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Preparation and Applications of Metal−Organic Frameworks


(MOFs): A Laboratory Activity and Demonstration for High School
and/or Undergraduate Students
Yoshie Sakamaki, Miu Tsuji, Zachary Heidrick, Olivia Watson, Jeremy Durchman, Christopher Salmon,
Stephen R. Burgin,* and M. Hassan Beyzavi*
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sı Supporting Information

ABSTRACT: The chemistry of metal−organic frameworks (MOFs), a new


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class of emerging crystalline porous solids with three-dimensional (3D)


networks composed of metals and multidentate organic molecules, was
introduced by using three differently shaped crystals. We reported new and
mild MOF synthesis methods that are simple and devised to be performed in
high school or primarily undergraduate school settings. MOF applications were
demonstrated by use of our synthesized MOFs in the capture of iodine as a
potentially hazardous molecule from solution and as a drug delivery system.
These applications can be visually confirmed in minutes. Students can gain
knowledge on advanced topics, such as drug delivery systems, through these
easy-to-prepare MOFs. Furthermore, students can gain an understanding of
powder X-ray analysis and ultraviolet−visible near-infrared spectroscopy. This
laboratory experience is practical, including synthesis and application of MOFs.
The entire experiment has also been recorded as an educational video posted on
YouTube as a free public medium for students to watch and learn. In this paper we first report the steps we took to synthesize and
analyze the MOFs, followed by a description of a simple demonstration that we verified to effectively exhibit adsorption by MOFs.
We conclude with a description of how the laboratory activity and demonstration were implemented in an undergraduate chemistry
laboratory.
KEYWORDS: High School/Introductory Chemistry, First-Year Undergraduate/General, Second-Year Undergraduate,
Upper-Division Undergraduate, Inorganic Chemistry, Hands-On Learning/Manipulatives, Applications of Chemistry,
Crystals/Crystallography, Nanotechnology, Separation Science

■ INTRODUCTION
Nanoporous materials, such as metal−organic frameworks
ces, without which these compounds can be very difficult to
prepare. This project aims to show that the synthesis and
(MOFs), have novel properties that are becoming of increasing testing process of MOFs can be simplified to the point that
scientific and technological importance as we continue to high school and undergraduate students can do it without the
discover new nanoporous materials with new applications.1 use of highly specific equipment, therefore enriching their
MOFs possess a wide variety of applications due to their large educational experience as they interact with cutting edge
internal surface area, porous nature, and strong bonds between chemistry.
metal and linkers.2 These characteristics allow them to be Educational approaches using MOFs have been reported.
suitable materials for applications such as catalysis, gas storage, Smith et al. reported gas adsorption using CD-MOF
drug delivery, gas vapor separation, luminescence, lithium-ion (cyclodextrin−metal−organic framework), and Jones et al.
batteries, water treatment, and carbon dioxide capture, as well reported removal of methylene blue using CD-MOF.8,9 Rood
as photo- and electrocatalysis.1,3 MOFs’ abilities to encapsulate et al. approaches α-Mg3(O2CH)6 synthesis and NMR
drugs and other substrates make them novel new drug delivery
systems and pollution control agents.4−7 With the increasing Received: December 15, 2019
importance of MOFs in a variety of chemical fields, it is Revised: February 19, 2020
important that we educate younger generations, specifically
high school and undergraduate students, in the function and
preparation of MOFs. The synthesis of these compounds
typically requires access to university-level laboratory resour-
© XXXX American Chemical Society and
Division of Chemical Education, Inc. https://dx.doi.org/10.1021/acs.jchemed.9b01166
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understanding, and Wriedt et al. introduces PCN-200 require strongly acidic and harsh conditions, unlike the
(porphyrinic metal−organic framework) synthesis and gas syntheses of some MOFs. In addition, we can perform the
adsorption.10,11 Sumida and Arnold also reported the syntheses for two of these MOFs, MOF-5 and ZIF-8, at room
preparation and characterization of MOFs for undergraduate temperature under normal pressure. We tested several reported
students.12 procedures and conditions in order to determine the most
The purpose of our pedagogical approach using MOFs is to ideal conditions to produce larger and clearer crystals, as these
introduce a new synthetic approach to MOFs tailored to high crystals allow further analysis using scanning electron
school facilities and various applied experiments using three microscopy (SEM) and tunneling electron microscopy
types of MOFs. Using three easily synthesized MOFs, students (TEM). Most high schools may not have access to TEM
can learn the difference in adsorption capacity, depending on and SEM, but the obtained crystal shapes can be identified
the kind of MOF, visually or with the use of UV−vis using a common optical microscope if the crystals are large
spectroscopy. In addition, we can learn how to encapsulate enough. The synthesis of MIL-101(Fe) has been reported in a
curcumin, a familiar drug, by encapsulation after MOF vessel at 110 °C in an oven.16 We successfully modified the
synthesis and encapsulation by de novo synthesis. We report condition to be milder for this project so that high school
for the first time a new synthesis method of MIL-101(Fe) and students would be able to successfully perform this experiment
de novo synthesis of ZIF-8 with curcumin. without the use of specific instruments. To show an application
For this project, we used three different metal−organic of MOFs, we demonstrated the adsorption of iodine (I2) and
frameworks (MOFs), each with different geometries and pore encapsulation of curcumin. Curcumin, a biologically active
sizes: MOF-5, ZIF-8 (ZIF = zeolitic imidazolate frameworks), component of turmeric, was chosen as a drug candidate for
and MIL-101(Fe) (MIL = Materials of Institute Lavois- student safety, simple extraction from the spice, and easily
ier)13−17 (Figure 1). The syntheses of these MOFs do not identifiable color change when absorbed by the MOF. On the
other hand, if radioactive iodine is released into the
environment by nuclear plant accidents, it could be very
hazardous and poses a serious health risk for humans.
Therefore, the development of a nanoporous material capable
of I2 adsorption is of high importance.
We have also prepared an educational video in which we
explain the concept of nanoporous materials, in particular
MOFs, and also demonstrate the laboratory techniques and
experiments described in this paper.18 We uploaded this video
to YouTube18 and made it publicly available so that teachers,
professors, TAs, and both high school and undergraduate
students could easily access it. For students to be able to better
understand the applications and preparation of MOFs, a
lecture by the instructor prior to class should be implemented.
The basic concepts of the characterization techniques used in
the experiments should also be taught (Table 1). Through this
instruction and activity, students would learn how to analyze
chemical substances through powder X-ray diffraction (PXRD)
and UV−vis spectroscopy, along with how to identify
structural differences between molecules using TEM, SEM,
and basic microscopes. The utilization of PXRD would teach
students how to calculate cellular dimensions and decipher
between amorphous and crystalline materials. Through UV−
vis spectroscopy, students would learn about using light
absorption to determine a substrate such as I2. Moreover, these
techniques can be used to enable students to better understand
Figure 1. Three kinds of MOFs (MOF-5, ZIF-8, MIL-101(Fe)) MOF mechanisms, structures, and applications.
prepared in this study and their structural representations. Synthesis
Syntheses for MOF-5, ZIF-8, and MIL-101(Fe) are in the
Supporting Information (SI). Large crystals of MOF-5 were

Table 1. Topics Addressed and Learning Outcomes Associated with the Activity

Topic Addressed Learning Outcomes


MOFs: application, importance, and Students will be able to understand what MOFs are, their applications and uses, how to make them, and their importance to
synthesis the scientific field.
Powder X-ray diffraction (PXRD) Students will be able to decipher between amorphous and crystalline materials and calculate cellular dimensions of MOFs.
analysis Students will also analyze PXRD data.
TEM, SEM, and basic microscope Students will be able to apply basic microscopy skills, while also being able to recognize and identify MOF structure via TEM
use and SEM images.
UV−vis spectroscopy analysis Students will be able to identify the different light absorptions in order to characterize different substrates.
Coordination and geometry Students will be able to explain how different metals and linkers can change the geometry of MOFs.

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Figure 2. (a) TEM (A) and SEM (B−F) images of MOF-5. (b) TEM
image of ZIF-8.

made at room temperature with stirring for 2.5 h. The TEM


and SEM images of MOF-5 clearly showed cubic crystals
(Figure 2a). MOF-5 was also analyzed by powder X-ray
diffraction (PXRD)13 (Figure S1a). Bigger crystals of ZIF-8
were also synthesized at room temperature, in a static state for
24 h. Condition 1 did not produce the expected standard
crystalline shape, but it did produce the same XRD pattern19,20
(Figure S1b). Therefore, we synthesized ZIF-8 using the
standard methods. The TEM image of ZIF-8 showed
hexagonal crystals as shown in Figure 2b. MIL-101(Fe) was
prepared with modified mild conditions so that it could be
performed with experimental equipment more likely to be
found in the high school science laboratory. The standard
preparation method for MIL-101(Fe) was reported. Con-
ditions 1, 2, 3, and 4 were modified from the standard which is
the originally reported preparation16 in order to be prepared in
the high school and undergraduate laboratory setting. For Figure 3. TEM and SEM images of MIL-101(Fe) and their synthesis
conditions.
Condition 1, MIL-101(Fe) was synthesized at 110 °C for 17 h
in an oil bath. Because high school laboratories typically do not
have access to oil baths, we attempted to decrease the heat and
setting, it is recommended that the instructor initiates the
get rid of the oil bath so that the synthesis would be feasible for
experiment before the class starts for students to see the final
high school students. Thus, in Condition 2, the capped vial was
results, as the MOF would not likely fully adsorb the iodine
placed in direct contact with the hot plate at 60 °C for 17 h.
before the end of the laboratory period.
The PXRD for Condition 2 revealed the correct hexagonal
In order to be analyzed, all MOFs were dried in a vacuum
crystalline shape, which differs from the standard MIL-101(Fe)
oven at 60 °C for 5 h. In cases where a vacuum oven or oven is
crystalline shape. Additionally, the PXRD of Condition 2
not available, longer air exposure time (2−3 days) would be
matched that of the standard MIL-101(Fe) condition, so we
sufficient to dry the MOFs. The dried MOFs were analyzed by
surmised that the crystal was still forming the familiar crystal-
PXRD to check their crystallinity before and after I2 adsorption
like standard MIL-101(Fe). To make the standard shape of
(Figures S3−S5). The PXRDs of both MIL-101(Fe) and
MIL-101(Fe), we increased the heating time for Conditions 3
MOF-5 changed upon exposure to methanol. To ensure that
and 4 by using a salt bath. Figure 3 shows the TEM and SEM
iodine or stirring was not responsible for the structural
images of each MIL-101(Fe) condition, and Figure S2 shows
degradation, control experiments were carried out. First, the
their PXRD spectra.
standard MOFs were stirred for 48 h in methanol and then
MOF Applications dried, and subsequent PXRD analysis revealed structural
I2 Adsorption. Iodine solutions (0.1, 0.2, and 0.3 mM) degradation as indicated by a loss of diffraction peaks (Figures
were prepared in methanol. Students then added 5 mg of the S10 and S11). The results confirmed that the changes in the
synthesized MOFs, MIL-101(Fe), ZIF-8, and MOF-5, to 10 PXRD spectra were indeed caused by methanol or stirring
mL of the solution, respectively, while being stirred at 300 rpm exposure rather than by adsorption of I2. Afterward, the MOFs
at room temperature. Pictures of the MOF solutions were were stirred in DMF for 48 h, and no loss of diffraction peaks
taken at the following time stamps: 30 min and 1, 2, 3, 4, 24, was observed in PXRD; this result indicates that methanol is
and 48 h (Figures 4−6). After 48 h, these solutions were the reason for the MOF degradation (Figure S12).
centrifuged, to separate the MOFs from the iodine solution. As The adsorptions of the iodine by MIL-101(Fe), MOF-5, and
the MOFs were exposed to the iodine solution, they began ZIF-8 were all analyzed by UV−vis spectroscopy. As conveyed
adsorbing the iodine, resulting in the opaque orange color. in Figure S6, all the standard peaks of iodine that were
Theoretically, if the MOFs have successfully adsorbed all of the dissolved in methanol solvent were detected when adsorbed by
iodine, the solution should be completely clear following the MOFs. MOF5 in particular shows an exceptional capacity
centrifugation. Of the three MOFs tested, MOF-5 had the for iodine adsorption because it has the most drastic change
most successful results, as the solutions visually had lost all from standard iodine.
pigment after being centrifuged. Since laboratory periods Figures 4−6 show the progression of iodine adsorption for
typically do not last more than a couple of hours in the each MOF with different concentrations of iodine solution.
undergraduate setting and often even less in a high school The more transparent and colorless the solution is, the better
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Figure 4. I2 adsorption with MIL-101(Fe) standard. The first, second, and third rows are 0.1, 0.2, and 0.3 mM of I2 in methanol, respectively. MIL-
101(Fe) itself has a pink to orange color.

Figure 5. I2 adsorption with ZIF-8. The first, second, and third rows are 0.1, 0.2, and 0.3 mM solutions of I2 in methanol, respectively.

Figure 6. I2 adsorption with MOF-5. The first, second, and third rows are 0.1, 0.2, and 0.3 mM of I2 solution in methanol, respectively.

the ability of the MOF to encapsulate the iodine. Thus, of the all three concentrations. The superior iodine capture of MOF-
MOFs tested, MOF-5 most effectively adsorbed the iodine at 5 when compared to those of MIL-101(Fe) and ZIF-8
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Figure 7. (a) UV−vis spectra of curcumin in ethanol encapsulation with MIL101, MOF-5, and ZIF-8. (b) PXRD comparison of standard ZIF-8
and curcumin@ZIF-8. (c) Curcumin encapsulation with MIL-101(Fe), MOF-5, and ZIF-8.

showcases the effect of high internal surface area on the ability of extracted curcumin solution were compared to known
of a MOF to absorb contaminates. MOF-5 has a reported spectra.27 As conveyed in Figure 7a, we first prepared a
surface area of 3800 m2 g−1 which is considerably higher than standard ethanol solution of curcumin which was used for
the reported surface areas of MIL-101(Fe) (3054 m2 g−1) and three encapsulation experiments using MOFs. All three MOFs
ZIF-8 (2800 m2 g−1).21−23 The enhancement of iodine capture show their capacity for curcumin encapsulation. Percentages of
in MOF-5 compared to the other MOFs tested is a result of a curcumin encapsulation were 78% for ZIF-8, 67% for MOF-5,
higher internal surface area. and 98% for MIL-101(Fe).
Curcumin Encapsulation The dried MOFs were analyzed via PXRD to check their
crystallinity before and after curcumin encapsulation (Figure
One spatula scoop of turmeric was dissolved in acetone and 7b and Figures S7 and S8). The PXRD spectra showed
filtered on filter paper before it was dried. A yellow substance changes following the addition of curcumin, but once again
that was collected on the walls of the glassware was these changes can be attributed to the stability of MOFs in
curcumin.24,25 The curcumin was dissolved in methanol and methanol. For the encapsulation of curcumin, we report here
used for the encapsulation. A 10 mL of the curcumin solution the new de novo synthesis of ZIF-8 with curcumin. The
(2.8 μM) was poured into each sample container; 20 mg of extracted curcumin and chemicals for the de novo synthesis of
MIL-101(Fe), MOF-5, and ZIF-8 was added to each solution, ZIF-8 were mixed for 1 h at room temperature. We obtained
and the solutions were stirred. The reported extinction the yellow ZIF-8 powder, which encapsulated curcumin while
coefficient of curcumin (ε = 55,000 L mol−1 cm−1) was used ZIF-8 was forming (Figure S9a). The PXRD comparison of
for calculation.26 The color changes were observed for 48 h (0 parent ZIF-8 with its de novo counterpart confirmed the
min, 30 min, 1 h, 2 h, 3 h, 4 h, 24 h, 48 h) (Figure 7c). Again, a successful formation of de novo synthesized ZIF-8 as shown in
more transparent and colorless mixture indicates a more Figure S9b.
effective encapsulation by the MOF. All three MOFs appeared
to encapsulate the curcumin rather well. The encapsulations of Results from an Undergraduate School
the curcumin in MIL-101(Fe), MOF-5, and ZIF-8 were all In order to examine the practicality of the work presented in
analyzed by UV−vis spectroscopy (Figure 7a). The UV spectra this paper, undergraduate chemistry students at the University
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of ArkansasFort Smith (UAFS) successfully performed the of MOFs, their synthesis, and their immense applicative value.
experiments and demonstrated the adsorption by MOFs by Students were able to relate gained knowledge of the
following the procedures described in this paper as mechanistic coordination geometry involved in the assembly
supplemented by the video we have uploaded to YouTube.18 process. Though electron microscopy was prohibitive for
As a group example, the students at UAFS were able to UAFS, students were able to derive important details about
successfully synthesize MOF-5 and test its application. Due to MOF characterization from the video. Additionally, UV−vis
lab time restraints, it is recommended that the instructor have was available for this sample study, and as such, students were
the compound already synthesized prior to class. This enables able to learn and apply this important analytical technique to
students to set up synthesis but not have to wait the 7.5−24 h confirm MOF-5 assembly via iodine adsorption.
for the experiment to finish, which makes the lab period more On the basis of these experiments, performed under
time efficient. These experiments are simple and relatively easy relatively low-cost conditions with basic equipment commonly
to follow so that students should not need significant found in undergraduate chemistry laboratories, it is proposed
assistance. that incorporation of MOF synthesis and analysis should be
In order to ascertain the applicability of MOF synthesis at a considered for addition to modern chemical education
primarily undergraduate institution with fairly limited curricula. Students quickly developed and appreciated a
instrumentation, students at UAFS took part in a sample sense of how varying the length and identity of linker systems
study encompassing two lab periods where MOF-5 was first involved could be employed to create materials of variable pore
synthesized and then assayed for iodine adsorption following size using common d-metal coordination geometry. Of the 19
the protocol described in this paper. Student feedback on respondents surveyed, 14 (73.7%) related that this same
learning objectives was then collected and compiled via technology could be tuned to adapt for different hazardous
student lab reports and completion of the survey provided in molecules and/or drugs. Ten students (52.6%) noted that
Section 5 of the Supporting Information (SI). Prior to this these frameworks could be further functionalized at free
process, all students had completed at least one semester of carboxylic acid positions on the surface to bind proteins such
organic chemistry; however, as determined by the survey, as antibodies, in turn serving as highly selective filters for
students had no prior knowledge of metal−organic frame- separation and purification for antigen counterparts. Respond-
works, their versatility, or their synthesis. ent students were universally excited to see how modern
For the first lab period, a brief lecture describing the chemical techniques like MOF synthesis may be potentially
synthesis was presented by the instructor which was followed employed to selectively remove toxic components from
by playing our YouTube video that highlights the scientific contaminated water and air systems to improve the way of
value and versatility of MOFs. Subsequently, MOF-5 synthesis life on our planet. It is important to note that the employment
at room temperature with a 7:3 ratio of DMF:EtOH was of media in relaying instruction and importance regarding
successful for all groups over a 3 h reaction time frame, as MOF synthesis, analysis, and application in the undergraduate
noted by the formation of white precipitate in solution. It is laboratory setting cannot be overstated. The video format
noteworthy to include that this occurred despite the variances instilled a palpable excitement that proved instrumental in
introduced by different sized round-bottom flasks, stir bars, creating a positive, instructional laboratory experiment.
and uncalibrated and dissimilar stir plates commonly found in We still believe that the content and methods used in this
teaching laboratories. This clearly showed the reproducibility paper are comprehensible to advanced high school chemistry
of our MOF simplified procedure. Two washes (first with students. We base this on our use of a video showcasing the
DMF followed by EtOH) were conducted in 1.5 mL demonstration with a high school student audience and their
Eppendorf tubes at 2000 rpm for 2 min with a small tabletop informed questions related to our work. We recognize that
microcentrifuge. Samples were then placed in a vacuum oven limitations such as class size, time, and resources exist in a high
to dry overnight in at 60 °C. school classroom when compared to an undergraduate
In lieu of electron microscopy (which students did view in laboratory and that as such implementation of this sort of
the YouTube video) for direct confirmation of MOF-5 work in a high school setting is challenging to say the least. We
assembly, students tested their MOF-5 samples to assay for continue to explore ways that we can make this sort of
iodine adsorption in order to visually confirm the removal of experience available to high school students including, but not
toxic iodine from solution and thus confirm successful MOF-5 limited to, providing opportunities for high school students to
volunteer in our lab as we perform MOF research.


synthesis via iodine sequestration. Dried MOF-5 samples
stored at room temperature from the previous week were
resuspended in 2.0 mL of 0.1 mM iodine in ethanol and CONCLUSION
incubated for a total of 1 h. Particles were centrifuged every 30 MOFs as emerging porous nanomaterials have a large internal
min, and 0.5 mL aliquots were removed for time lapse surface area with a porous nature which makes them novel
visualization. After 30 min and centrifugation, the once drug delivery systems and pollution control agents due to their
distinctly yellow solutions of iodine were visibly transparent ability to encapsulate drugs and toxic materials. MOFs’ abilities
and free of color. Additionally, due to the relatively dilute to encapsulate compounds, such as curcumin, are demon-
iodine concentrations involved and availability of instrumenta- strated through an easily identifiable color change that can be
tion, samples were analyzed via UV−vis spectroscopy at 360 seen by the students. As new MOF applications continue to be
nm to confirm >98% iodine removal after just 30 min as discovered, it is important that younger generations are taught
corroborated independently in Figure 6. about new nanoscience in their undergraduate and high school
Students then prepared lab reports to confer their newfound chemistry courses. Most prior reports of MOF syntheses
knowledge on the learning objectives presented in this paper. mandate the use of high-pressure solvothermal reactions,
Upon examination of the lab reports, students were, without which are not safely feasible in the high school setting. Our
exception, able to relate learning about the overall significance simplified approach to MOF synthesis has set the groundwork
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for MOF-5, ZIF-8, and MIL-101(Fe) to be instituted into high ACKNOWLEDGMENTS


school and undergraduate chemistry education. This work M.H.B. gratefully acknowledges the financial support through
includes a synthesis for MOFs in a simple round-bottom flask the startup funds from the University of Arkansas and the
at ambient pressure, making it possible to include MOFs in the NIH-NIGMS (GM132906).We acknowledge Jarod Meredith
curriculum of high school chemistry laboratories. The use of and Nicholas Barnett at UAFS who assisted with aspects of this
nontoxic curcumin derived from store-bought turmeric lowers project.


the cost of repeating this experiment. Students repeating this
experiment can characterize MOFs with an optical microscope. REFERENCES
Students’ abilities to learn about and simply prepare these
advanced drug carriers will enrich high school and under- (1) Kuppler, R. J.; Timmons, D. J.; Fang, Q.-R.; Li, J.-R.; Makal, T.
A.; Young, M. D.; Yuan, D.; Zhao, D.; Zhuang, W.; Zhou, H.-C.
graduate chemistry courses and allow them to better Potential Applications of Metal-Organic Frameworks. Coord. Chem.
understand real world concepts such as drug delivery systems Rev. 2009, 253, 3042−3066.
and pollution control. Selected new methods and applications (2) Yap, M. H.; Fow, K. L.; Chen, G. Z. Synthesis and Applications
developed in this paper were successfully reproduced by of MOF-derived Porous Nanostructures. Green Energy Environ. 2017,
students at the University of ArkansasFort Smith (UAFS) 2, 218−245.
which illustrated that advanced chemistry research can be (3) Sakamaki, Y.; Ozdemir, J.; Heidrick, Z.; Watson, O.; Shahsavari,
performed in the high school and undergraduate settings. H. R.; Fereidoonnezhad, M.; Khosropour, A. R.; Beyzavi, M. H.


Metal−Organic Frameworks and Covalent Organic Frameworks as
ASSOCIATED CONTENT Platforms for Photodynamic Therapy. Comments Inorg. Chem. 2018,
38, 238−293.
* Supporting Information
sı (4) Ibrahim, M.; Sabouni, R.; Husseini, G. A. Anti-cancer Drug
The Supporting Information is available at https://pubs.ac- Delivery Using Metal Organic Frameworks (MOFs). Curr. Med.
Chem. 2017, 24, 193−214.
s.org/doi/10.1021/acs.jchemed.9b01166.
(5) Wyszogrodzka, G.; Dorozynski, P.; Gil, B.; Roth, W. J.;
Information about reagents, hazards, instrumentation Strzempek, M.; Marszalek, B.; Weglarz, W. P.; Menaszek, E.;
and the syntheses of MOFs and PXRD analyses (PDF, Strzempek, W.; Kulinowski, P. Iron-Based Metal−Organic Frame-
DOCX) works as a Theranostic Carrier for Local Tuberculosis Therapy.
Pharm. Res. 2018, 35, 144.

■ AUTHOR INFORMATION
Corresponding Authors
(6) Almásǐ , M.; Zeleňaḱ , V.; Palotai, P.; Beňová, E.; Zeleňaḱ ová, A.
Metal-Organic Framework MIL-101(Fe)-NH2 Functionalized with
Different Long-Chain Polyamines as Drug Delivery System. Inorg.
Chem. Commun. 2018, 93, 115−120.
Stephen R. Burgin − Department of Curriculum and (7) Della Rocca, J.; Liu, D.; Lin, W. Nanoscale Metal−Organic
Instruction, University of Arkansas, Fayetteville, Arkansas Frameworks for Biomedical Imaging and Drug Delivery. Acc. Chem.
72701, United States; Email: srburgin@uark.edu Res. 2011, 44, 957−968.
M. Hassan Beyzavi − Department of Chemistry and (8) Smith, M. K.; Angle, S. R.; Northrop, B. H. Preparation and
Biochemistry, University of Arkansas, Fayetteville, Arkansas Analysis of Cyclodextrin-Based Metal−Organic Frameworks: Labo-
ratory Experiments Adaptable for High School through Advanced
72701, United States; orcid.org/0000-0002-6415-8996; Undergraduate Students. J. Chem. Educ. 2015, 92, 368−372.
Email: beyzavi@uark.edu; https://beyzavigroup.uark.edu/ (9) Jones, D. R.; DiScenza, D. J.; Mako, T. L.; Levine, M.
Environmental Application of Cyclodextrin Metal−Organic Frame-
Authors works in an Undergraduate Teaching Laboratory. J. Chem. Educ.
Yoshie Sakamaki − Department of Chemistry and Biochemistry, 2018, 95, 1636−1641.
University of Arkansas, Fayetteville, Arkansas 72701, United (10) Rood, J. A.; Henderson, K. W. Synthesis and Small Molecule
States Exchange Studies of a Magnesium Bisformate Metal−Organic
Miu Tsuji − Department of Chemistry and Biochemistry, Framework: An Experiment in Host−Guest Chemistry for the
University of Arkansas, Fayetteville, Arkansas 72701, United Undergraduate Laboratory. J. Chem. Educ. 2013, 90, 379−382.
(11) Wriedt, M.; Sculley, J. P.; Aulakh, D.; Zhou, H.-C. Using
States Modern Solid-State Analytical Tools for Investigations of an
Zachary Heidrick − Department of Chemistry and Advanced Carbon Capture Material: Experiments for the Inorganic
Biochemistry, University of Arkansas, Fayetteville, Arkansas Chemistry Laboratory. J. Chem. Educ. 2016, 93, 2068−2073.
72701, United States (12) Sumida, K.; Arnold, J. Preparation, Characterization, and
Olivia Watson − Department of Chemistry and Biochemistry, Postsynthetic Modification of Metal−Organic Frameworks: Synthetic
University of Arkansas, Fayetteville, Arkansas 72701, United Experiments for an Undergraduate Laboratory Course in Inorganic
States Chemistry. J. Chem. Educ. 2011, 88, 92−94.
Jeremy Durchman − Department of Physical Sciences, (13) Yang, J.-M.; Liu, Q.; Sun, W.-Y. Shape and Size Control and
University of ArkansasFort Smith, Fort Smith, Arkansas Gas Adsorption of Ni(II)-doped MOF-5 Nano/Microcrystals.
72913-3649, United States Microporous Mesoporous Mater. 2014, 190, 26−31.
(14) Jian, M.; Liu, B.; Liu, R.; Qu, J.; Wang, H.; Zhang, X. Water-
Christopher Salmon − Department of Chemistry and based Synthesis of Zeolitic Imidazolate Framework-8 with High
Biochemistry, University of Arkansas, Fayetteville, Arkansas Morphology Level at Room Temperature. RSC Adv. 2015, 5, 48433−
72701, United States 48441.
Complete contact information is available at: (15) Taylor-Pashow, K. M. L.; Della Rocca, J.; Xie, Z.; Tran, S.; Lin,
https://pubs.acs.org/10.1021/acs.jchemed.9b01166 W. Postsynthetic Modifications of Iron-Carboxylate Nanoscale
Metal−Organic Frameworks for Imaging and Drug Delivery. J. Am.
Chem. Soc. 2009, 131, 14261−14263.
Notes
(16) Cui, F.; Deng, Q.; Sun, L. Prussian Blue Modified Metal−
The authors declare no competing financial interest. Organic Framework MIL-101(Fe) With Intrinsic Peroxidase-Like

G https://dx.doi.org/10.1021/acs.jchemed.9b01166
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education pubs.acs.org/jchemeduc Laboratory Experiment

Catalytic Activity As a Colorimetric Biosensing Platform. RSC Adv.


2015, 5, 98215−98221.
(17) Xie, Q.; Li, Y.; Lv, Z.; Zhou, H.; Yang, X.; Chen, J.; Guo, H.
Effective Adsorption and Removal of Phosphate from Aqueous
Solutions and Eutrophic Water by Fe-based MOFs of MIL-101. Sci.
Rep. 2017, 7, 3316.
(18) https://www.youtube.com/watch?v=lqTQfnK9DEU.
(19) Jian, M.; Liu, B.; Liu, R.; Qu, J.; Wang, H.; Zhang, X. Water-
based Synthesis of Zeolitic Imidazolate Framework-8 with High
Morphology Level at Room Temperature. RSC Adv. 2015, 5, 48433−
48441.
(20) Li, Y.; Quan, X. Adsorption of Sulfamethoxazole on
Nanoporous Carbon Derived from Metal−Organic Frameworks. J.
Geosci. Environ. Prot. 2017, 5, 1−8.
(21) Kaye, S. S.; Dailly, A.; Yaghi, O. M.; Long, J. R. Impact of
Preparation and Handling on the Hydrogen Storage Properties of
Zn4O(1,4-benzenedicarboxylate)3 (MOF-5). J. Am. Chem. Soc. 2007,
129, 14176−14177.
(22) Mao, P.; Qi, B.; Liu, Y.; Zhao, L.; Jiao, Y.; Zhang, Y.; Jiang, Z.;
Li, Q.; Wang, J.; Chen, S.; Yang, Y. AgII doped MIL-101 and Its
Adsorption of Iodine with High Speed in Solution. J. Solid State Chem.
2016, 237, 274−283.
(23) Chin, M.; Cisneros, C.; Araiza, S. M.; Vargas, K. M.; Ishihara,
K. M.; Tian, F. Rhodamine B Degradation by Nanosized Zeolitic
Imidazolate Framework-8 (ZIF-8). RSC Adv. 2018, 8, 26987−26997.
(24) Anderson, A. M.; Mitchell, M. S.; Mohan, R. S. Isolation of
Curcumin from Turmeric. J. Chem. Educ. 2000, 77, 359−360.
(25) Pawar, H. A.; Gavasane, A. J.; Choudhary, P. D. A Novel and
Simple Approach for Extraction and Isolation of Curcuminoids from
Turmeric Rhizomes. Nat. Prod Chem. Res. 2018, 6, 300.
(26) Priyadarsini, K. I. The Chemistry of Curcumin: From
Extraction to Therapeutic Agent. Molecules 2014, 19, 20091−20112.
(27) Călinescu, M.; Fiastru, M.; Bala, D.; Mihailciuc, C.; Negreanu-
Pîrjol, T.; Jurcă, B. Synthesis, Characterization, Electrochemical
Behavior and Antioxidant Activity of New Copper(II) Coordination
Compounds with Curcumin Derivatives. J. Saudi Chem. Soc. 2019, 23,
817−827.

H https://dx.doi.org/10.1021/acs.jchemed.9b01166
J. Chem. Educ. XXXX, XXX, XXX−XXX

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