Study of a new 3D MOF and its adsorption, slow release and biological activity in water-soluble and oil-soluble pesticides

Article abstract of DOI:10.1016/j.poly.2020.114752

The ligands of (E)-bis(p-3-nitrobenzoic acid) vinyl (C₁₆H₁₀N₂O₈) were synthesized in three steps, and then the MOF-Zn₂(EBNB)₂(BPY)₂·2H₂O was synthesized by solvotherma

Full text of DOI:10.1016/j.poly.2020.114752

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Study of a new 3D MOF and its adsorption, slow release and biological activi‐
ty in water-soluble and oil-soluble pesticides
Deng Linxin, Junjie He, Li Borui, Wang Nana, Li Song
PII:
S0277-5387(20)30409-5
DOI:
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https://doi.org/10.1016/j.poly.2020.114752
POLY 114752
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Accepted Date:
22 June 2020
12 August 2020
Please cite this article as: D. Linxin, J. He, L. Borui, W. Nana, L. Song, Study of a new 3D MOF and its
adsorption, slow release and biological activity in water-soluble and oil-soluble pesticides, Polyhedron (2020),
doi: https://doi.org/10.1016/j.poly.2020.114752
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Study of a new 3D MOF and its adsorption, slow release and
biological activity in water-soluble and oil-soluble pesticides
+
a
+c
b
c
d
Deng Linxin , Junjie He , Li Borui , Wang Nana , Li Song *
a
(
Yunnan Police Officer College, Kunming 650223, China)
(b Faculty of Science and Engineering, University of Nottingham Ningbo China, Ningbo 315100, China)
(c College of Architectural Engineering, Yunnan Agricultural University, Kunming 650201, China)
(d College of Science, Yunnan Agricultural University, Kunming 650201, China)
Abstract: The ligands of (E)-bis(p-3-nitrobenzoic acid) vinyl (C16
steps, and then the MOF-Zn (EBNB) (BPY) ·2H O was synthesized by solvothermal method. This structure was
characterized by X-ray single crystal diffraction, SEM and TG. The pesticide loading and release of
Zn (EBNB) (BPY) ·2H O were also studied with jinggangmycin and avermectin as model pesticides,
representing water-soluble and oil-soluble pesticides respectively. The results show that the highest loading
amount of Zn (EBNB) (BPY) ·2H O to jinggangmycin and avermectin was 0.346g/g and 0.304g/g. The pesticide
10 2 8
H N O ) were synthesized in three
2
2
2
2
2
2
2
2
2
2
2
2
delivery system was a two-phase mode and the cumulative release of jinggangmycin was 76.8%, of avermectin
was 73.8% in 84 hours, which show obvious slow release effect. Meanwhile, compared with the control group of
jinggangmycin·avermectin wettable powder, the sustained-release system has better effect on the inhibition of
rhizoctonia graminearum.
Keywords: MOFs; jinggangmycin; avermectin; pesticide loading; pesticide release; biological activity
environmental pollution, long-term residue and
1
Introduction
safety problems. Therefore, it has become the
trend of pesticide development to develop
environmentally friendly pesticide formulations,
improve the deposition rate and effective
utilization rate of the target, and reduce the
number of pesticide uses. With the development
of pesticide processing industry and the
enhancement of people's awareness of
environmental protection, the research and
development of "water-based, granular and
slow-release" dosage forms has become a
The improper use of pesticides will bring
great harm to the environment and human
beings. At present, pesticide formulations are
generally backward and the application methods
are
unreasonable.
Extensive
farmland
management and one-sided pursuit of control
results lead to low utilization of pesticides. A
large number of active ingredients migrate into
the environment (such as leaching, drifting,
volatilization, etc.), enter the surface,
groundwater and other areas, and become an
important source of agricultural non-point source
[4]
hotspot in the field of pesticide processing .
Slow and controlled release pesticide is a
new type of pesticide preparation. It can change
the structure of pesticide preparation by physical
and chemical methods, so that the active
ingredients of pesticide can be slowly released
into the environment in set space and
predetermined time, and the drug concentration
can be maintained in the effective level for a
long time. Comparing with conventional
pesticide formulations, slow-release and
[1, 2]
pollution
.
The utilization rate of conventional
pesticides is only 20%~30%. Theoretically, the
needed amount of pesticides is much less than
the actual amount of pesticides used, and the loss
rate through various ways is as high as 50% -
[3]
6
0% . The unreasonable use of a large amount
of pesticides will not only increase the cost of
agricultural production, but also bring serious
*
Corresponding author. Tel: +86 15198701727
E-mail: sirleee@live.cn;
+] These authors contributed equally to this work.
[
Project supported by the National Natural Science Foundation of China / Regional Science Foundation Project. No.21965038 and Basic Research Program of
Yunnan Province / General Projects of Basic Research. No.2019FB024.
1

controlled-release pesticides have the advantages
of prolonging the validity period, reducing the
application times, reducing the decomposition
and loss of pesticide active components, and
improving the efficacy, which has become a
research hotspot of pesticide formulations in
pesticides and environmental pollution.
Experimental
.1 Reagents
All chemical reagents used in this
2
2
[5]
experiment are commercial reagents, which are
used directly.
recent years .
As one of the advanced frontier materials,
metal organic frameworks （ MOFs ） is the
fastest developing direction of coordination
chemistry in recent ten years[6,7]. It has a super
molecular network structure and combines with
the characteristics of composite polymer and
coordination compound, and has the advantages
2
.2 Synthesis
2
.2.1 Synthesis of (E) - bis (p-3-nitrobenzoic
acid) ethylene ligand (C H N O )
1
6
10
2
8
[8]
of both inorganic and organic compounds . The
structure of this kind of frame material can
realize diversified design and adjustable pore
size and structure, so it can realize semi
directional design synthesis[9,10]. The research of
this kind of molecular functional materials has
spanned many fields, such as crystallography,
Figure 1 structure diagram of (E)-di(p-3-nitrobenzoic acid)
ethylene (C H N O )
1
6
10
2
8
materials
coordination chemistry, organic chemistry, etc.,
and successfully realized the field
science,
inorganic
chemistry,
Figure 2 synthetic route of (E)-di(p-3-nitrobenzoic acid)
10 2 8
ethylene (C16H N O )
crossing[11,12,13]. MOFs have been widely used in
the fields of gas capture, storage and
[
14]
[15]
separation ; pesticide release ; substance
[
16]
[17,18, 19]
detection ; optical
, magnetic, electrical
[20]
[21]
science ;
resolution[22]
catalytic
and
science ;
so
chiral
on.
Zn (EBNB) (BPY) ·2H O is a new type of 3D
2
2
2
2
[23]
porous MOFs material . It has excellent gas
adsorption performance in study of many kinds
of gas molecules, but it has not been reported as
a pesticide carrier.
1
Figure 3 H NMR (200MHz DMSO) of
(
10 2 8
E)-di(p-3-nitrobenzoic acid) ethylene (C16H N O )
In this study, Zn (EBNB) (BPY) ·2H O
2
2
2
2
was used to encapsulate pesticides with high
specific surface area and large pore size to carry
out pesticide release and biological activity
experiments on water-soluble and oil-soluble
representative pesticides. So as to achieve the
2
00ml concentrated sulfuric acid was
pouring into a 400ml flask, and 100ml fuming
nitric acid was added under 0℃ ice water bath
while stirring constantly.
p-chloromethylbenzoic acid was added in small
parts. After 90 minutes of reaction,
p-chloromethylbenzoic acid was completely
dissolved into the mixed acid. All substances in
Then
10g
of
development
environmental
of
new
formulations
pesticides,
of
the
protection
improvement of the effective utilization rate of
pesticides, the extension of the duration of
pesticide efficacy, and the reduction of the use of
2

[
26]
the bottle was pouring into 600ml of ice water, a
large amount of white solid is precipitated
immediately. The residual mix-acid was filtered
and washed, and then the product was
recrystallized in toluene solvent. The white
crystal of 3-nitro-p-chloromethylbenzoic acid
software . The main crystallographic data of
Zn (EBNB) (BPY) ·2H O are listed in table 1.
2
2
2
2
Pore structure parameters are also given in table
2.
CCDC: 910300 for compound 1.
Table 1 Crystallographic data and structural correction
[24]
was obtained and dried in an oven (89%) .
0ml anhydrous ethanol was poured into a
00ml beaker, and 5.7g KOH was dissolved in it.
2 2 2 2
conditions of Zn (EBNB) (BPY) ·2H O
5
Empirical formula
C
26
H
18
N
4
O
9
Zn
3
Fomular weight
Crystalsystem
Space group
Wavelength(Å)
Temperature(K)
a（Å）
595.81
Then 5.00g of 3-nitro-p-chloromethylbenzoic
acid was poured in to form brown precipitate,
Triclinic
P-1
which is potassium salt of (E)
-
di
0.71073
(p-3-nitrobenzoic acid) ethylene. After reaction
293(2)
at room temperature for 45 min, the solid was
vacuumed and dissolved in 70ml water. Adding
HCl to the aqueous solution to adjust pH=1 then
form a precipitate. The solid was collected and
recrystallized with tetrahydrofuran solvent. The
yellow crystal (E)-di(p-3-nitrobenzoic acid) vinyl
8.1862（9）
11.4220
b（Å）
（
14）
c（Å）
14.2863（17）
°
α（ ）
96.8030（10）
93.0450（10）
102.472（2）
1290.8
°
β（ ）
(
C H N O ) compound was obtained and dried
16 10 2 8
°
γ（ ）
[25] 1
in an oven (78%) . H NMR(200MHz DMSO)
3
V（Å ）
δ7.62（s,2H）;7.89(d,2H);8.52(d,2H);9.06(s,2H).
（
3）
2
.2.2 Synthesis of Zn (EBNB) (BPY) ·2H O
Z
2
1.533
1.013
608
2
2
2
2
Density (g/cm3)
The (E)-di(p-3-nitrobenzoic acid) ethylene
ligand (C H N O ) (0.15mmol), 4,4'-bipyridine
ligand
-
1
μ(mm )
1
6
10
2
8
F(000)
(BPY,0.15mmol),
zinc
nitrate
θ range (°)
GOF on F2
2.557 to 26.079
1.008
=0.0499
（
Zn(NO ) ·6H O，0.15mmol), ethanol 2ml and
3
2
2
H O 10ml were put into a 50ml high-pressure
2
R
1, wR
2
[I>2σ(I)]
=0.1067
(all data)
R
1
reactor, and the pH was adjusted to 9,
ultrasounded, 150 ℃ for two days. The rhombic
yellow crystal (E)-di(p-3-nitrobenzoic acid)
ethylene can be obtained after filtration and
washing. Element analysis: C 52.45, n 9.34, H
wR
2
R
1, wR
2
R
1
=0.0750
7
45.86
2
BET surface area（m /g）
3
9
.11, Zn 10.89%; theoretical value: C 52.37, n
.40, H 3.02, Zn 10.98%. The product is
2
Langmuir surface area（m /g）
1021.59
6.43
Average diameter of mesopore(nm)
Average pore size of micropore
mesopore volume(nm)
composed of C H N O Zn (595.81).
2
6
18
4
9
0.38
0.0589
0.411
0.401
2
.3 Determination of structure
The single crystal
Zn (EBNB) (BPY) ·2H O were measured by
3
micropore volume (cm /g)
data
of
3
Vtotal (cm /g)
2
2
2
2
wR
2
=0.1153
Bruker smart-1000 CCD single crystal X-ray
diffraction analyzer. Crystal structure analysis
and structure refinement was using shell XTL
Table 2 Pore structure parameters of Zn
2
2 2 2
(EBNB) (BPY) ·2H O
3

2
.4 Study on pesticide adsorption and slow
wavelength was measured, and the pesticide
loading of Zn (EBNB) (BPY) ·2H O was
calculated.
pesticide loading = (amount of pesticide in
MOFs / total mass of MOFs) ×100％
release of Zn (EBNB) (BPY) ·2H O
2
2
2
2
2
2
2
2
jinggangmycin and avermectin were
selected as model pesticides, representing
water-soluble
respectively. Thus the pesticide loading, release
and biological activity of
Zn (EBNB) (BPY) ·2H O were studied.
and
oil-soluble
pesticides
2
.4.3
Determination
of
the
release
performance of Zn (EBNB) (BPY) ·2H O
2
2
2
2
containing target pesticidesp
2
2
2
2
Table 3 Solvents, measuring wavelengths and release
Take 2 mg of Zn (EBNB) (BPY) ·2H O
2 2 2 2
media of target pesticides
loaded with the target pesticide and put it into 20
ml release medium. Under the constant
temperature oscillator of (37 ± 1 ℃) (oscillation
Target
solvent
Measuring
wavelength
215nm
Release media
pesticide
-1
speed of 100r. Min ), take 1ml of solution every
2h and add equal amount of release medium.
After centrifuging the extracted solution
12000rpm, 20min), take the supernatant and
jinggangmycin
water
Deionized water
1
/
isopropanol
7/3
Anhydrous methanol
=
(
Avermectin
methanol
245nm
measure its absorbance with ultraviolet spectrum.
According to the established standard curve of
target pesticide, the content of target pesticide in
solution was calculated, and the relation curve
between cumulative release and time was drawn.
2
.4.1 Standard curve
Accurately weigh appropriate amount of
target pesticide and prepare appropriate
concentration solution with appropriate solvent.
The maximum absorption peak was found by
wavelength scanning with solvent as blank. The
standard curve of absorbance (A) and
concentration (c) at this wavelength was
established. The standard curve is suitable for
pesticide loading environment.
Thus,
the
performance
releasing
2
of
target
Zn (EBNB) (BPY) ·2H O
2
2
2
pesticide was investigated.
.4.4 Determination of biological activity of
Zn (EBNB) (BPY) ·2H O containing target
pesticide
2
2
2
2
2
Accurately weigh appropriate amount of
target pesticide and prepare solution with release
medium solvent. The maximum absorption peak
was found by wavelength scanning with solvent
as blank. Then the concentration gradient of the
standard solution is prepared, and the standard
curves of absorbance (A) and concentration (c) at
this wavelength are established. The standard
curve is suitable for pesticide loading
environment.
The growth rate method was used to
determine the control effect of pesticides loaded
by Zn (EBNB) (BPY) ·2H O on the tested
2
2
2
2
strains. According to the pre-experimental
results, the mass concentration of
Zn (EBNB) (BPY) ·2H O loaded with the target
2
2
2
2
pesticide was set as 2.500 μg/ml. Then, the
bacteriostatic effect on Rhizoctonia cerealis was
determined. Using sterile water as blank control,
jinggangmycin·avermectin wettable powder as
medicament control. Each process is set to repeat
three times.
2
.4.2 Target pesticides loading
Accurately weigh
2mg
of
Zn (EBNB) (BPY) ·2H O after drying and
2
2
2
2
activation, and add 1ml of corresponding solvent
containing 10mg of target pesticide. Then mixing
it with ultrasound for 24 hours. After that,
centrifuges the solution (10000rpm, 10min).
Take 100 μl of the supernatant and dilute it to
PDA medium was prepared and ready to
use after sterilization. Under sterile condition, a
certain number of bacteria-cake with diameter of
5
mm was made on the edge of the colonies of the
tested strains, which have been cultured in
1
0ml. Then the absorbance at the corresponding
4

advance for standby. Use a micropipette to inject
high concentration mother liquor (the
concentration of mother liquor is 100 times of
the test concentration) into each bottle of PDA
culture medium successively. Each of it contains
quantitative sterilization and was melted by heat.
Shake it well, divide it into 3 Petri dishes, and
a 2D plane. Along the c-axis direction, the layers
and the interlayer are connected with Zn (Ⅱ) ion
via bipyridine column ligand to build a 3D
network structure, and finally a 3D metal organic
framework material with one-dimensional pore
structure is formed (Figure 5, Figure 6, Figure 7).
make
corresponding
a
pesticide containing plate of
concentration. In aseptic
condition, the 5 mm bacteria-cake was moved to
the center of the culture medium with pesticide,
and the hypha was face down to make the hypha
face contact with the culture medium. One
bacteria-cake is placed in each culture dish and
was placed in the incubator with the culture
temperature of 28 ℃. After one week of culture,
the colony diameter was measured by the cross
method of Vernier caliper and the average value
was taken.
Figure 4 Secondary building unit of
3
Results
.1
Zn (EBNB) (BPY) ·2H O
2 2 2 2
Zn (EBNB) (BPY) ·2H O
3
Crystal
structures
of
2
2
2
2
The results of X-ray single crystal structure
test show that Zn (EBNB) (BPY) ·2H O crystal
2
2
2
2
is triclinic system and P-1 space group. There are
two Zn (Ⅱ) ions, two (E) - di (p-3-nitrobenzoic
acid) ethylene ligands and two bipyridine ligands
in its secondary building unit. Figure 4 shows the
metal
coordination
environment
of
Zn (EBNB) (BPY) ·2H O. It can be seen that
2
2
2
2
Zn1 and Zn2 are in the form of 6-coordination,
and the four oxygen coordination atoms are from
two carboxyl oxygen atoms and two water
molecules with double tooth chelation structure,
and the two nitrogen coordination atoms are
from two coordination bipyridine.
2 2 2 2
Figure 5 2D layer structure of Zn (EBNB) (BPY) ·2H O
Figure 4 also shows that a single
(E)-di(p-3-nitrobenzoic acid) ethylene ligand is
coordinated with two Zn (Ⅱ) ions along the AC
plane, and each Zn (Ⅱ) ion is also coordinated
with an oxygen coordination atom in a water
molecule and two (E)-di(p-3-nitrobenzoic acid)
ethylene ligands, thus extending outward to form
5

Figure 8 Microscopic characterization of
Zn (EBNB) (BPY) ·2H
2
2
2
2
O
Figure 6 Three dimensional structure of
Zn (EBNB) (BPY) ·2H
2
2
2
2
O
Figure 9 SEM characterization of
Zn (EBNB) (BPY) ·2H
2
2
2
2
O
3
.3 Powder XRD characterization of
Zn (EBNB) (BPY) ·2H O
2
2
2
2
Figure 10 is the powder XRD
characterization of Zn (EBNB) (BPY) ·2H O
2
2
2
2
Figure 7 The frame structure of Zn
2
(EBNB)
2
(BPY)
2
·2H
2
O
which are actual measured, software simulation’s
and ligand’s. Among it, A is the ligand
3
.2 Microscope and SEM characterization of
bipyridine’s
E)-di(p-3-nitrobenzoic acid) ethylene ligand’s
XRD, C is the Zn (EBNB) (BPY) ·2H O’s
XRD,
B
is
the
Zn (EBNB) (BPY) ·2H O
2
2
2
2
(
The
morphology
of
2
2
2
2
Zn (EBNB) (BPY) ·2H O was characterized by
actual measured powder XRD, and D is the
Zn (EBNB) (BPY) ·2H O’s simulated XRD. It
2
2
2
2
microscope and SEM. Figure 8 is a microscope
picture of Zn (EBNB) (BPY) ·2H O. It can be
2
2
2
2
can be seen from the figure that the measured
value of Zn (EBNB) (BPY) ·2H O is in good
2
2
2
2
seen that it is yellow diamond crystal. Figure 9
shows the surface morphology of
2
2
2
2
agreement with the simulated value of the
software, which shows that the compound is a
pure phase, and there are obvious differences
between the two ligands.
Zn (EBNB) (BPY) ·2H O in SEM. It can be
2
2
2
2
seen
that
the
surface
structure
of
Zn (EBNB) (BPY) ·2H O is of like fish scale.
2
2
2
2
6

The ratio of jinggangmycin, avermectin
mass to carrier mass and the relationship
between the loading time and the amount of
Zn (EBNB) (BPY) ·2H O were given in table 4
and table 5 respectively. It can be seen that with
the increase of the ratio of the target pesticide
mass to carrier mass (fixed carrier mass,
Figure 10 Powder XRD characterization of
Zn (EBNB) (BPY) ·2H
2
2
2
2
O
(
A the ligand bipyridine’s XRD. B the (E)-di(p-3-nitrobenzoic acid) ethylene
ligand’s XRD. C the Zn (EBNB) (BPY) ·2H O’s actual measured powder
XRD. D the Zn (EBNB) (BPY) ·2H
2
2
2
2
2
2
2
2
2
2
2
2
O’s simulated XRD.)
3
.4
Thermal
analysis
of
increased pesticide mass), the pesticide loading
of Zn (EBNB) (BPY) ·2H O is increasing. The
Zn (EBNB) (BPY) ·2H O
2
2
2
2
2
2
2
2
The thermal gravimetric analysis of
Zn (EBNB) (BPY) ·2H O was carried out by
loading of Zn (EBNB) (BPY) ·2H O also
2 2 2 2
increased with the prolongation of the action
time. However, the highest pesticide loading of
Zn (EBNB) (BPY) ·2H O appeared on the 5th
2
2
2
2
DSC-TG in the temperature range of 0 ℃ to
00 ℃. Figure 11 is the DSC-TG diagram of
Zn (EBNB) (BPY) ·2H O. It can be seen from
6
2
2
2
2
day, Under different mass ratio of pesticides and
carriers. The result shows that the pesticide
loading amount of Zn (EBNB) (BPY) ·2H O
2
2
2
2
the figure that Zn (EBNB) (BPY) ·2H O can be
2
2
2
2
stabilized
up
to
350
lost
℃.
3.78%
2
2
2
2
Zn (EBNB) (BPY) ·2H O
reached the maximum value at the 5th day of
adsorption.
2
2
2
2
(theoretical value 3.65%) of its first thermal
weight in the temperature range of 50-200 ℃,
which can be attributed to the loss of guest
molecules. However, in the temperature range
of 350 ℃ ~ 560 ℃, the structure collapses,
resulting in 46.58% (theoretical value 45.45%)
weight loss and 49.15% (theoretical value
When the action time was extended to 7
days, the pesticide loading begin to decrease,
This may be caused by the falling off of some
pesticides which were adsorbed on the surface of
Zn (EBNB) (BPY) ·2H O due to too long
soaking time. Therefore, the best time is 5 days.
It can be seen from table 4 that the best
experimental condition is that the mass ratio of
the pesticide to the carrier is 5:1, the action time
is 5 days, and the highest pesticide loading can
be obtained is 0.346 g / g carrier.
2
2
2
2
4
8.78%) main component ZnO.
When avermectin was used as the model
pesticide, the highest pesticide loading appeared
on the 5th day, when the ratio of pesticide to
carrier was 5:1. It can be seen from table 5 that
the highest loading of avermectin is 0.304 g / g
carrier.
Figure 11 DSC-TG analysis results of
2 2 2 2
Zn (EBNB) (BPY) ·2H O
3
3
.5 Study on sustained release of pesticide
.5.1 Determination of pesticide loading of
Zn (EBNB) (BPY) ·2H O
2
2
2
2
The maximum absorption peaks of
jinggangmycin and avermectin were 215nm and
45nm respectively by measurement.
2
7

release of pesticide loaded in
Zn (EBNB) (BPY) ·2H O’s channel, forming a
2
2
2
2
stable release period.
Table 4 Loading amount of jinggangmycin (m
2
) on
Zn (EBNB) (BPY) ·2H O (m ) (n = 3)
2
2
2
2
1
Figure 12 Release properties of jinggangmycin (a) and
avermectin(b) loaded by Zn (EBNB) (BPY) ·2H
2
2
2
2
O
Table 5 Loading amount of avermectin (m
2
) on
(Percentage by mass, 100% based on maximum loading capacity)
Zn (EBNB) (BPY) ·2H O (m ) (n = 3)
2
2
2
2
1
3
.5.3 Biological activity evaluation of
jinggangmycin and avermectin loaded by
Zn (EBNB) (BPY) ·2H O
2
2
2
2
The antibacterial effect of jinggangmycin
and avermectin loaded by
Zn (EBNB) (BPY) ·2H O on Rhizoctonia
2
2
2
2
graminearum is shown in table 6 and figure 13.
The data were colony diameters of sterile water,
jinggangmycin·avermectin wettable powder,
jinggangmycin loaded by
3
.5.2 Slow release properties of jinggangmycin
and avermectin loaded by
Zn (EBNB) (BPY) ·2H O
Zn (EBNB) (BPY) ·2H O and avermectin
2
2
2
2
2
2
2
2
loaded by Zn (EBNB) (BPY) ·2H O on the 4th,
2
2
2
2
As shown in Figure 12, the first half of the
7th, 10th and 14th day. It can be seen clearly in
the figure that the loading of jinggangmycin and
avermectin by Zn (EBNB) (BPY) ·2H O have
better retention than the original pesticides. With
the extension of time, the wettable powder was
absorbed and decomposed by mycelium, and the
amount of effective pesticides is gradually
pesticide release curve is steep, and the first 4
hours shows sudden release. The sudden release
of jinggangmycin and avermectin were 27.4%
and 32.6% respectively. Then it followed with a
smooth slow release, the cumulative release of
jinggangmycin was 76.8%, of avermectin was
2
2
2
2
7
3.8% in 84 hours, which show obvious slow
release effect.
Zn (EBNB) (BPY) ·2H O fully loaded with
reduced. However, the target pesticide loaded by
Zn (EBNB) (BPY) ·2H O has the characteristics
of slow release, and the pesticide was releasing
gradually, so it shows a better antibacterial effect
in the later stage.
2
2
2
2
2
2
2
2
pesticide shows a saturated adsorption state, so
the pesticide was released suddenly at the initial
stage of release. This is mainly due to the
diffusion of the pesticide which was adsorbed on
the surface of Zn (EBNB) (BPY) ·2H O and get
2
2
2
2
into the release medium. Then the steady and
slow release was mainly because of the slow
8

oil-soluble model pesticides were selected to
study the pesticide loading, releasing
performance and biological activity of
Zn (EBNB) (BPY) ·2H O to these pesticides.
2
2
2
2
The results showed that the sustained-release
system had the characteristics of long duration.
Therefore, it could reduce the times of pesticide
use. According to the annual control plan and
dosage of the crop, the reasonable use of
slow-release preparation can effectively prolong
the control cycle of the crop.
Acknowledgements
We acknowledge the support for this study
by the National Natural Science Foundation of
China / Regional Science Foundation Project.
No.21965038 and Applied Basic Research
Program of Yunnan Province / General Projects
of Basic Research. No.2019FB024.
Figure 13 Bacteriostatic effect of jinggangmycin and
avermectin loaded by Zn (EBNB) (BPY) ·2H
2
2
2
2
O
(A: sterile water; B: jinggangmycin·avermectin wettable powder; C:
jinggangmycin loaded by Zn (EBNB) (BPY) ·2H O; D: avermectin
2
2
2
2
2 2 2 2
loaded by Zn (EBNB) (BPY) ·2H O)
Table 6 Effects of jinggangmycin and abamectin loaded
by Zn (EBNB) (BPY) ·2H O and
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Dear Data Administrator,
The editable format Tables 4 and 5 of POLY 114752 has been enclosed in the attachment
file. We didn't realize this problem when we provided the manuscript. Are these tables in this
format acceptable? If there is anything else need to do, please let us know.
Best Regards,
Dr. Li Song
2
020/8/19
Table 4 Loading amount of jinggangmycin (m
2
) on Zn
2
(EBNB)
2
(BPY)
2
·2H
2
O (m
1
) (n = 3)
Drug loading ratio m /m
2
1
m1/m2
1day
3 day
5 day
7 day
1
1
1
1
:1
:3
:5
:6
0.254±0.0013
0.259±0.0017
0.265±0.0020
0.289±0.0012
0.280±0.0020
0.301±0.0007
0.324±0.0012
0.321±0.0013
0.313±0.0025
0.301±0.0019
0.346±0.0010*
0.328±0.0015
0.298±0.0021
0.301±0.0013
0.332±0.0008
0.307±0.0011
Table 5 Loading amount of avermectin (m
2
) on Zn
2
(EBNB)
2
(BPY)
2
2 1
·2H O (m ) (n = 3)
Drug loading ratio m /m
2
1
m1/m2
1day
3 day
5 day
7 day
1
1
1
1
:1
:3
:5
:6
0.134±0.0015
0.268±0.0017
0.288±0.0020
0.295±0.0011
0.145±0.0015
0.272±0.0014
0.297±0.0015
0.296±0.0011
0.158±0.0021
0.279±0.0016
0.304±0.0017*
0.302±0.0016
0.144±0.0023
0.267±0.0017
0.291±0.0010
0.287±0.0014
►
A new 3D MOF Zn (EBNB) (BPY) ·2H O has been synthesized through a three steps synthesized
2
2
2
2
ligand. ►The compound's chemical properties such as the pesticide loading, releasing performance
and biological activity of Zn (EBNB) (BPY) ·2H O to selected water-soluble and oil-soluble model
2
2
2
2
11

pesticides were characterized systematically. ►The sustained-release system had the characteristics of
long duration, so it could reduce the times of pesticide use, and the reasonable use of slow-release
preparation can effectively prolong the control cycle of the crop.
12