molecules

Article
Solvothermal Preparation of a Lanthanide Metal-Organic
Framework for Highly Sensitive Discrimination of
Nitrofurantoin and L-Tyrosine
Tian-Tian Wang 1 , Jing-Yi Liu 1 , Rui Guo 1 , Jun-Dan An 1 , Jian-Zhong Huo 1 , Yuan-Yuan Liu 1 , Wei Shi 2, * and
Bin Ding 1, *

1 Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, College of Chemistry,

Tianjin Normal University, 393 Binshui West Road, Tianjin 300387, China;
[email protected] (T.-T.W.); [email protected] (J.-Y.L.); [email protected] (R.G.);
[email protected] (J.-D.A.); [email protected] (J.-Z.H.); [email protected] (Y.-Y.L.)
2 Department of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry,
College of Chemistry, Nankai University, Tianjin 300071, China
* Correspondence: [email protected] (W.S.); [email protected] (B.D.)

Abstract: Metal-organic frameworks (MOFs) have been rapidly developed for their broad appli-
cations in many different chemistry and materials fields. In this work, a multi-dentate building
block 5-(4-(tetrazol-5-yl)phenyl)-isophthalic acid (H3 L) containing tetrazole and carbolxylate moieties
was employed for the synthesis of a two-dimensional (2D) lanthanide MOF [La(HL)(DMF)2 (NO3 )]
(DMF = N,N-dimethylformamide) (1) under solvothermal condition. The fluorescent sensing ap-





 plication of 1 was investigated. 1 exhibits high sensitivity recognition for antibiotic nitrofurantoin
Citation: Wang, T.-T.; Liu, J.-Y.; Guo,
(Ksv : 3.0 × 103 M−1 and detection limit: 17.0 µM) and amino acid L-tyrosine (Ksv : 1.4 × 104 M−1
R.; An, J.-D.; Huo, J.-Z.; Liu, Y.-Y.; Shi, and detection limit: 3.6 µM). This work provides a feasible detection platform of 2D MOFs for highly
W.; Ding, B. Solvothermal Preparation sensitive discrimination of antibiotics and amino acids.
of a Lanthanide Metal-Organic
Framework for Highly Sensitive Keywords: metal-organic frameworks; fluorescence; fluorescent probe; antibiotics; amino acid
Discrimination of Nitrofurantoin and
L -Tyrosine. Molecules 2021, 26, 3673.
https://doi.org/10.3390/
molecules26123673 1. Introduction
Metal-organic frameworks (MOFs) are coordination compounds with open-framework
Academic Editor: Mei Pan
structure. In the past few decades, MOFs have been widely studied in many fields such
as gas storage and separation, adsorption and separation of small chemical species, sens-
Received: 14 May 2021
Accepted: 8 June 2021
ing, catalysis and drug delivery [1–6]. By improving the synthesis method, adjusting
Published: 16 June 2021
the proportion of metal salts, ligands and solvents, and changing the pore structures or
porosities, the catalytic, gas adsorption and separation or fluorescence performance can be
Publisher’s Note: MDPI stays neutral
optimized [7–9]. MOFs can be used as chemical sensors because the interactions between
with regard to jurisdictional claims in
MOFs and analytes could influence their luminescent properties [10–12]. Usually, the
published maps and institutional affil- chemical sensors could have a “turn on” or “turn off” response to small molecules [13–15].
iations. The characteristic of a good sensor is usually summarized as “4S”: sensitivity, selective,
stability and speed of response [16–22].
Since antibiotics were discovered, these molecules have showed applications for
disease cure. However, antibiotic pollution has become more and more serious, which is
Copyright: © 2021 by the authors.
caused by the abuse of antibiotics [23–25]. Nitrofurantoin is an antibiotic that is widely
Licensee MDPI, Basel, Switzerland.
used in the prevention and treatment of animal infectious diseases [26,27], but it has
This article is an open access article
been banned in many countries because of its carcinogenicity and mutagenicity. In 2008,
distributed under the terms and the Ministry of Agriculture of China set the maximum limit of nitrofurantoin in aquatic
conditions of the Creative Commons products at 0.5 µg/kg [28].
Attribution (CC BY) license (https:// On the other hand, L-tyrosine is an essential amino acid. The deficiency of L-tyrosine
creativecommons.org/licenses/by/ may cause phenylketonuria (PKU) [29,30]. PKU is an inborn metabolic error that prevents
4.0/). the conversion of L-tyrosine, causing damage to the central nervous system [31,32]. In

Molecules 2021, 26, 3673. https://doi.org/10.3390/molecules26123673 https://www.mdpi.com/journal/molecules

Molecules 2021, 26, x 2 of 13

Molecules 2021, 26, 3673 2 of 13

may cause phenylketonuria (PKU) [29,30]. PKU is an inborn metabolic error that pre-
vents the conversion of L-tyrosine, causing damage to the central nervous system [31,32].
In addition,
addition, L-tyrosine is associated with dopamine (associated with Parkinson’s disease),
L -tyrosine is associated with dopamine (associated with Parkinson’s disease),
norepinephrine
norepinephrine and andepinephrine
epinephrinesynthesis
synthesis[33].
[33].
Basedononthethe
Based above
above consideration,
consideration, we arewe are interested
interested in developing
in developing fluorescentfluorescent
probes for
probes for both nitrofurantoin and L-tyrosine [34–36]. In this work,
both nitrofurantoin and L-tyrosine [34–36]. In this work, 5-(4-(tetrazol-5-yl)phenyl)-isophthalic
5-(4-(tetrazol-5-yl)phenyl)-isophthalic
acid acid (Hmoieties
(H3 L) containing tetrazole and carbolxylate 3L) containing tetrazole and carbolxylate
was employed as a bridging ligand.
moieties was employed as a bridging ligand.
Through the solvothermal method, a lanthanide MOF, Through the solvothermal
[La(HL)(DMF) method, a lan-
2 (NO3 )] (1) was synthe-
thanide MOF, [La(HL)(DMF) 2(NO3)] (1) was synthesized. We investigated the pho-
sized. We investigated the photo-luminescence sensing performance of 1, which showed
to-luminescence
highly sensing
sensitive sensing performance
function for bothofnitrofurantoin
1, which showed (Ksv :highly sensitive
3.0 × 10 sensing
3 M−1 and func-
detection
tion for both nitrofurantoin (K : 3.0 × 10 3 M −1
4 and
− 1 detection limit: 17.0
limit: 17.0 µM) and L-tyrosine (Ksv : 1.4 × 10 M and detection limit: 3.6 µM) with high
sv μM) and L -tyrosine
(Ksv: 1.4 × efficiency
quenching 104 M−1 andanddetection limit: limit
low detection 3.6 μM) with 1).
(Scheme high quenching efficiency and low
detection limit (Scheme 1).

Scheme1.1.Preparation
Scheme Preparationofofthe
thelanthanide metal-organic
lanthanide framework
metal-organic for for
framework highly sensitive
highly discrimination
sensitive discrimina-
of nitrofurantoin and L -tyrosine.
tion of nitrofurantoin and L-tyrosine.

2. Results and Discussion

2. Results and Discussion
2.1. Structural Description of 1
2.1. Structural Description of 1
1 belongs to monoclinic space group C2/c. As shown in Figure 1a, the asymmetric
unit of1 1belongs
consiststoofmonoclinic space(La1),
one LaIII center group C2/c.
one As shown HL
de-protonated in Figure
− , two 1a, the asymmetric
mono-coordinated
unit of 1 consists of one La III center
− (La1), one
− de-protonated HL −, two mono-coordinated
DMF and one bi-coordinated NO3 . The HL ligand serves as a µ4 -bridge to link four La
DMF and
centers by aone
µ4 -ηbi-coordinated NO3−. The
1 :η1 :η1 :η2 coordination modeHL−through
ligand serves as a μ4-bridge
four carboxylate to link
oxygen four
atoms La
(O1,
centers by a μ -η 1:η1:η1:η2 coordination mode through four carboxylate oxygen atoms
O2, O3 and O4). Two DMF molecules are mono-coordinated to La1 through the terminal
4

oxygen atoms (O8 and O9). Besides, two oxygen atoms (O5 and O6) from the nitrate
ion are coordinated to La1 forming a bidentate chelating coordination mode [37,38]. The
 range.
Figure 1b shows that two neighboring lanthanide atoms (La1A and La1B) are con-
nected by the carboxylate oxygen atoms (O3 and O4) of HL− forming a binuclear build-
ing block. The intermetallic distance of La1A and La1B is 4.1258(4) Å. These binuclear
Molecules 2021, 26, 3673 building blocks are further linked through HL− to form a two-dimensional network.3 It is
of 13
noted that the tetrazole group of HL− is not coordinated and protruded out of the
two-dimensional network. There are hydrogen bonding interactions between the
two-dimensional networks: N(1)–H(1)···O(5), 2.9651(1) Å and C(3)–H(3)···O(7), 3.3256(1)
bond
Å. Thelengths of La-O are ininteractions
hydrogen-bonding the range of further
2.443(2)–2.741(2)
assemble Å.
theThe angle range of O-La-O
two-dimensional networksis
72.49(7)–151.40(8) ◦ . All the bond lengths and angles fell into the normal range.
into a three-dimensional supramolecular structure [39].

(a)

(b)

Figure 1. (a) The fundamental structure of 1 (symmetry codes: A 0.5 − x, 1.5 − y, 1 − z; B x,1 − y,
0.5 + z; C x,1 − y, 0.5 + z.); (b) two-dimensional framework of 1.

Figure 1b shows that two neighboring lanthanide atoms (La1A and La1B) are con-
nected by the carboxylate oxygen atoms (O3 and O4) of HL− forming a binuclear building
block. The intermetallic distance of La1A and La1B is 4.1258(4) Å. These binuclear building
blocks are further linked through HL− to form a two-dimensional network. It is noted that
the tetrazole group of HL− is not coordinated and protruded out of the two-dimensional
network. There are hydrogen bonding interactions between the two-dimensional networks:
N(1)–H(1)···O(5), 2.9651(1) Å and C(3)–H(3)···O(7), 3.3256(1) Å. The hydrogen-bonding
interactions further assemble the two-dimensional networks into a three-dimensional
supramolecular structure [39].
Molecules 2021, 26, x 4 of 13

Molecules 2021, 26, 3673 Figure 1. (a) The fundamental structure of 1 (symmetry codes: A 0.5 − x, 1.5 − y, 1 − z; B x,1 − y,40.5 +
of 13
z; C x,1 − y, 0.5 + z.); (b) two-dimensional framework of 1.

2.2. PXRD, FT-IR and SEM Characterizations of 1

2.2. PXRD, FT-IR and
The powder SEM
X-ray Characterizations
diffraction (PXRD) of 1
pattern of 1 is shown in Figure 2a. The ex-
The powder
perimental X-ray
peaks are diffraction
consistent with(PXRD) pattern one
the theoretical of 1obtained
is shownbyinsingle-crystal
Figure 2a. The ex-
X-ray
perimental
data [40–42].peaks are investigated
We also consistent with
thethe theoretical
stability of 1 inone obtained
different by single-crystal
solvents X-ray
such as ethanol,
data [40–42].
DMF and DMA. WeAfter
also investigated
24 h soakingthe1 instability of 1 in different
these solvents, solvents such
the experimental PXRD aspatterns
ethanol,
DMF
of and DMA.
1 were After 24 hwith
also consistent soaking 1 in these
theoretical solvents,
pattern, the experimental
indicating that 1 wasPXRD patterns
stable of
in these
1 were also consistent with theoretical pattern, indicating that 1 was stable in
solvents (Figure 2b). The slight variation of diffraction intensity may be related to thethese solvents
(Figure 2b).
different Theorientation
crystal slight variation of diffraction
or solvent intensity may be related to the different
effects [43,44].
crystal orientation or solvent effects [43,44].

1
Simulated

5 10 15 20 25 30 35 40 45 50
2θ / degree

(a)

DMA

DMF

Ethyl alcohol

Synthesized

Simulated

5 10 15 20 25 30 35 40 45 50

2θ / degree

(b)
Figure
Figure2.2.(a)
(a)PXRD
PXRDpatterns
patternsof
of1;1;(b)
(b)PXRD
PXRDpatterns
patternsof
of11soaked
soakedin
indifferent
different solutions
solutions for
for 24
24 h.
h.

FT-IR
FT-IR spectrum of 11 ininthe
therange
rangeofof4000–400
4000–400cmcm −1−1was
wasmeasured
measured(Figure
(Figure
S1,S1, Sup-
Supple-
plementary Materials).
mentary Materials). TheThe strong
strong and
and widepeak
wide peakclose
closetoto3412
3412cmcm−−1
1 can be ascribed toto the
the
presence
presence of
of N–H
N–H stretching
stretching vibration.
vibration. The
Thestrong
strong peaks
peaks ofof carboxyl
carboxyl groups
groups appear
appear inin the
the
region of 1648–1584
region of 1648–1584cmcm −1−1(antisymmetric
(antisymmetric stretching
stretching vibrations)
vibrations) cm−1 (sym-
and 1384–1420
and 1384–1420 cm−1
metric stretching vibrations) [45–47]. No FT-IR peaks around 1700 cm−1 also demonstrated
complete deprotonation of carboxyl groups [48–52]. The peaks located at 1499 cm−1 are
from the tetrazole group. The band located at 1296 cm−1 can be ascribed to the vibration
Molecules 2021, 26, x 5 of 13

Molecules 2021, 26, 3673 5 of 13

(symmetric stretching vibrations) [45–47]. No FT-IR peaks around 1700 cm−1 also
demonstrated complete deprotonation of carboxyl groups [48–52]. The peaks located at
1499 cm−1 are from the tetrazole group. The band located at 1296 cm−1 can be ascribed to
of C–N [53–55]. The [53–55].
vibration bands from bands −1 to 719 cm−1 are from the aromatic
779 cmfrom
the vibration of C–N The vibration 779 cm−1 to 719 cm−1 are from the
benzene rings.
aromatic benzene rings.
The morphology
The morphologyof of11 was
was also
also investigated
investigated byby the
the scanning
scanning electron
electron microscope
microscope
(SEM) [56–62]. As shown in Figure 3a,b, 1 has a blocky morphology
(SEM) [56–62]. As shown in Figure 3a,b, 1 has a blocky morphology with a length with a length of
of 54.94
54.94 µm and a width of 21.38 µm [63–67], which is different to that of H L (Figure
μm and a width of 21.38 μm [63–67], which is different to that of H3L3 (Figure S2a,b, S2a,b,
SupplementaryMaterials)
Supplementary Materials)under
underthe
thesame
samescale.
scale.

(a) (b)
Figure
Figure3.3.(a)
(a)The
TheSEM
SEMimage
imageof
of11at
ataascale
scaleof
of20
20μm;
µm;(b)
(b)The
TheSEM
SEMimage
imageof
of11at
ataascale
scale of
of 55 μm.
µm.

2.3.Photo-Luminescent
2.3. Photo-LuminescentProperties Propertiesofof11
ItItisis well
well known
known thatthat luminescence
luminescence can can be
be divided
divided intointo two
two basic
basic modes
modes according
according
tothe
to the spin
spin state
state of
of electrons
electrons during
during radiation
radiation relaxation:
relaxation: fluorescence
fluorescenceand andphosphores-
phosphores-
cence[68–70].
cence [68–70].The Theorigin
originofoflanthanide
lanthanideMOFsMOFscan can be
be mainly
mainly ascribed
ascribed to to four
four kinds
kinds of
of
mechanismslisted
mechanisms listed below:
below: (1) (1) the
the luminescence
luminescence based
based on onthetheorganic
organicligand,
ligand,(2) (2)the
thelumi-
lu-
nescence based
minescence basedononmetalmetalcenter,
center,(3)
(3)the
theluminescence
luminescence basedbased on on the charge transfer,
the charge transfer, and
and
(4) the luminescence based on guest emission. Lanthanide metal
(4) the luminescence based on guest emission. Lanthanide metal ions contain 4f electrons ions contain 4f electrons
shieldingby
shielding 5s225p
by5s 5p6 6orbits,
orbits,which
whichisishardly
hardlyperturbed
perturbedby byitsitschemical
chemicalsurroundings,
surroundings,which which
enable lanthanide ions to have good optical performance
enable lanthanide ions to have good optical performance [71–73]. [71–73].
UV-Vis spectra
UV-Vis spectra of of HH33LL and
and 11 were
weremeasured
measuredatatroomroomtemperature
temperature(Figure
(Figure S3,S3,
Supple-
Sup-
mentary Materials). The maximum absorption peak positions
plementary Materials). The maximum absorption peak positions of H3L and 1 were dif- of H 3 L and 1 were different,
which which
ferent, can be ascribed to the coordination
can be ascribed between H
to the coordination 3 L and the
between H3Lmetal
and center.
the metal Solid-state
center.
fluorescence spectra of H 3 L and 1 were also measured, as shown
Solid-state fluorescence spectra of H3L and 1 were also measured, as shown in Figure S4, in Figure S4, Supplemen-
tary Materials. Materials.
Supplementary The peak value The peakof 1 value
appeared
of 1 at the same
appeared atwavelength of H3 L excited
the same wavelength of H3L at
300 nm, indicating that the fluorescence emission of 1 is from the
excited at 300 nm, indicating that the fluorescence emission of 1 is from the ligand [74– ligand [74–76].
In order to explore different photo-luminescence responses to antibiotics [77,78], the
76].
powder of 1 was evenly distributed in ethanol solution with a concentration of 0.1 mg/mL
In order to explore different photo-luminescence responses to antibiotics [77,78], the
by the ultrasonic method at room temperature (ultrasonic power: 100 W; ultrasonic time:
powder of 1 was evenly distributed in ethanol solution with a concentration of 0.1
20 min). The antibiotics used are listed below: nitrofurantoin (NFT), ronidazole (RNZ),
mg/mL by the ultrasonic method at room temperature (ultrasonic power: 100 W; ultra-
furazolidone (FZD), nitrofurazone (NFZ), dimetridazole (DMZ), ornidazole (ORN), thi-
sonic time: 20 min). The antibiotics used are listed below: nitrofurantoin (NFT), ronida-
amphenicol (THI), metronidazole (MDZ), chloramphenicol (CHL), sulfamethazine (SMZ)
zole (RNZ), furazolidone (FZD), nitrofurazone (NFZ), dimetridazole (DMZ), ornidazole
and sulfadiazine (SDZ). In the fluorescence detection experiments, different antibiotics with
(ORN), thiamphenicol (THI), metronidazole (MDZ), chloramphenicol (CHL), sulfame-
the concentration of 0.001 mol/L were added to the 3 mL suspended solutions containing
thazine (SMZ) and sulfadiazine (SDZ). In the fluorescence detection experiments, dif-
1, drop by drop. The fluorescence quenching results are shown in Figure 4a. The results
ferent antibiotics with the concentration of 0.001 mol/L were added to the 3 mL sus-
show that the quenching efficiency is different, among which NFT shows the most obvious
pended solutions containing 1, drop by drop. The fluorescence quenching results are
quenching result.
Molecules 2021, 26, x 6 of 13

Molecules 2021, 26, 3673 6 of 13

shown in Figure 4a. The results show that the quenching efficiency is different, among
which NFT shows the most obvious quenching result.

(a)

(b)
Figure 4.
Figure 4. (a) Photo-luminescent intensities at 353
(a) Photo-luminescent 353nmnmfor
for11ininthe
thepresence
presenceof
ofdifferent
differentantibiotics;
antibiotics;(b)
(b)photo-luminescent
photo-luminescent
intensities at
intensities at 353
353 nm
nm for
for 11 in
in the
the presence
presenceof
ofdifferent
differentamino
aminoacids.
acids.

On the
theother
otherhand,hand,diverse
diverse amino
amino acids were
acids added
were into into
added the suspensions
the suspensions of 1 toofstudy
1 to
the photo-luminescence
study the photo-luminescence response of 1. Different
response amino acids,
of 1. Different aminoincluding L-tyrosine
acids, including (L-Tyr),
L-tyrosine
creatine, L -malic acid(
(L-Tyr), creatine, L-H2 MI),
L-malic -malic
acid(DL-H 2MI), acid (D-H2 MI),
D-malic acid L(-methionine (L-Met), L-glycine(
D-H2MI), L-methionine (L-Met),L-
Gly), -cysteine ( -Cys), camphorsulfonic acid, -tartaric acid(
L-glycine(L-Gly), L-cysteine (L-Cys), camphorsulfonic acid, L-tartaric acid(L-TA) and
L L L L -TA) and thiomalic acid
were studied.
thiomalic acidAswere
shown in Figure
studied. As 4b, L-Tyrinshowed
shown Figure the 4b,most
L-Tyr obvious
showed fluorescence quench-
the most obvious
ing result. The fluorescence emission intensities of 1 are highly depended
fluorescence quenching result. The fluorescence emission intensities of 1 are highly de- on the addition
of L -Tyr,on
pended indicating
the additionthat 1ofcould
L-Tyr,be used as the
indicating thatfluorescence
1 could be usedprobeasofthe L -Tyr.
fluorescence probe
The Stern–Volmer (SV) curves for NFT and L-Tyr were plotted, respectively [79]. The
of L-Tyr.
SV curves of NFT and L-Tyr
The Stern–Volmer (SV)were approximately
curves for NFT and linear in the
L-Tyr concentration
were range of 0–0.54
plotted, respectively [79].
and 0–0.6 mM, respectively. I /I = K [A] + 1 was used
The SV curves of NFT and L-Tyr were approximately linear in the concentration
0 sv to determine the valuerange
of Ksvof,
in which I and I
0–0.54 and 0–0.60mM, respectively. I0/I = Ksv[A] + 1 was used to determine the value of Kis
represent the emission intensities with or without NFT or L -Tyr, [A] sv,
the concentration
in which of NFT orthe
I and I0 represent L -Tyr, and K
emission sv is the quenching
intensities coefficient.
with or without NFT or The detection
L-Tyr, [A] is
limit of NFT/L-TyrofisNFT
the concentration 17.0/3.6 µM and
or L-Tyr, andKKsvsv isis3.0 104 M−1 (Figure
103 /1.4 × coefficient.
the×quenching 5). The
The detection
PXRD
limit ofpatterns
NFT/L-Tyr of 1 isimmersed in the
17.0/3.6 μM ethanol
and Ksv is solution of NFT
3.0 × 103/1.4 × 10or
4 ML -Tyr for 24 5).
−1 (Figure h are
TheinPXRD
good
agreement with the simulated PXRD of 1, indicating the structure
patterns of 1 immersed in the ethanol solution of NFT or L-Tyr for 24 h are in good of 1 did not collapse
in the detection
agreement with theprocess (Figure
simulated PXRDS5, Supplementary
of 1, indicating the Materials).
structure Therefore, is a good
of 1 did not1collapse in
candidate as a fluorescence probe for NFT or L -Tyr.
the detection process (Figure S5, Supplementary Materials). Therefore, 1 is a good can-
didate as a fluorescence probe for NFT or L-Tyr.
Molecules 2021, 26,
Molecules 2021, 26, 3673
x 77 of
of 13
13

(a) (b)

(c) (d)
Figure 5.
Figure 5. (a)
(a) The
The luminescence
luminescence spectra
spectra of
of 11 with
with different concentrations of
different concentrations of NFT; (b) The
NFT; (b) The emission
emission spectra
spectra by
by adding
adding
different concentration NFT buffer excited at 300 nm; (c) The luminescence spectra of 1 under different concentrations of
different concentration NFT buffer excited at 300 nm; (c) The luminescence spectra of 1 under different concentrations of
L-Tyr; (d) The emission spectra by adding different concentration L-Tyr buffer excited at 300 nm.
L -Tyr; (d) The emission spectra by adding different concentration L -Tyr buffer excited at 300 nm.

Fluorescence
Fluorescence lifetime
lifetime isis an
an important
important parameter
parameter for
for judging
judging thethe mechanism
mechanism of of fluo-
fluo-
rescence quenching [80]. We investigated the fluorescence lifetimes
rescence quenching [80]. We investigated the fluorescence lifetimes for the suspensions for the suspensions
of
of 11 with
with the the addition
addition of of NFT
NFT or or LL-Tyr at room
-Tyr at room temperature,
temperature, as shown in
as shown in Figure
Figure 66 and
and
Table 1. When NFT or L -Tyr was added into the suspensions of 1, the
Table 1. When NFT or L-Tyr was added into the suspensions of 1, the fluorescence lifetimes fluorescence life-
times
changechange from
from 4.44 ns4.44 ns ns
to 4.77 to or
4.77 nsns,
2.82 orindicating
2.82 ns, indicating the of
the existence existence
a dynamic of fluorescent
a dynamic
fluorescent quenching mechanism. The results also suggested
quenching mechanism. The results also suggested that NFT and L-Tyr may interact that NFT and L-Tyr with
may
1interact
through with 1 through
weak weaksuch
interactions interactions such as
as hydrogen hydrogen
bonding bonding interactions.
interactions. ConsideringCon- that
sidering that the photo-luminescent
the photo-luminescent origin of 1 is fromorigin of 1 is fromluminescent
ligand-based ligand-based luminescent
emission and theemis-
2D
sion and the 2D coordination framework of 1 have uncoordinated
coordination framework of 1 have uncoordinated tetrazole moieties of HL , these unco- tetrazole− moieties of
HL −, these uncoordinated tetrazole moieties could have hydrogen bonding interactions
ordinated tetrazole moieties could have hydrogen bonding interactions with the analytic
with
species,thewhich
analytic
canspecies,
reduce which can reduce the photo-luminescent
the photo-luminescent emission of 1 and causeemission of 1 and
the dynamic
cause
quenchingthe dynamic quenching
phenomenon [81]. phenomenon [81].
We also investigated the cycling performance of 1 (Figure 7). 7). After four cycles, the
efficiency of NFT or L-Tyr was 62.98 62.98 or
or 76.48%,
76.48%, indicating
indicating medium
medium cycling
cycling performance.
performance.
Molecules
Molecules 2021, 26, 3673
2021, 26, x 88 of
of 13
13
Molecules 2021, 26, x 8 of 13

(a) (b)
(a) (b)
Figure 6. (a) The decay curve of 1 with the addition of NFT; (b) The decay curve of 1 with the addition of
of L-Tyr.
Figure 6. (a)
Figure 6. (a) The
The decay
decay curve
curve of
of 11 with
with the
the addition
addition of
of NFT;
NFT; (b)
(b) The
The decay
decay curve
curve of
of 11with
withthe
theaddition
addition ofLL-Tyr.
-Tyr.
Table 1. The lifetimes of 1 with or without the addition of NFT and L-Tyr.
Table 1. The
Table lifetimes
1. The of 1 with
lifetimes or without
of 1 with the addition
or without of NFT
the addition and and
of NFT L -Tyr.
L-Tyr.
Caption T1/ns T2/ns B1/% B2/% Combined Life Rating/ns
Caption
Caption T1 /ns T1/ns T2 /ns T2/ns B1/%
B1 /% BB
2/%
2 /% Combined
CombinedLife
LifeRating/ns
Rating/ns
1 3.487773 6.584965 69.38 30.62 4.436
1 1 3.487773 3.487773 6.584965
6.584965 69.38
69.38 30.62
30.62 4.436
4.436
1 + NFT 1.997302 3.409927 41.78 58.22 2.820
1 + NFT
1 + NFT 1.997302 1.997302 3.409927
3.409927 41.78
41.78 58.22
58.22 2.820
2.820
1 + L11 + L-Tyr
-Tyr
+ L-Tyr 2.5289502.528950 10.37314
2.528950 10.37314
10.37314
71.39
71.39
71.39
28.61
28.61
28.61
4.773
4.773
4.773

(a) (b)
(a) (b)
Figure 7. Cycling performance of luminescence intensities at 300 nm of 1 for detecting NFT (a) and L-Tyr (b).
Figure 7.
Figure 7. Cycling
Cycling performance
performance of
of luminescence
luminescence intensities
intensities at
at 300
300 nm
nm of
of 11 for
for detecting
detectingNFT
NFT(a)
(a)and
andLL-Tyr
-Tyr(b).
(b).
3. Materials and Methods
3.
3. Materials and Methods
3.1.
3.1. General Remarks
3.1. General
General Remarks
Remarks
H
H 3L was purchased from Jinan Henghua Technology Co., Ltd., Shan Dong, China.
L was
All
3
other was purchased
H3L chemicalspurchased
were
from
from Jinan
purchased
Henghua
Henghua Technology
Jinancommercially Technology
and applied
Co.,
Co., Ltd.,
Ltd., Shan
directly. Shan Dong,
Dong, China.
Perkin-Elmer China.
240
All
All other
other chemicals
chemicals were
were purchased
purchased commercially
commercially and
and applied
applied directly.
directly. Perkin-Elmer
Perkin-Elmer 240
240
element
element analyzer
analyzer (PerkinElmer,
(PerkinElmer, Dublin,
Dublin, Ireland)
Ireland) isisused
used for
formicroanalysis
microanalysis of C,
of H
C, and
H N
and
element
elements. analyzer
The (PerkinElmer,
ultraviolet-visible Dublin, Ireland)
spectrophotometer is used
(modelfor microanalysis
UV-2600) of C, H
manufactured andbyN
N elements.
elements. TheThe ultraviolet-visible
ultraviolet-visible spectrophotometer
spectrophotometer (model
(model UV-2600)
UV-2600) manufactured
manufactured by
Shimadzu
by Shimadzu Company
Company (Shimadzu,
(Shimadzu, Kyoto,
Kyoto, Japan),
Japan),waswasused
usedto tomeasure
measure the the absorption
absorption
Shimadzu
spectra at Company
room (Shimadzu,
temperature, with Kyoto,
the test Japan),
wavelength was used
ranging to measure
from 200–800thenm.absorption
Powder
spectra
spectra at room temperature,
at room temperature, with the test wavelength ranging from 200–800 nm. Pow-
X-ray diffraction
der X-ray analysis
diffraction waswith
analysis was
the test wavelength
characterized
characterized by Rigaku
by Rigaku
ranging
D/Max-2500from 200–800
D/Max-2500 (Rigaku, nm. Powder
Tokyo,
(Rigaku, Ja-
Tokyo,
X-rayX-ray
pan) diffraction analysis equipped
diffractometer was characterized
with by Rigaku
Cu-Kα radiation D/Max-2500
at a (Rigaku,
wavelength of Tokyo,
0.154 Ja-
nm.
Japan) X-ray diffractometer equipped with Cu-Kα radiation at a wavelength of 0.154 nm.
pan) X-ray diffractometer
Photo-luminescence equipped with Cu-Kα radiation at a wavelength of 0.154 nm.
Photo-luminescence lifetimeslifetimes and
and solid-state
solid-state fluorescence
fluorescence spectra
spectra werewere measured
measured by by FS5
FS5
Photo-luminescence
fluorescence lifetimes and solid-state fluorescence spectraUK). wereThemeasured by FS5
fluorescence spectrometer (Edinburgh Instruments, Edinburgh, UK). The RF-5301 fluo-
spectrometer (Edinburgh Instruments, Edinburgh, RF-5301 fluo-
fluorescence spectrometer (Edinburgh
rescence Instruments, Edinburgh,usedUK). The RF-5301 fluo-
rescence spectrophotometer
spectrophotometer (Shimadzu,
(Shimadzu, Kyoto, Japan) Japan) was used
was tocarry
to carry outthe
out thephoto-
pho-
rescence spectrophotometer
to-luminescence sensing (Shimadzu,
experiment, equippedKyoto, Japan)
with was unit
usedand to 1carry
cm××out the pho-
luminescence sensing experiment, equipped with a aplotter
plotterunit and 1 cm 1 cm quartz
to-luminescence
battery sensing experiment, equipped with a plotter unit and 1 cm × 1 cm quartz
battery in phosphorescent mode.
battery in phosphorescent mode.
 Molecules
Molecules 2021,
2021, 26,26, x
3673 9 of
9 of 1313

3.2.Preparation
3.2. Preparationofof[La(HL)(DMF)
[La(HL)(DMF)(NO 2(NO3)] (1)
2 3 )] (1)
La(NO 3 ) 2 ·
La(NO3 )2 ·6H2 (129.9 mg, 0.3 mmol), HH33LL (31.0
6H 2O (129.9 mg, 0.3 mmol), (31.0mg,
mg,0.1 0.1mmol),
mmol),ethanol
ethanol(3(3mL) mL)andand
DMF(1(1mL)
DMF mL)were wereadded
addedtotoa abeaker
beakerand andstirred
stirredforfor0.50.5h,h,and
andthen
thenthe themixture
mixturewas was
transferredtotoaasteel
transferred steelhigh-pressure
high-pressurereaction
reactionkettle
kettlewhich heatedtoto9090◦ C
whichisisheated °Cfor
for7272h,h,and
and
cooledtotothe
cooled theambient
ambienttemperature
temperaturewithin
within3636h.h.The Theresulting
resultingpalepaleyellow
yellowpowder
powderwas was
cleanedwith
cleaned withethanol
ethanol several
several times
times (Scheme
(Scheme 2). room
2). At At room temperature,
temperature, the powder
the powder of 1 wasof 1
evenly distributed in ethanol solution with a concentration of 0.1 mg/mL
was evenly distributed in ethanol solution with a concentration of 0.1 mg/mL by the ul- by the ultrasonic
method,
trasonicwhich
method, waswhich
used was
for further fluorescent
used for measurement.
further fluorescent Yield: 36%Yield:
measurement. based36%on H 3 L.
based
Elemental analysis calculations
on H3L. Elemental (%) for C21(%)
analysis calculations H22for
LaN C721O
H922: LaN
C 38.49, H 38.49,
7O9: C 3.38, NH14.96;
3.38, Found:
N 14.96;
CFound:
38.57, H
C 3.49,
38.57,NH15.13. 3.49, FT-IR
N 15.13. (cm−1data
dataFT-IR , KBr):(cm3412(w),
−1, KBr): 1649(m),
3412(w), 1621(m),
1649(m),1584(w),
1621(m),
1500(w),
1584(w),1449(w),
1500(w), 1421(w),
1449(w), 1384(s), 1296(w),
1421(w), 1112(w),
1384(s), 779(w),
1296(w), 719(w),779(w),
1112(w), 674(w).719(w),
The prepared
674(w).
sample needs to be pretreated before FT-IR and other characterization.
The prepared sample needs to be pretreated before FT-IR and other characterization.

Scheme 2. Synthesis route for 1.

Scheme 2. Synthesis route for 1.

3.3.X-ray
3.3. X-rayCrystallography
Crystallography
TheBruker
The Bruker SMART
SMART 1000
1000 CCD CCD diffractometer
diffractometer (Bruker,
(Bruker, AVANCE,AVANCE, Billerica,
Billerica, MA, USA) MA,
USA)
was was
used to used to measure
measure the diffraction
the diffraction data of a data
singleofcrystal
a single
of crystal of 1, with
1, equipped equipped with
graphite
graphite monochromatic
monochromatic Mo-Kα apertureMo-Kα aperture
radiation (λ radiation (λ =The
= 0.71073 Å). 0.71073 Å). The ω-φ
ω-ϕ scanning scanning
strategy was
applied
strategywith
wasLorentz
appliedpolarization
with Lorentzand empirical and
polarization absorption correction.
empirical absorption By correction.
utilizing the By
SHELXS97 program, the structure 2 was improved by2 utilizing a full matrix least squares
of Fthe
utilizing the SHELXS97 program, structure of F was improved by utilizing a full
calculation.
matrix least The anisotropic
squares temperature
calculation. factor was temperature
The anisotropic assigned to allfactor
atomswasexcept hydrogen
assigned to all
atoms,
atomsand the isotropic
except hydrogentemperature
atoms, and factor was arbitrarily
the isotropic selected
temperature to bewas
factor 1.2 times that of
arbitrarily se-
the parent [82,83]. The R(F), WR(F 2 ) and goodness of fit protocol factors, details of data
lected to be 1.2 times that of the parent [82,83]. The R(F), WR(F ) and goodness of fit
2

collection and analysis

protocol factors, detailsareofshown in Table and
data collection 2. The selected
analysis arebond
shown lengths,
in Tableangle hydrogen
2. The selected
bonds ◦
bond [Å] and angles
lengths, angle [hydrogen
] are given in Table
bonds [Å] S1,
andSupplementary
angles [°] are Materials. CCDC-1873742
given in Table S1, Supple-
represents the crystalCCDC-1873742
mentary Materials. data for this work. The data
represents theiscrystal
available
datafree
forofthis
charge
work.through
The data theis
Cambridge Crystal
available free Data through
of charge Center. the Cambridge Crystal Data Center.

Table2.2.Crystal
Table CrystalData
Dataand
andStructure
StructureRefinement
RefinementInformation
Informationfor
for1.1.

11
Formula
Formula CC HH
2121 LaN
2222 LaN
7O7O9
9
·mol−1−1
MM(g(g·mol )) 655.36
655.36
Crystal system
Crystal system Monoclinic
Monoclinic
Space group C2/c
Space group C2/c
Temperature 133.32(16)
Temperature
a (Å) 133.32(16)
28.2179(10)
b a(Å)
(Å) 28.2179(10)
14.0169(5)
c b(Å)
(Å) 14.3437(5)
14.0169(5)
◦)
αc((Å) 90
14.3437(5)
β (◦ ) 99.720(4)
α (°) 90
β (°) 99.720(4)
Molecules 2021, 26, 3673 10 of 13

Table 2. Cont.

1
γ (◦ ) 90
V (Å3 ) 5591.9(3)
Z 8
F (000) 2608
ρcalc (Mg·m−3 ) 1.557
µ (mm−1 ) 1.586
Data/restraints/parameters 4916/36/362
GOF on F2 1.069
R1 a (I ≥ 2σ(I)) 0.0273
wR2 b (all data) 0.0643
a R1 = Σ||Fo | − |Fc ||/|Fo |, b wR2 = [Σw(Fo 2 − Fc 2 )2 /Σw(Fo 2 )2 ]1/2 .

4. Conclusions
In summary, the preparation, structural characterization and photo-luminescent sens-
ing performance of a 2D lanthanide metal-organic framework was reported. It can be
utilized to detect trace nitrofurantoin (Ksv : 3.0 × 103 M−1 and detection limit: 17.0 µM)
and L-tyrosine (Ksv : 1.4 × 104 M−1 and detection limit: 3.6 µM) with high sensitivity and
good recyclability. This work not only enriches the research of lanthanide MOFs, but also
provides a theoretical basis for 2D MOF-based chemical sensors.

Supplementary Materials: Table S1: Selected bond lengths (Å) and angles (◦ ), Figure S1: FT-IR
spectrum of 1, Figure S2: (a) The SEM images of H2 L showed that the powder is needle-like with the
length between 0.54–5.99 m at a scale of 5 µm (b) The SEM images of H2 L showed that the powder is
acicular on a 2 µm scale., Figure S3: UV-Vis spectra of H3 L and 1, Figure S4: Solid-state fluorescence
of H3 L and 1, Figure S5: powder X-ray patterns for 1, 1 + NFT and 1 + L-Tyr.
Author Contributions: Conceptualization, B.D.; data collocation and analysis, T.-T.W., J.-Y.L., J.-D.A.
and Y.-Y.L.; Validation, R.G. and J.-Z.H.; Writing—original draft, T.-T.W.; Writing—review and editing,
W.S. and B.D. All authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the National Natural Science Foundation of China
(21931004), the Natural Science Foundation of Tianjin (18JCJQJC47200), the Ministry of Education of
China (B12015) and the Natural Science Foundation of the Science and Technology Development
Fund of Tianjin Education Commission for Higher Education (2019ZD15).
Data Availability Statement: The data presented in this study are available with the authors.
Acknowledgments: The authors are grateful to Tianjin Normal University and Nankai University
for the necessary research works and instruments.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Sample of the compound 1 is available from the authors.

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