reaction, the same mixtures were kept at the temperature of 130°C and extended the reaction time for 5 min, 6 min, 7 min and 10 min, respectively. The resulting solids were obtained. All the products were centrifuged and washed with DMF for several times and dried by a vacuum pump. Synthesis of nanosized medi-MOF-1 by microwave heating and modulation: A typical synthetic procedure for nanosized medi-MOF-1 was dissolving curcumin (30 mg, 0.0815 mmol) and Zn(OAc)2·2H2O (10 mg, 0.045 mmol) in the mixture of N,N’-dimethylformamide (4.0 mL) and absolute ethanol (1.0 mL). A certain amount of L1 (225 mg, 1.629 mmol) was added into the solution and stirred at room temperature. Finally the reaction mixture was sealed and placed into


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a microwave reactor and heated to 130°C within 5 min. Then the reaction was kept at this temperature for another 5 min. The resulting solid was centrifuged and washed with DMF for several times to remove the excess ligands and then dried under vacuum. RESULTS AND DISCUSSION Microwave-assisted synthesis is widely recognized as an efficient method to achieve the formation of nanosized crystals. This is because that the microwave causes the movement of polar molecules directly and thus accelerates the heating process and nucleation. Therefore, we tried to conduct the synthesis of nanosized medi-MOF-1 under microwave heating. Different reaction temperature of 100°C, 130°C, 150°C and 180°C was executed respectively under microwave for 5 min to examine the effect of heating temperature. Powder X-ray diffraction (PXRD) confirmed that all the samples were crystalline medi-MOF-1 (Fig. 1) except the products synthesized at 180°C, which is amorphous as indicated in Fig. S1. In order to study the microwave heating effects to the growth of medi-MOF-1, Scanning Electron Microscope (SEM) was conducted. As it can be seen from the SEM images in Fig. 2, with the increase of the temperature from 100 -150°C, the size of the particles reduced from tens of micrometers by conventional heating (Fig. S2) to about 3-5 μm by microwave heating. The crystals obtained at different temperatures by microwave heating did not show obvious differences in sizes and shapes. When the temperature increased to 180°C, the particle sized is less than 1μm but the PXRD indicates it is less crystalline or amorphous. Meanwhile, when the temperature was kept at 130°C and the reaction time was extended (Fig. 2e to 2h), it is observed that the size of the particles getting bigger. Based on the experiment results above, we can come to the conclusion to the synthesis of medi-MOF-1 under microwave heating: temperature has little effect on the size and shape of particles and the reaction time strongly influences the particle sizes. However,


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although the microwave synthesis could reduce the size of the particles, the sizes of the crystals obtained under microwave are still at the scale of micrometers which can not satisfy the requirement for biological applications.

Figure 1. The PXRD patterns for representative samples obtained by microwave synthesis: (a, e): simulated pattern of medi-MOF-1, (b): T = 100°C, (c): T = 130°C, (d): T = 150°C, (f): t = 5 min, (g): t = 6 min, (h): t = 7 min, (i): t = 10 min.

Figure 2. The SEM images of medi-MOF-1 samples obtained by microwave synthesis under different reaction temperatures of (a) 100 °C, (b) 130 °C, (c) 150 °C, (d) 180 °C for 5 min and at 130 °C for (e) 5 min, (f) 6 min, (g): 7 min, (h): 10 min, respectively.


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In order to further reduce the crystal sizes, we tried to combine capping ligands as modulation agents with microwave heating. Modulation growth was first reported by Kitagawa et al.[40] They used a monodentate capping agent to block the extensive growth of MOF frameworks so that the sizes and shapes are controlled through this route. Curcumin is the natural extract contains two guaiacol segments and there are many derivatives possess the same backbone with only one guaiacol. Taking their biocompatibility into account, we choose several compounds as the modulation capping agents as shown in Scheme 1. Through the above experiment results, the reaction condition for microwave heating was optimized at 130°C and 5 min. Without the addition of capping agents, medi-MOF-1 was obtained as spindle-shaped crystals with size of 10 ×15 (μm) by hydrothermal synthesis, while the size was remarkably decreased to 3 × 4 (μm) under microwave-assisted heating. With the same Zn2+ and curcumin concentration for the synthesis of bulky medi-MOF-1, a certain amount of capping ligands were added into the reaction system and r was defined as the ratio of capping ligands to curcumin. PXRD patterns confirmed all the products were medi-MOF-1 without any impurity (Fig. 4a). As illustrated in Fig. 3, the addition of capping ligand strongly influenced the morphology and the size of the crystals and the SEM images of the resulting samples for all sets of experiments were summarized. When r = 0, the products were obtained under microwave so the morphology was unchanged. With the value of r gradually increased, there was an obvious reduction in the size and significant change in morphology as well. As it can be seen, the spindle shape crystals changed to cubic morphology after addition of capping ligand 1. With the addition of capping agent to adjust the value of r to 2, 5, 10, 15 and 20, the particles size decreased continuously to 5 μm, 2.5 μm, 1 μm, 500 nm, and 200 nm, respectively. The decrease of the crystal sizes can be ascribed to the competitive coordination between capping ligand and curcumin, which finally


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modulates the crystal growth. To be noted, the amount of capping agents used are much higher, which is different from the reported modulating growth. [40] The decrease of the crystal size can be observed until the addition of capping agents reached 5 times of curcumin ligand, implying the poor coordinating ability of the capping agents. The sizes of the nanoparticles were further determined by DLS. As shown in Fig. 4b, the size of the samples was about 1 μm, 500 nm and 200 nm when the r values were 10, 15 and 20, respectively, which is consistent with satisfactory uniformity. The crystals present a cubic morphology due to the selective coordination of the capping agent to metal sites. Single crystal structural determination demonstrates curcumin has 1,3-diketone and guaiacol as two coordinating sites, however, the capping agent only possess guaiacol. The different binding modes between curcumin and capping ligands is considered as the reason to the control of crystal morphology. Satisfied particle size of 200 nm was achieved when r = 20 with cubic crystal shape and purity. Consequently, we could obtain nanosized mediMOF-1 and further control the size and the morphology via the microwave-assisted coordination modulation method.

Scheme 1. The synthetic process and the capping ligands applied in this work.


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Figure 3. The SEM images of medi-MOF-1 samples obtained by microwave synthesis under different concentrations of the capping ligand (L1). (a) r = 0; (b) r = 2; (c) r = 5; (d) r = 10; (e) r = 15; (f) r = 20.

Figure 4. a. The PXRD patterns for representative samples: (a): simulated pattern of medi-MOF-1(black), (b): r = 0 (red), (c): r = 2 (green), (d): r = 5 (dark blue), (e) r = 10 (light blue), (f): r = 15 (pink), (g): r = 20 (yellow). (h) The size and the size distribution of the samples. r = 10 (black), r = 15 (green), r = 20 (red).

With the addition of capping agents under microwave heating, we also checked the effects of the microwave heating times to the crystal growth. Fig 5 showed the SEM pictures of nanosized medi-MOF-1 crystals when r = 10 and the microwave heating time ranges from 10 min to 60 min. Different from the crystal growth under microwave without capping agent, the crystal size


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reaches 1 μm after 5-min heating but no further growth was observed. The maximum crystal size of medi-MOF-1 obtained with the existence of capping agents under microwave is submicrometer sized, while the crystals obtained without the addition of capping agents tens of micrometers. Furthermore, the further extension of reaction time in the presence of capping agents doesn’t affect the crystal size any more, indicating the crystal growth is completely blocked by capping agents after 10-min microwave heating.

Figure 5. The SEM images of medi-MOF-1 samples obtained as the heating time increased (a) t = 10 min; (b) t = 20 min; (c) t = 30 min; (d) t = 60 min.

Beyond our expectation, through the SEM images of nano-medi-MOF-1 under microwave assisted modulation growth, unique textures and surface features have been observed. As shown in Fig 6a, there are pinholes on the surface of medi-MOF-1 obtained with the existence of capping agent. TEM shows the crystals contain channels and holes from inside to the surface, indicating the MOF crystals are hierarchical porous structure. In comparison, the crystals obtained without capping agent exhibit smooth surface without pinholes. Therefore we could conclude that the hierarchical structure is caused by the capping agent which coordinates to the metal site and block the extensive growth of the medi-MOF-1 structure. N2 adsorption isotherm


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of the hierarchical medi-MOF-1 is shown in Fig. 6b. At relative pressure from 0 to 0.1 p/p0, the N2 uptake is ascribed to the micropore filling; from 0.1 to about 0.8 p/p0, the N2 uptake increased from 100 cm3/g to 150 cm3/g due to the multilayer gas adsorption and a desorption hysteresis was observed at the relative pressure of 0.5, indicating the existence of mesopores in the crystals. At high relative pressure above 0.8, the gas absorbed amount further increased to about 350 cm3/g, which is ascribed to the multilayer gas adsorption at the defects and surface of the nanoparticles. Pore size distribution indicates the existence of three pore opening centered at 1.4 nm, 3.6nm and 5.1nm, further certifying the crystals possess hierarchical structures. The hierarchical porous structures are considered to accelerate the mass transfer inside the crystals and allocate larger molecules, which are beneficial properties for the applications of catalysis, adsorption and drug delivery. The unique structure of nano-medi-MOF-1 is manifested by the dye adsorption properties as shown in Fig. 7. Three dyes with different molecular weight were selected and their adsorptions by nano-medi-MOF-1 were investigated. These dyes with increasing molecular weight are methylene blue (MB) of 320 g mol-1, brilliant blue G (BB-G) of 854 g mol-1 and Rose Bengal (RB) of 1018g mol-1, respectively. The results in Fig. 7 showed the MB was completely absorbed either by medi-MOF-1 or nanosized medi-MOF-1. However, for BB-G and RB, the dyes were only absorbed by nanosized medi-MOF-1 but the medi-MOF-1 showed no adsorption at all. The reason to these results was the pore size of medi-MOF-1 was as small as 0.91 nm and only allows the access of small molecules. In contrast, the nano-mediMOF-1 has both micropores and mesopores, therefore allows the absorption of MB and lager dyes molecular BB-G and RB. The hierarchical structure is beneficial to drug delivery, because the diffusion of drug molecules inside the crystals would be accelerated by the hierarchical structures and bigger pores allow larger drug molecules such as peptide to be loaded.


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Figure 6. (a). the SEM images of medi-MOF-1 samples synthesized by the hydrothermal method; (b) the SEM images of nanosized medi-MOF-1 samples (r = 15); (c) the SEM images of nandosize medi-MOF-1 samples. (r= 20); (d) the TEM images of nanosized medi-MOF-1 samples. (r = 20). (e) the N2 adsorption isotherm of nanosized medi-MOF-1, pore size distribution is shown as an inset.

Figure 7. The UV adsorption of dyes with different molecular weight (MW). (a) MB; (b) BB-G; (c) RB. (black: 0.01 mmol/L dyes before adsorption, red: after adsorption by medi-MOF-1, green: after adsorption by nano-medi-MOF-1).


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Scheme 2. The schematic synthesis routes to medi-MOF-1 by conventional heating and microwave assisted modulation.

Besides capping ligand L1, other capping ligands with similar guaiacol segment were applied for modulating growth and similar effects were found indicating our strategy is successful. Another two capping ligands, 4-ethyl-2-methoxyphenol (L2) and isoeugenol (L3), were selected as capping agents as well (Scheme 1). The synthetic procedures to nanosized medi-MOF-1 with L2 or L3 were similar to L1 and described in the supporting information. PXRD pattern and SEM images showed the synthesis with L2 or L3 exhibited the same behavior as L1.The crystal size started to decrease after the ratio of capping agents to curcumin was above 5. The morphology changed to cubic with the addition of capping agents. (Fig. S3 and Fig. S4) The modulation of the shape, size and the hierarchical structure of medi-MOF-1 can be demonstrated as shown in Scheme 2. The coordination between the curcumin and metal under hydrothermal condition gives big crystals with spindle shape. When the capping agent was added to the system, the competitive coordination between curcumin and the capping agent to the metal ions occurred as they possess similar coordination functional groups. The capping agent only has


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one coordination functional group so it blocked the extensive growth of MOF structures. Under microwave condition, nanosized crystals were finally achieved due to the fast heating. At the same time, capping agent created defects and mesopores inside the crystals because of the competitive coordination between curcumin and capping agents to the metal ions was happened simultaneously. Capping agents selectively coordinated to the certain surface of medi-MOF-1 and cause the shape control of the modulation growth. The control of the crystal size and shape of medi-MOF-1 only happened when the ratio of capping agents to curcumin reached above 5, indicating the coordinating ability of capping agent to the metal ions is weaker than that of curcumin. CONCLUSION In this work, we have successfully synthesized the nanosized counterpart of medi-MOF-1, and controlled the morphology and size of the crystal by adding different concentration of monodentate capping ligand with the assisted microwave heating. The size and morphology control was achieved via the competitive coordination between capping agents and curcumin, which modulated the extent of the crystal growth. The nanosized particles from tens of micrometers to about 200 nm were rapidly and conveniently obtained through this method. The nanosized medi-MOF-1 particles possess hierarchical pores from 1.4 nm to 5 nm, which is beneficial to molecules diffusion and loading of large molecules. The nanocrystals are currently under investigation and will allow the fabrication of multifunctional nanocrystals for more advanced biological applications. ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website.


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Figure S1. The PXRD patterns of the samples obtained by microwave synthesis under the temperatures of 180°C. Figure S2. The SEM images of medi-MOF-1 samples obtained by microwave synthesis. Figure S3. The SEM images and the PXRD patterns of medi-MOF-1 samples obtained by microwave synthesis under different concentrations of the capping ligand (L2). Figure S4. The SEM images and the PXRD patterns of medi-MOF-1 samples obtained by microwave synthesis under different concentrations of the capping ligand (L3). ACKNOWLEDGMENTS We are grateful for the financial support from the NSFC (Grant No. 21501064, 21601031), the Opening Project of Key Laboratory of Polyoxometalate Science of Ministry of Education, the Major International (Regional) Joint Research Project of NSFC (grant no. 21120102034) and the National Basic Research Program of China (973 Program, Grant No. 2014CB931804). REFERENCES (1) Yaghi, O. M.; O’Keeffe, M.; Ockwing, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Reticular synthesis and the design of new materials. Nature, 2003, 423, 705-714. (2) Zhou, H. C.; Kitagawa, S. Metal–Organic Frameworks (MOFs). Chem. Soc. Rev. 2014, 43, 5415-5418. (3) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O'Keeffe, M.; Yaghi, O. M. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science, 2002, 295, 469-472. (4) He, H. M.; Sun, Q.; Gao, W. Y.; Perman, J. A.; Sun, F. X.; Zhu, G. S.; Aguila, B.; Forrest, K.; Space, B.; Ma, S. Q. Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation. Angew. Chem. Int. Ed. 2018, 57, 4657-4662. (5) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Introduction to Metal–Organic Frameworks. Chem. Rev. 2012, 112, 673-674. (6) Zhao, N.; Sun, F. X.; Li, P.; Mu, X.; Zhu, G. S. An Amino-Coordinated Metal–Organic Framework for Selective Gas Adsorption. Inorg. Chem. 2017, 56, 6938-6942. (7) Millward, A. R.; Yaghi, O. M. Metal−Organic Frameworks with Exceptionally High Capacity for Storage of Carbon Dioxide at Room Temperature J. Am. Chem. Soc. 2005, 127, 17998-17999.


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(8) Liang, X. Q.; Jia, J. T.; Wu T.; Li D. P.; Liu, L.; Zhu, G. S. A spontaneously resoluted zinc–organic framework with nonlinear optical and ferroelectric properties generated from tetrazolate-ethyl ester ligand. CrystEngComm, 2010, 12, 3499-3501. (9) Stavila, V.; Talin, A. A.; Allendorf, M. D. MOF-based electronic and opto-electronic devices. Chem. Soc. Rev. 2014, 43, 5994-6010. (10) He, H. M.; P, J.; A.; Zhu, G. S.; Ma, S. Q. Metal-Organic Frameworks for CO2 Chemical Transformations. Small, 2016, 12, 6309-6324. (11) Zhou, X.; Huang, W. Y.; Shi, J.; Zhao, Z. X.; Xia, Q. B.; Li, Y. W.; Wang, H. H.; Li, Z. A novel MOF/graphene oxide composite GrO@MIL-101 with high adsorption capacity for acetone. J. Mater. Chem. A, 2014, 2, 4722-4730. (12) He, C. Lu, K. Liu, D. Lin, W. Nanoscale Metal–Organic Frameworks for the Co-Delivery of Cisplatin and Pooled siRNAs to Enhance Therapeutic Efficacy in Drug-Resistant Ovarian Cancer Cells. J. Am. Chem. Soc. 2014, 136, 5181–5184. (13) Zhuang, J. Kuo, C. H. Chou, L. Y. Liu, D. Y. Weerapana, E. Tsung, C. K. Optimized Metal–OrganicFramework Nanospheres for Drug Delivery: Evaluation of Small-Molecule Encapsulation. ACS Nano. 2014, 8, 2812-2819. (14) He, H. M; Sun, F. X.; Aguila, B.; Perman, J. A.; Ma, S. Q.; Zhu, G. S. A bifunctional metal-organic framework featuring the combination of open metal sites and Lewis basic sites for selective gas adsorption and heterogeneous cascade catalysis. J. Mater. Chem. A, 2016, 4, 15240-15246. (15) Davis, M. E.; Chen, Z.; Shin, D. M. Nanoparticle therapeutics: an emerging treatment modality for cancer. Nat. Rev. Drug Discovery, 2008, 7, 771-782. (16) Taylor-Pashow, K. M. L.; Della Rocca, J.; Huxford, R. C.; Lin,W. B. Hybrid nanomaterials for biomedical applications. Chem. Commun. 2010, 46, 5832-5849. (17) De Jong, W. H.; Borm, P. J. A. Drug delivery and nanoparticles: Applications and hazards. Int. J. Nanomed. 2008, 3, 133-149. (18) Peer, D.; Karp, J. M.; Hong, S.; Farokhzad, O. C.; Margalit, R.; Langer, R. Nanocarriers as an emerging platform for cancer therapy. Nat. Nanotechnol. 2007, 2, 751-760. (19) Na, H. B.; Song, I. C.; Hyeon, T.; Inorganic Nanoparticles for MRI Contrast Agents. Adv. Mater. 2009, 21, 2133-2148. (20) He, C.; Lu, K.; Liu, D.; Lin, W. Nanoscale Metal–OrganicFrameworks for the Co-Delivery of Cisplatin and Pooled siRNAs to Enhance Therapeutic Efficacy in Drug-Resistant Ovarian Cancer Cells. J. Am. Chem. Soc. 2014, 136, 5181-5184. (21) Zhuang, J. Chun, H. K.; Chou, L. Y.; Liu, D. Y.; Weerapana, E.; Tsung, C. K. Optimized Metal–OrganicFramework Nanospheres for Drug Delivery: Evaluation of Small-Molecule Encapsulation. ACS Nano, 2014, 8, 2812-2819. (22) Tamames-Tabar, C.; Cunha, D.; Imbuluzqueta, E.; Ragon, F.; Serre, C.; Blanco-Prieto, M. J.; Horcajada,


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P. Cytotoxicity of nanoscaled metal–organic frameworks. J. Mater. Chem. B, 2014, 2, 262-271. (23) Cunha, D.; Yahia, M. B.; Hall, S.; Miller, S. R.; Chevreau, H.; Elkaïm, E.; Maurin, G.; Horcajada, P.; Serre, C. Rationale of Drug Encapsulation and Release from Biocompatible Porous Metal–Organic Frameworks. Chem. Mater. 2013, 25, 2767-2776. (24) Sebastien, V.; Vincent, G.; Qingyuan, Y.; Andrew, W. D.; Bartosz, M.; Barbara, G ; Vimont, A.; Marco, D.; Thomas, D.; Philip, L. L.; Christian, S.; Guillaume, Maurin.; Guy, W. D. A robust amino-functionalized titanium(IV) based MOF for improved separation of acid gases. Chem. Commun. 2013, 49, 10082-10084 (25) Li, T.; Li, D.; C, Chen.; Sullivan, J. E.; Kozlowski, M. T.; Johnson, J. K.; Rosi, N. L. Systematic modulation and enhancement of CO2:N2 selectivity and water stability in an isoreticular series of bio-MOF-11 analogues. Chem. Sci. 2013, 4, 1746-1755. (26) Sona, S.; Stuart, J. R. Nucleobases as supramolecular motifs. Chem. Soc. Rev. 2005, 34, 9-21. (27) Mon, M.; Bruno, R.; Tiburcio, E.; Casteran, P. E.; Ferrando-Soria, J.; Armentano, D.; Pardo, E. Efficient capture of organic dyes and crystallographic snapshots by a highly crystalline amino acid-derived metalorganic framework. DOI:10.1002/chem.201803547. (28) Su, H. M.; Sun, F. X.; Jia J. T.; He, H. M.; Wang, A. F.; Zhu, G. S. A highly porous medical metal– organic framework constructed from bioactive curcumin. Chem. Commun. 2015, 51, 5774-5777 (29) C-ıkrıkc-ı, S.; Mozioglu. E.; Yılmaz, H. Biological activity of curcuminoids isolated from curcuma longa. Rec. Nat. Prod. 2008, 2, 19-24. (30) Hatcher, H.; Planalp, R.; Cho, J.; Torti, F. M.; Torti, S. V. Curcumin: From ancient medicine to current clinical trials (review). Cell. Mol. Life Sci. 2008, 65, 1631-1652. (31) Mahady, G. B.; Pendland, S. L.; Yun, G; Lu, Z. Z. Turmeric (Curcuma longa) and curcumin inhibit the growth of Helicobacter pylori, a group 1 carcinogen. Anticancer Res. 2002, 22, 4179-4181. (32) Sugiyama, Y.; Kawakishi, S.; Osawa, T. Involvement of the betadiketone moiety in the antioxidative mechanism of tetrahydrocurcumin. Biochem. Pharmacol. 1996, 52, 519-525. (33) Ruby, A. J.; Kuttan, G.; Babu, K. D.; Rajasekharan, K. N.; Kuttan, R. Anti-tumour and antioxidant activity of natural curcuminoids. Cancer Lett. 1995, 94, 79–83. (34) Sanphui, P.; Goud, N. R.; Khandavilli, U. B. R.; Nangia, A. Fast Dissolving Curcumin Cocrystals. Cryst. Growth Des. 2011, 11, 4135-4145. (35) Rieter, W. J.; Taylor, K. M. L.; An, H.; Lin, W. Nanoscale Metal−Organic Frameworks as Potential Multimodal Contrast Enhancing Agents. J. Am. Chem. Soc. 2006, 128, 9024-9025. (36) Qiu, L. G.; Xu, T.; Li, Z. Q.; Wang, W.; Wu, Y.; Xing, X. J.; Tian, Y.; Zhang, L. D. Hierarchically Micro and Mesoporous Metal–Organic Frameworks with Tunable Porosity. Angew. Chem. Int. Ed. 2008, 47, 94879491 (37) Albuquerque, G. H.; Fitzmorris, R. C.; Ahmadi, M.; Wannenmacher N.; Thallapally, P. K.; McGrail B. P.; Herman, G. S. Gas–liquid segmented flow microwave-assisted synthesis of MOF-74(Ni) under moderate pressures. CrystEngComm. 2015, 17, 5502-5510.


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(38) Rijnaarts, T.; Mejia-Ariza, R.; Egberink, R. J. M.; Roosmalen, W.; Huskens, J. Metal–Organic Frameworks (MOFs) as Multivalent Materials: Size Control and Surface Functionalization by Monovalent Capping Ligands. Chem. Eur. J. 2015, 21, 10296-10301. (39) Diring, S.; Furukawa, S.; Takashima, Y.; Tsuruoka, T.; Kitagawa, S. Controlled Multiscale Synthesis of Porous Coordination Polymer in Nano/Micro Regimes. Chem. Mater. 2010, 22, 4531-4538. (40) Tsuruoka, T.; Furukawa, S.; Takashima, Y.; Yoshida, K.; Isoda, S.; Kitagawa, S. Nanoporous Nanorods Fabricated by Coordination Modulation and Oriented Attachment Growth. Angew. Chem. 2009, 121, 48334837.


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For Table of Contents Use Only

Size, Shape and Porosity Control of Medi-MOF-1 via Growth Modulation under Microwave Heating Xiaodong Feng,† Faheem Muhammad,† Fuxing Sun,‡ Yuyang Tian,*,† and Guangshan Zhu,†

Synopsis: Nanosized medi-MOF-1 with hierarchical porosity, and controlled the sizes and shapes are successfully synthesized via growth modulation and microwave heating.


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Size, Shape and Porosity Control of Medi-MOF-1 via Growth

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