Anthracene-Tagged UiO-67-MOF as Highly Selective Aqueous Sensor for Nanoscale Detection of Arginine Amino Acid

Leila Mohammadi and Hamid Reza Khavasi*

Article

Anthracene-Tagged UiO-67-MOF as Highly Selective Aqueous

Sensor for Nanoscale Detection of Arginine Amino Acid

Cite This: https://dx.doi.org/10.1021/acs.inorgchem.0c01045

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sı Supporting Information

ABSTRACT: In the present paper, new functionalized UiO-67

metal−organic frameworks (MOF) which contain aromatic tagged

groups such as phenyl, naphthyl, and anthracene have been

synthesized, characterized, and used for sensing water-soluble

amino acids. The results show that anthracene-tagged UiO-67-

MOF is shown to act as a highly eﬃcient and selective aqueous

sensor for arginine over other water-soluble amino acids in

nanoscale. Upon adding an increasing amount of arginine, PL

bands of the anth-UiO-67 MOF quenched completely, while there

is no perturbation in the PL bands for other amino acid observed.

This MOF allows a selective ratiometric detection of arginine

without any interference from other amino acids.

INTRODUCTION

porosities, and their ability to be easily modiﬁed with the

■

18−22

demanded functionality.

Additionally, utilization of water-

Amino acids are inseparable components of biological

substances and are crucially embroiled in a variety of

phenomena. Identiﬁcation of diﬀerent amino acids has played

a great role in the history of nutritional analysis and also in the

recognition of diseases like pancreatitis and Alzheimer’s

stable MOFs as aqueous sensors, biomimetic catalysts, and

separators has been investigated recently. In this context,

functionalization of the MOFs will be discussed as a method

for the targeted preparation of the desired sensor com-

26−28

pounds.

It is well-known that according to the tagged

dementia. They also take part in some metabolic trajectories,

such as in vitamins and secondary metabolites, and also the

functional groups, various analytes such as chlorine, chiral

−6

biosynthesis of nucleotides as fundamental participants.

substances, oxidizing gases, and other organic com-

32,33

this regard, arginine is known as one of the most important and

operational amino acids due to its speciﬁc features and also its

signiﬁcant impact in diﬀerent functions of the human body,

such as immune function, wound healing, and promotion of

the release of multiple hormones such as growth hormone and

pounds

can be speciﬁcally sensed by MOFs. In this

regard, ﬂuorescent MOFs, as a class of ﬂuorescence-based

chemical sensors, have been used to conveniently detect

33−37

organic pollutants and heavy-metal ions.

Although there

are a large number of papers on the usage of ﬂuorescent MOFs

as chemical sensors, there are only a few reports on the

application of these materials in the detection of organic

−10

insulin.

It also has a great impact in relaxing blood vessels,

resulting in better blood ﬂow in the body. The development of

eﬃcient receptors capable of binding speciﬁc amino acids

selectively is recognized as a key factor to solving a number of

biological problems such as sensing amino acids in aqueous

media. In spite of recent advancements in analytical methods

and instrumentation, the frugal and trustworthy detection of

chemical substances is still highly sought after. In this regard,

ﬂuorescence-based chemical sensors are commonly used by

scientists due to their advantages of fast response, high

selectivity and sensitivity, low-detection limit, and real-time

38−40

compounds in aqueous solutions.

It is well-known that

the HOMO−LUMO energy gaps of large conjugated π-

systems of many aromatic compounds are in the energetic

range of visible light. So, these molecules can be considered as

a suitable ﬂuorophor group for the emission of ﬂuorescence.

Therefore, we hypothesized that by hanging anthracene, as a

ﬂuorophor group, into a MOF backbone, we could

signiﬁcantly obtain a ﬂuorescent MOF sensor which works

1−13

detection.

dynasty of micro porous materials, metal−organic frameworks

MOFs), a hybrid of both an organic linker and inorganic

As a proportionately novel yet rapidly growing

Received: April 9, 2020

(

node, have gained an enormous amount of attention from

scientists in diﬀerent areas, such as gas storage and

separation, catalysis, energy storage, light harvesting,

and sensing, due to their large internal surface area, high

XXXX American Chemical Society

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

as a detector of amino acids in aqueous media. For testing this

hypotheses, we have synthesized three aromatic-tagged MOFs

by incorporating benzene, naphthalene, and anthracene groups

into a UiO-67 backbone by a condensation reaction between

amine and aldehyde groups and then investigated the activities

of these materials by sensing amino acids in a water solution.

As a famous class of MOFs, the UiO-67-type MOF was chosen

21,43−46

due to its excellent stability under harsh conditions.

Our results show that anthracene-tagged UiO-67-MOF act as a

highly eﬃcient and selective turn-oﬀ ﬂuorescent sensor for the

detection of arginine amino acid over the other 16 water-

soluble amino acids in aqueous media. It must be noted that

luminescent MOF-based sensing of glutathione tripeptide

and homocysteine (an intermediate in the conversion of

methionine to cysteine) has been reported, but to the best

our knowledge, no report on the selective sensing of an amino

acid over other amino acids using MOFs is yet reported in the

literature and the present paper is the ﬁrst report on this

matter.

Figure 1. ORTEP view of the crystal structure of the 2-[(anthracen-9-

ylmethylene)-amino]-biphenyl-4,4′-dicarboxylic acid dimethyl ester

precursor. Thermal ellipsoids are shown at the 30% probability level.

RESULTS AND DISCUSSION

For the synthesis of functionalized aromatic-tagged UiO-67

MOFs, Scheme 1, a direct method is used.

■

introducing the Zr O (OH) cluster nodes along the edges

through carboxylates groups. UiO-67 MOFs have high porosity

and are very stable in aqueous media. By incorporating suitable

ﬂuorophor groups, UiO-67 should be expected to be a

potential candidate for the detection of organic molecules in

aqueous media. The aromatic-tagged UiO-67 MOFs with

covalently substituted benzene, naphthalene, and anthracene

groups through an imidic bond were prepared by the

48,49

First, the

Scheme 1. Procedure of Synthesizing Aromatic-Tagged

UiO-67 MOFs

solvothermal reaction of ZrCl (as the zirconium source),

benzene-tagged, naphthalene-tagged, or anthracene-tagged

,4′-biphenyldicarboxylic acid ligands, and acetic acid as the

modulator in DMF solution at 120 °C for 24 h in closed glass

vessels (Scheme 1 ). For experimental details, see the

Supporting Information. Prepared crystalline materials were

activated by washing them with DMF and methanol solvents

(

repeatedly, three times every 24 h), followed by leaving them

under vacuum at 90 °C overnight to dry. The PXRD patterns

of the resulting white solids, Figure 2a, are identical to that of

the experimental UiO-67, conﬁrming that the incorporation of

NC-aromatic groups did not aﬀect the ﬁnal motif of the

UiO-67 MOFs. In order to ﬁnd the permanent porosities of

functionalized ligands are synthesized according to previously

50,51

reported methods.

The syntheses of the benzene-tagged,

naphthalene-tagged, and anthracene-tagged 4,4′-biphenyldicar-

boxylic acid ligands were carried out by the condensation

reaction between benzaldehyde, 1-naphthaldehyde, or 9-

anthraldehyde and 2-amino-biphenyl-4,4′-dicarboxylic acid to

cleanly produce the imine products. For experimental details,

see the Supporting Information . We tried to prepare suitable

single crystals of the precursors, but only suitable crystals for

diﬀraction analysis of the anthracene-tagged reagent, 2-

the synthesized MOFs, N adsorption/desorption analyses

were performed at 77 K (Figure 2b). All MOFs show a type-I

isotherm for nitrogen physisorption, which conﬁrms the

microporous features of these substances. The Brunauer−

Emmett−Teller (BET) surface areas were 1320.02, 1121.05,

−1

1084.11, and 1000.01 m

for the benzene-tagged,

naphthalene-tagged, and anthracene-tagged UiO-67 MOFs,

respectively. For the morphological study of the aromatic-

tagged UiO-67 MOFs, SEM images are recorded. As seen in

Figure 2 c−e, the SEM images indicate that all three MOFs

have uniform habits. The SEM images reveal that the benzene-

tagged and naphthalene-tagged UiO-67 crystals have an

average size of less than 90 nm, while the average size of the

anthracene-tagged UiO-67 particles is about 200 nm. The

thermal stabilities of the prepared MOFs are studied by TGA

experiments under air in the range of 30−900 °C. UiO-67

MOF lost almost 20% of its weight at 30−500 °C, which is

attributed to the removal of solvents and residual molecules.

For aromatic-tagged UiO-67 MOFs, solvents and residual

molecules are removed at 30−440 °C. The second phase of

55%, 40%, 40%, and 45% weight loss occurs at 500−620 °C for

UiO-67 and 440−550 °C for aromatic-tagged UiO-67, which

[(anthracen-9-ylmethylene)-amino]-biphenyl-4,4′-dicarboxylic

acid dimethyl ester, the product of the condensation of

dimethyl-2-aminobiphenyl-4,4′-dicarboxylate and anthracene

aldehyde, were prepared in DMF solution through slow

evaporation after 3 weeks (Figure 1). As illustrated in this

ﬁgure, the crystal structure determination conﬁrmed the

preparation of 2-[(anthracen-9-ylmethylene)-amino]-biphen-

yl-4,4′-dicarboxylic acid dimethyl ester ligand. This compound

crystallizes in the triclinic crystal system with the centrosym-

metric P1 space group (Table S1 ). In the crystalline state, this

molecule lies on a 2-fold axis of symmetry, so the asymmetric

unit of this compound includes one independent molecule.

The UiO-67 MOF containing 4,4′-biphenyldicarboxylate

linkages and hexanuclear [Zr O (OH) ] building units were

ﬁrst reported in 2008. A cubic 3D framework is obtained by

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

Figure 2. (a) PXRD pattern of benzene-tagged, naphthalene-tagged, and anthracene-tagged UiO-67 MOFs. (b) Adsorption and desorption

isotherms of N at 77 K for benzene-tagged, naphthalene-tagged, and anthracene-tagged UiO-67 MOFs. (c−e) SEM images of benzene-tagged,

naphthalene-tagged, and anthracene-tagged UiO-67 MOFs, respectively. (f) TGA proﬁles of benzene-tagged, naphthalene-tagged, and anthracene-

tagged UiO-67 MOFs.

can be assigned to the complete decomposition of the MOF

frameworks, as shown in Figure 2f.

To study the sensing properties of the prepared MOFs

toward amino acids in aqueous solution, solid-state lumines-

cent properties of activated aromatic-tagged UiO-67 MOFs

were observed at room temperature. For amino acid sensing

properties, 5 μg of the desolvated aromatic-tagged UiO-67

MOF was dispersed in 2.5 mL of water as a solvent in a

ﬂuorescent cell and sonicated for 15 min, and then the cell was

immersed for 1 h to form a stable emulsion before ﬂuorescence

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

of arginine, which exhibited an interesting upward curvature

Article

Figure 3. PL spectral changes observed for UiO-67, ban-UiO-67, naph-UiO-67, and anth-UiO-67 upon the addition of 10⁻⁴M solution of arginine

(

a−d) amino acid in water. The black arrow indicates the decrease of the emission band during titration. Gray bands show the absorption spectra of

the MOF.

experiments. Upon excitation at 320 nm for UiO-67 and 360

nm for aromatic-tagged UiO-67 MOFs, the ﬂuorescence

spectrum of UiO-67, benz-UiO-67, and naph-UiO-67 MOFs

exhibits strong ﬂuorescence bands at 655, 460, and 455 nm,

respectively, while for anth-UiO-67 MOF, the ﬂuorescence

spectrum shows three emission peaks at 388, 405, and 430 nm.

A simple way to determine whether interactions between the

diﬀerent 17 amino acids and UiO-67, benz-UiO-67, naph-UiO-

In order to understand the mechanism of the process and

the quantiﬁcation of the sensing ability of anth-UiO-67 MOF,

emissive spectra of diﬀerent amounts of the analyte were

studied and the I /I ratio was plotted against the concentration

7, and anth-UiO-67 MOF are present or not is to look for

changes in the photoluminescence (PL) spectrum of the MOF

upon the addition of amino acids. So, the PL response of these

four MOFs upon titration of 10 M solution of the diﬀerent

−

7 amino acids was investigated. As exempliﬁed for the

simplest amino acid in Figure S1 , upon the addition of alanine

to all four of the MOFs, no perturbation in the PL bands was

observed and the quenching eﬃciency (QE) of all four MOFs,

upon the addition, is almost 0%.

The same behavior was observed for the other amino acids

except for arginine, Figures S2 −S16 . So it can be concluded

that there is no strong intercalative interaction between the

synthesized MOFs and these amino acids. Also, as it is clear

from Figures 3a-c, upon the addition of arginine, no

perturbations in the PL spectrum of UiO-67, benz-UiO-67,

and naph-UiO-67 is observed. Surprisingly, the addition of an

increasing amount of arginine amino acid induced important

perturbation in the PL spectrum of the anth-UiO-67 MOF and

caused a signiﬁcant turnoﬀ quenching eﬀect on ﬂuorescent

intensities (Figure 3d). In the presence of 280 nM arginine, PL

bands of anth-UiO-67 MOF dramatically decreased with a

quenching eﬃciency of more than 97%. The limit of detection

Figure 4. Stern−Volmer plot obtained by plotting the I /I ratio of the

PL of the anth-UiO-64 MOF as a function of arginine concentration

and ﬁtting the data to the adequate equation.

(Figure 4). Such a remarkable curve ﬁts well to the modiﬁed

Stern−Volmer equation:

I /I = (1 + K [Arg])(1 + K [Arg])

(LoD) and limit of quantiﬁcation (LoQ) of anth-UiO-67

In which, I and I are luminescent intensities before and after

MOF sensor for the detection of arginine in water was

evaluated by using PL titrations. From the titration proﬁle,

Figure S17 , the LoD and LoQ of the anth-UiO-67 MOF sensor

are calculated as 17.344 nM and 57.812 nM, respectively.

the addition of arginine, respectively, [Arg] is concentration of

−

arginine (M ), and K and K are the static quenching

−

constant and dynamic quenching constant (M ), respectively.

It seems that both the dynamic and static quenching processes

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

The Supporting Information is available free of charge at

Article

4,55

are involved with the same ﬂuorophore (here, arginine).

Such mechanism is also observed in other MOFs.

56−58

Fitting

the Stern−Volmer equation by OriginPro resulted in the K

and K values of 5.1 × 10 and 4.8 × 10 , respectively. This

values are comparable with the ones from other reported MOF

9−62

sensors.

The formation of a ground-state nonﬂuorescent

complex between the anth-UiO-67 and arginine can be

considered as the static quenching mechanism. The dynamic

quenching mechanism may be dominated by the diﬀusive

collisions of arginine into the channel of the MOF. The IR

spectra of anth-UiO-67 after immersing it in arginine solution

for 3 h have also been recorded. As it is clear from Figure 5, the

Figure 6. Fluorescence response of anth-UiO-67 MOF (5 μg in 2.5

mL of H O) (gray bar) upon the addition of arginine (280 nM)

(

green bar) and upon the addition of other amino acids (280 nM)

blue bar) in water as the solvent. The red bars represent the change

of the emission that occurs upon the subsequent addition of 280 nM

arginine to the earlier mentioned solution.

background amino acid did not show any obvious disturbance

with the signal response induced by anth-UiO-67/arginine. So,

the anth-UiO-67 MOF shows a reliable ratiometric detection

for arginine amino acid even in the presence of the other 16

amino acids. Although no meaningful correlation can be

suggested between amino acid structures and their quenching

behavior, in this case, the lack of quenching by other amino

acids shows that they either are not capable of quenching or

those that can quench cannot establish the required vicinity

with the imine-anthracene group central core.

CONCLUSION

■

To summarize, we prepared a functionalized UiO-67 metal−

organic framework (MOF) which has anthracene as a

chromophor group. This anthracene-tagged-UiO-67 MOF

has been successfully approved as a ﬂuorescent sensor for

highly eﬃcient and selective detection of arginine over the

other 16 water-soluble amino acids in aqueous media in

nanoscale values. Our remarkable results will provide a great

potential tool for the sensing of arginine in clinical samples.

Figure 5. IR spectra of the anth-UiO-67, arginine, and anth-UiO-67

after immersing them in arginine solution for 3 h. The black and blue

star-labeled peaks correspond to the bands of arginine and the out-of-

and in-plane stretching of the carboxylate groups of the linker,

respectively.

ASSOCIATED CONTENT

sı Supporting Information

https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c01045.

■

host−guest interaction and presence of arginine can be

concluded from the presence of the remarkable peaks of

Synthetic procedures, details of single-crystal diﬀraction

analysis, table of crystal data and structural reﬁnement,

and LoD diagram (PDF )

arginine (labeled with black stars). The out-of- and in-plane

stretching of the carboxylate groups of the linker appeared as

−

intense and sharp bands at 1410 and 1610 cm (labeled with

blue stars), respectively. Also, all the remarkable peaks of the

MOFs are red-shifted because of the possible interaction

between the MOF and arginine. The red-shift of these peaks

can occur because of the possible hydrogen bonding

interaction between the linker of MOF and arginine NH₂

and COOH groups.

Accession Codes

CCDC 1976227 contains the supplementary crystallographic

data for this paper. These data can be obtained free of charge

via www.ccdc.cam.ac.uk/data_request/cif , or by emailing

data_request@ccdc.cam.ac.uk , or by contacting The Cam-

bridge Crystallographic Data Centre, 12 Union Road,

Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

To study the interference of other amino acids on the

sensing of arginine, the PL response of anth-UiO-67 MOF in

the presence of the other 16 amino acids, including alanine,

asparagine, aspartic acid, glutamine, glutamic acid, glycine,

histidine, leucine, lysine, isoleucine, methionine, phenylalanine,

proline, serine, threonine, and valine, has been measured

AUTHOR INFORMATION

Corresponding Author

■

Hamid Reza Khavasi − Department of Inorganic Chemistry and

Catalysis, Shahid Beheshti University, Evin, Tehran

1983963113, Iran; orcid.org/0000-0003-2303-3668;

(Figure 6). The results conﬁrm that the presence of the

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Farha, O. K. Metal −organic framework materials for light-harvesting

Article

Phone: +98 21 29903105; Email: khavasihr@gmail.com;

Fax: +98 21 22431661

(17) So, M. C.; Wiederrecht, G. P.; Mondloch, J. E.; Hupp, J. T.;

and energy transfer. Chem. Commun. 2015, 51, 3501−3510.

(18) Sang, X.; Zhang, J.; Xiang, J.; Cui, J.; Zheng, L.; Zhang, J.; Wu,

Z.; Li, Z.; Mo, G.; Xu, Y.; Song, J.; Liu, C.; Tan, X.; Luo, T.; Zhang,

B.; Han, B. Ionic liquid accelerates the crystallization of Zr-based

metal-organic frameworks. Nat. Commun. 2017, 8, 1−7.

Author

Leila Mohammadi − Department of Inorganic Chemistry and

Catalysis, Shahid Beheshti University, Evin, Tehran

983963113, Iran

(

19) Mason, J. A.; Oktawiec, J.; Taylor, M. K.; Hudson, M. R.;

Complete contact information is available at:

https://pubs.acs.org/10.1021/acs.inorgchem.0c01045

Rodriguez, J.; Bachman, J. E.; Gonzalez, M. I.; Cervellino, A.;

Guagliardi, A.; Brown, C. M.; Llewellyn, P. L.; Masciocchi, N.; Long,

J. R. Methane storage in flexible metal-organic frameworks with

intrinsic thermal management. Nature 2015, 527, 357−361.

(20) Yang, S.; Lin, X.; Lewis, W.; Suyetin, M.; Bichoutskaia, E.;

Parker, J. E.; Tang, C. C.; Allan, D. R.; Rizkallah, P. J.; Hubberstey, P.;

Notes

The authors declare no competing ﬁnancial interest.

Champness, N. R.; Mark Thomas, K.; Blake, A. J.; Schroder, M. A

ACKNOWLEDGMENTS

We would like to thank the Graduate Study Councils of Shahid

Beheshti University, General Campus, for ﬁnancial support.

■

partially interpenetrated metal-organic framework for selective

hysteretic sorption of carbon dioxide. Nat. Mater. 2012, 11, 710−716.

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21) Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi,

E.; Yazaydin, A.O.; Snurr, R. Q.; O ’Keeffe, M.; Kim, J.; Yaghi, O. M.

Ultrahigh porosity in metal-organic frameworks. Science 2010, 329,

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