Role of Zr6Metal Nodes in Zr-Based Metal-Organic Frameworks for Catalytic Detoxification of Pesticides

Catalytic Detoxi ﬁ cation of Pesticides

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Role of Zr Metal Nodes in Zr-Based Metal−Organic Frameworks for

Dongsik Nam, Yeongjin Kim, Miyeon Kim, Joohan Nam, Seonghoon Kim, Eunji Jin, Chang Yeon Lee,

and Wonyoung Choe*

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sı Supporting Information

ABSTRACT: Pesticides are chemicals widely used for agricultural

industry, despite their negative impact on health and environment.

Although various methods have been developed for pesticide

degradation to remedy such adverse eﬀects, conventional materials

often take hours to days for complete decomposition and are

diﬃcult to recycle. Here, we demonstrate the rapid degradation of

organophosphate pesticides with a Zr-based metal−organic

framework (MOF), showing complete degradation within 15

min. MOFs with diﬀerent active site structures (Zr node

connectivity and geometry) were compared, and a porphyrin-

based MOF with six-connected Zr nodes showed remarkable

degradation eﬃciency with half-lives of a few minutes. Such a high eﬃciency was further conﬁrmed in a simple ﬂow system for

several cycles. This study reveals that MOFs can be highly potent heterogeneous catalysts for organophosphate pesticide

degradation, suggesting that coordination geometry of the Zr node signiﬁcantly inﬂuences the catalytic activity.

INTRODUCTION

■

Although pesticides have contributed signiﬁcantly to agricul-

tural production worldwide, most of them are toxic, leading to

increasing health and environmental concerns for humans and

−9

other living organisms.

A marked toxicity of pesticides can

be seen in recent reports showing that acute exposure to

pesticides has caused 110,000 fatalities globally each year by

self-poisoning. Among pesticide types, organophosphate-

based pesticides (OPs) are one of the most commercialized

classes. The acute toxicity of OPs is originated from the

inhibition of acetylcholinesterase, resulting in neurological

disorders. Although registered pesticides are veriﬁed not to

persist in the environment beyond the intended periods,

residues of OPs in groundwater have been found to range

between ng/L and low μg/L concentrations. Exposure of

nontarget ecosystems to OPs has caused serious health and

environmental issues, for example, surface water contamina-

tion, wildlife poisonings, brain anomalies in children,₉

Figure 1. Adverse eﬀects of pesticides.

prenatal exposure, and adverse birth outcomes (Figure 1).

Since the adverse eﬀects of OPs are global threats, delivering

solutions to evaluate, sense, and detoxify OPs becomes an

extremely urgent issue.

Received: March 4, 2021

Published: May 26, 2021

An eﬀective pesticide detoxiﬁcation method is degradation

to nontoxic species, advantageous for complete toxicity

clearance. Conventional methods to detoxify pesticides include

ozonation, Fenton treatment, photocatalysis, and micro-

13,14

bial degradation.

materials, for example, oximes, surfactants, metal ox-

A number of diﬀerent approaches and

2021 American Chemical Society

Inorg. Chem. 2021, 60, 10249−10256

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Inorganic Chemistry

Article

6−18

ides,

silica nanoparticles,

organometallic com-

treatment was conducted to remove benzoate in the NU-1000 sample.

After the solvent was decanted, a mixed solution of DMF (12 mL)

and 8 M HCl (0.5 mL) was added. Then, the sample was heated in an

oven at 100 °C. The solid was washed with DMF (10 mL ×3) for 2 d

and acetone (10 mL ×3) for 2 d. The NU-1000 sample was stored in

acetone.

0−22

plexes,

and enzymes, have been reported for the

degradation of OPs. However, conventional physicochemical

approaches are not cost-eﬀective and often result in incomplete

conversions.

surfactants, are diﬃcult to recycle.

require light sources or result in stoichiometric not catalytic

0,11

Nucleophilic species, such as oximes and

4,15

Metal oxides often

Pesticide Degradation Experiments. Degradation proﬁles of

organophosphate pesticides (OPs) were obtained by in situ P NMR

1,18

reactions.

Enzymes are easily inactivated under non-

measurement at room temperature. PCN-224, MOF-808, and NU-

1000 samples were activated under vacuum at 100 °C for 12 h, 150

°C for 24 h, and 120°C for 12 h, respectively. The activated MOF

physiological conditions, and the process is accompanied by

high costs and diﬃculties in recovery. Therefore, heteroge-

neous catalysts with high catalytic activities and facile recycling

are appealing candidates for pesticide degradation.

Metal−organic frameworks (MOFs), porous materials

composed of metal clusters and organic linkers, are one of

the leading classes of heterogeneous catalysts due to the

tunable catalytic activities of metal clusters, diverse chemical

functionalization, and high density of active sites with regular

samples (0.75 μmol Zr ) of PCN-224 (1.6 mg), MOF-808 (1.1 mg),

and NU-1000 (1.7 mg) were dispersed in a buﬀer solution (1 mL) of

H O (0.9 mL), D O (0.1 mL), and 4-ethylmorpholine (50 μL)

through sonication for 1 min. Separately, 25 μmol OP [5.4 μL for

POX, 3.9 μL for dichlorvos (DDVP), and 4.9 μL for naled] was mixed

with acetonitrile (0.1 mL). Caution: OPs are highly toxic. Experi-

ments should be conducted with appropriate safety procedures. After

the OP solution (0.1 mL) was added to the dispersed MOF sample,

the mixture was shaken for 10 s and moved to an NMR tube. Then,

4−28

distributions.

In particular, Zr-based MOFs with high

the immediate P NMR measurement was conducted. The NMR

spectra were collected every minute for 30 min. The ﬁrst spectrum

was obtained at around 2.5 min after the OP solution was added to

the MOF sample.

chemical stabilities have shown notable catalytic degradation of

organophosphate species, that is, chemical warfare agents.

Nevertheless, only a few studies have explored MOFs for the

degradation of OPs.

the only pesticide type studied with Zr-based MOFs.

Here, we report the outstanding OP degradation with Zr-

based MOFs. Interestingly, a porphyrin-based MOF, PCN-

29−41

42−47

For example, paraoxon (POX) was

DDVP Degradation with PCN-224 in a Simple Continuous

Flow System. A buﬀer solution of H O (10 mL) and 4-

ethylmorpholine (0.5 mL) was prepared. PCN-224 (16.4 mg, 7.5

μmol Zr ) was homogeneously dispersed in the buﬀer solution (3

24, with six-connected Zr nodes reveals striking OP

mL) through sonication for 1 min. The mixture was ﬁltered through a

syringe ﬁlter (PTFE with 0.2 μm pore size; 13 mm diameter) so that

PCN-224 was loaded on the ﬁlter. The syringe ﬁlter was washed with

a new syringe containing the buﬀer solution (1 mL) on a syringe

pump (0.1 mL/min). Separately, DDVP solution for ﬁve injections

was prepared by mixing the buﬀer solution (5 mL), DDVP (9.75 μL,

degradation performance without signiﬁcant activity variation,

depending on pesticide types. Furthermore, PCN-224 retained

high degradation eﬃciency for several cycles in a simple

continuous ﬂow system. Such a high catalytic activity is

attributed to the active site structure: Zr node connectivity and

geometry, potential factors governing degradation eﬃciency.

This work represents a signiﬁcant advance of conventional OP

degradation materials to a highly eﬃcient MOF catalyst with

recycle capability, suggesting that coordination geometry of the

Zr active site is a crucial factor for enhancing the catalytic

activity of the Zr-based MOF.

2.5 μmol), and acetonitrile (0.5 mL). The DDVP solution (1 mL)

was injected through the MOF ﬁlter using the syringe pump (0.1 mL/

min). With the same MOF ﬁlter, ﬁve injections continuously

proceeded. For each injection, the ﬁltrate was mixed with D O (0.1

mL) and then analyzed with P NMR spectroscopy.

RESULTS AND DISCUSSION

■

We targeted three commercial pesticides, POX, DDVP, and

naled. POX has been extensively studied for its acute toxicity

EXPERIMENTAL SECTION

■

to mammals. DDVP is one of the most widely used indoor

Synthesis of PCN-224. The PCN-224 sample was synthesized

pesticides, but there are concerns about indoor air pollution

following a reported recipe with some modiﬁcations. To a 100 mL

vial, ZrOCl ·8H O (125 mg), meso-tetra(4-carboxyphenyl)porphine

52,53

and toxicity to nontarget organisms, such as ﬁsh.

Naled,

(

H TCPP) (25 mg), DMF (50 mL), and acetic acid (12.5 mL) were

used for mosquito control, has adverse eﬀects following

added. After sonication, the mixture was heated at 65 °C for 72 h in

prenatal exposure. Regarding MOF candidates for eﬃcient

an oven. The resulting powder was washed with DMF (20 mL ×3) for

OP degradation, we compared the structures of Zr-based

d and acetone (20 mL ×9) for 4 d through centrifugation. After the

MOFs with high chemical stabilities, PCN-224, MOF-808,

solvent was decanted, the powder was dried at 90 °C for 12 h. The

dried powder of PCN-224 was stored in a desiccator.

NU-1000, and UiO-66 (Figure 2). These MOFs have Zr₆

clusters with diﬀerent connectivities (12 for UiO-66, 8 for NU-

1000, and 6 for MOF-808 and PCN-224), derived from their

diﬀerent organic linkers. Sites unoccupied by linkers typically

Synthesis of MOF-808. The synthesis of MOF-808 was based on

a reported method. To a 50 mL vial, ZrOCl ·8H O (160 mg), 1,3,5-

benzenetricarboxylic acid (H BTC) (110 mg), and a mixed solution

have solvents, H O/OH, or monocarboxylate species, which

of DMF (20 mL) and formic acid (20 mL) were added. The sample

was heated at 100 °C for 7 d in an oven. The resulting powder was

washed with DMF (20 mL ×3) for 2 d and acetone (20 mL ×4) for 2

d through centrifugation. After the solvent was decanted, the powder

was dried at 80 °C for 3 h. The dried sample of MOF-808 was stored

in a desiccator.

can be replaced with substrates. Hence, the lower connectivity

of the Zr node yields a larger number of potential catalytic

active sites. A previous study by Farha, Hupp, and co-workers

on organophosphate nerve agent hydrolysis has revealed that

Zr-based MOFs with lower node connectivities displayed

Synthesis of NU-1000. The NU-1000 sample was synthesized

higher degradation eﬃciencies. A possible explanation is that

following a reported recipe. To a 20 mL vial, ZrOCl ·8H O (97

mg), benzoic acid (2.7 g), and DMF (8 mL) were added. The mixture

was heated in an oven at 80 °C for 1 h. After heating, 1,3,6,8-

tetrakis(p-benzoic acid)pyrene (H TBAPy) (40 mg) was added.

the Zr−OH bond strength becomes weaker with decreasing

connectivity, thus facilitating the replacement of water with

7,58

substrates.

While MOF-808 has the lowest node

connectivity among the most investigated Zr-based MOFs

for nerve agent hydrolysis, we hypothesized that PCN-224,

also with six-node connectivity, could be a highly active OP

Then, the mixture was sonicated for 20 min. The sample was stirred at

00 °C for 24 h on a hot plate. The resulting solid was washed with

DMF (10 mL ×3) through centrifugation. After washing, acid

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ppm, corresponding to diethyl phosphate (DEP), appeared.

During the degradation of DDVP and naled, peaks

corresponding to dimethyl phosphate (DMP), at 2.8 ppm,

were observed. The formation of DEP and DMP indicates that

the pesticides are hydrolyzed by the cleavage of P−O−C

bonds, a well-known mechanism for the degradation of nerve

5,59

agent simulants.

Based on the NMR results, simple

hydrolysis schemes are shown in Scheme 1.

We compared the degradation eﬃciencies of PCN-224,

MOF-808, and NU-1000 for the three OPs (Figure 4).

Pesticide conversions were calculated from the integrated peak

ratios. Initial reaction rates and half-lives were calculated with a

ﬁrst-order kinetic equation (Table 1 and Figures S14 −S21).

Interestingly, PCN-224 demonstrated rapid hydrolysis of all

the pesticides, while MOF-808 and NU-1000 showed relatively

slower degradation (Figure 4a−c). The initial half-lives of

degradation by PCN-224 were 2.1, <1, and 1.1 min for POX,

DDVP, and naled, respectively. However, MOF-808 and NU-

000 showed half-lives of <5 min for only one pesticide. In

particular, the conversion of POX, DDVP, and naled by PCN-

24 reached almost 100% within 15 min, and the hydrolysis

rate of the respective pesticide did not vary signiﬁcantly

Figure 4a). In contrast, 68 and 38% conversions were

observed for DDVP and naled by MOF-808, respectively

Figure 4b). NU-1000 showed conversions of 65% for DDVP

(

and 40% for POX (Figure 4c). When we rearranged the

degradation plots in terms of pesticide, PCN-224 showed the

highest activity for the three pesticides (Figure 4d−f). In the

case of DDVP, the degradation eﬃciency of PCN-224 was

notably greater than those of MOF-808 and NU-1000 (Figure

Figure 2. Framework structures, Zr₆node connectivities, and

simpliﬁed node geometries of PCN-224, MOF-808, NU-1000, and

UiO-66.

e). As control experiments, we ﬁltered MOF catalysts 1 min

after injection of pesticides. The ﬁltrate samples were analyzed

degradation catalyst. Therefore, PCN-224, MOF-808, and NU-

1000 were prepared and their OP degradation eﬃciencies were

with P NMR. POX, DDVP, and naled were not degraded in a

short time without MOF catalysts (Figure S22). We also

compared crystallinity of PCN-224, MOF-808, and NU-1000

after pesticide degradation (Figure S23). Powder X-ray

diﬀraction patterns of those MOFs showed that crystallinity

was retained after the catalytic reactions. Through an overall

comparison of the three MOFs, we conﬁrmed that PCN-224

has a high catalytic activity for OP degradation, which is less

pesticide-type-dependent than those of MOF-808 and NU-

1000.

compared.

MOF-808 and NU-1000 samples were synthesized and

9,50

activated following previously reported procedures,

modiﬁed method was used to obtain the pure phase of PCN-

24. The structural integrity of the activated MOF samples was

while a

conﬁrmed with powder X-ray diﬀraction patterns (Figure 3a).

N adsorption analysis at 77 K at P/P = 1.0 revealed uptake

amounts of 840, 580, and 970 cm /g for PCN-224, MOF-808,

and NU-1000, respectively (Figure 3b). The pore size

distribution data of PCN-224 and MOF-808 showed pore

sizes of 19 and 18 Å, respectively (Figure S1), while 12 and 29

Å pores were observed for NU-1000. The gas sorption results

The remarkable OP degradation eﬃciency of PCN-224

motivated us to determine the factors inﬂuencing its high

activity. We ﬁrst compared modulator amount in Zr nodes of

corresponded to reported values for N uptake and pore size

PCN-224, MOF-808, and NU-1000 because the number of

modulator ligands has a signiﬁcant impact on node

accessibility, according to a recent report by Hupp, Lu, and

co-workers. H NMR spectra of activated PCN-224, MOF-

808, and NU-1000 samples showed 5.6 acetate, 3.0 formate,

8,49,55

distribution.

The particle sizes of the as-synthesized

samples were conﬁrmed by scanning electron microscopy

(

Figure 3c). Particle sizes of ∼2.5, ∼10, and ∼2 μm were

observed for PCN-224, MOF-808, and NU-1000, respectively.

The characterization results revealed successful sample

preparation for OP degradation experiments.

and 2.9 formate per Zr node, respectively, while maximum

potential active sites are 6, 6, and 4 for the MOFs (Figures

S24 −S26 ). PCN-224 has the most modulator ligands among

the analyzed MOFs, thus meaning initially more blocked active

sites. We also identiﬁed that most of the acetate and formate

ligands were removed when the MOF samples were soaked in

N-ethylmorpholine solution following the OP degradation

experimental condition. Hence, the high catalytic activity of

PCN-224 is not simply explained with the eﬀects of the

Before degradation analysis, the formula weights of the

activated MOFs were determined from the H NMR spectra of

the digested MOF samples (Figures S2 −S4 ). The activated

MOF sample (3 mol %, 0.75 μmol Zr ) was dispersed in water

buﬀered with N-ethylmorpholine. After the pesticide solution

in acetonitrile was added, hydrolysis progress was monitored

by P NMR spectroscopy. As the reaction proceeded, the

intensity of the peaks at approximately −6.8, −3.3, and −3.0

ppm for POX (Figures S5 −S7), DDVP (Figures S8 −S10), and

naled (Figures S11 −S13), respectively, decreased in all the

MOF samples. During the POX degradation, a peak at ∼0.5

modulator ligand. Assuming that all Zr node active sites are

fully accessible by pesticide molecules, we focused on node

connectivity and geometry. For the degradation of the nerve

agent, less Zr node connectivity leads to higher degradation

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Figure 3. Characterizations of Zr-based MOFs to be used for pesticide degradation. (a) Simulated and experimental powder X-ray diﬀraction

patterns, (b) N isotherms at 77 K, and (c) scanning electron microscopy images of PCN-224, MOF-808, and NU-1000. Scale bars indicate 5 μm.

Scheme 1. Simple Degradation Schemes for the OPs, POX,

DDVP, and Naled

Recently, Snurr and co-workers reported computational studies

on the eﬀects of node connectivity and topology on the

binding of nerve agents. In the study, the binding energy of

coordinated H O varies with node topology as well as

connectivity. For example, the binding energy of H O within

the small pore is stronger than that within the large pore in

NU-1000. This indicates that node geometry is important for

water displacement, one of the potential rate-limiting steps.

Therefore, we compared the node topologies of PCN-224 and

MOF-808 (Figure 5). The Zr node of PCN-224 has six

equatorial linker-binding sites (Figure 5a). The remaining six

active sites are at the axial positions. In contrast, the node of

MOF-808 has six active sites at the equatorial positions and six

axial linker-binding sites (Figure 5b). We speculate that such

distinct node geometries lead to diﬀerent free energies of water

displacement, the binding of the organophosphate, and the

displacement of the degraded product, which are three

potential rate-determining steps, as suggested in the computa-

tional works. Although quantitatively evaluating the degra-

dation eﬃciency of MOFs remains challenging, we suggest that

calculating the free energy diﬀerences of the PCN-224 model

for these steps will provide meaningful qualitative insights into

eﬃciency, possibly due to the increased number of active site

and the lower bond strength between Zr and coordinated H O,

as described in the ﬁrst paragraph of this section. While PCN-

24 and MOF-808 have the same six-node connectivity,

signiﬁcantly diﬀerent catalytic activities in OP degradation

suggest that other factors are involved in the eﬃciency.

how Zr node geometry aﬀects catalytic activity.

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Figure 4. Degradation proﬁles of OPs. The conversion of POX, DDVP, and naled in the presence of (a) PCN-224, (b) MOF-808, and (c) NU-

000. The rearranged graphs for comparing catalytic activities of PCN-224, MOF-808, and NU-1000 for (d) POX, (e) DDVP, and (f) naled.

Table 1. Initial Half-Lives (min) for OP Degradation by

PCN-224, MOF-808, and NU-1000

POX

DDVP

naled

PCN-224

MOF-808

NU-1000

2.1

3.9

24.9

7.6

11.6

1.1

15.9

2.2

Figure 6. Degradation of DDVP with PCN-224 in a simple

continuous ﬂow system. For each injection, the conversion of the

ﬁltrate was conﬁrmed with P NMR spectroscopy.

^Fⁱ^g^u^r^e⁵^.^Z^r6 node topologies of PCN-224 and MOF-808. The

structure and simpliﬁed model of the Zr node with peripheral linker

phenyl groups in (a) PCN-224 and (b) MOF-808, respectively. The

potential active sites are depicted with red rods on the respective node

of PCN-224 and MOF-808.

24-loaded ﬁlter using a syringe pump (0.1 mL/min). The

next injection proceeded with a new DDVP solution. After

each respective injection, the ﬁltrate was collected and

To further assess the high catalytic activity of PCN-224,

degradation of DDVP was investigated using a simple

continuous ﬂow system (Figure 6). The activated powder of

PCN-224 was dispersed in a buﬀer solution, loaded onto a

syringe ﬁlter by ﬁltration, and washed with the buﬀer solution.

DDVP solution (1 mL) was then injected through the PCN-

analyzed using P NMR spectroscopy. Almost 100%

conversion was observed after the ﬁrst run, slightly decreasing

to 95% after 5 injections. During the ﬂow system experiment,

the purple color of the ﬁltrate was observed, indicating

leaching of tetrakis(4-carboxyphenyl)porphyrin (TCPP). The

amount of TCPP in the ﬁltrate samples from MOF loading,

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Inorganic Chemistry

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washing, and following ﬁ ve injection steps was identiﬁed using

UV−vis spectroscopy (Figure S27 and Table S1). After the

washing step, leaching of 2 mol % was observed, while <1 mol

Seonghoon Kim − Department of Chemistry, Ulsan National

Institute of Science and Technology, Ulsan 44919, Republic of

Korea

Eunji Jin − Department of Chemistry, Ulsan National Institute

of Science and Technology, Ulsan 44919, Republic of Korea

Chang Yeon Lee − Department of Energy and Chemical

Engineering/Innovation Center for Chemical Engineering,

Incheon National University, Incheon 22012, Republic of

Korea; orcid.org/0000-0002-1131-9071

was found after the other steps (Figure S28). From the

second injection onward, the leaching amount of TCPP was

only ∼0.2 mol %. Based on these results, the high catalytic

activity of PCN-224 for DDVP degradation was conﬁrmed in

the ﬂow system, with reusability for several cycles.

CONCLUSIONS

■

https://pubs.acs.org/10.1021/acs.inorgchem.1c00653

In this work, we showed catalytic degradation of OPs, widely

used pesticides toxic to humans and other organisms. For three

commercial OPs, POX, DDVP, and naled, we investigated

degradation eﬃciencies of Zr-based MOFs, PCN-224, MOF-

Notes

The authors declare no competing ﬁnancial interest.

08, and NU-1000, with diﬀerent active site structures.

Compared to other MOFs, PCN-224 exhibited remarkable

conversion rates with POX, DDVP, and naled, showing half-

lives of a few minutes. Moreover, degradation eﬃciencies of

PCN-224 were not signiﬁcantly varied depending on pesticide

types. The high activity of PCN-224 was further explored in a

simple continuous ﬂow system, showing conversions of >95%

for several cycles. By comparing node connectivity and

geometry in Zr-based MOFs, we attribute the high activity

of PCN-224 to node coordination geometry, determined by

the positions of linker-binding sites. This work demonstrates

that Zr-based MOFs can be utilized as extremely eﬃcient

heterogeneous catalysts for OP degradation, suggesting node

geometry as a critical factor governing organophosphate

degradation eﬃciency.

ACKNOWLEDGMENTS

■

This work was supported by the Korea Environment Industry

and Technology Institute (KEITI) through the Public

Technology Program based on the Environmental Policy

Program, funded by the Korea Ministry of Environment

MOE) (2018000210002), and by the National Research

Foundation (NRF) of Korea (NRF-2016R1A5A1009405 and

NRF-2020R1A2C3008226.)

(

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ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00653.

■

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Dongsik Nam − Department of Chemistry, Ulsan National

Institute of Science and Technology, Ulsan 44919, Republic of

Korea

Yeongjin Kim − Department of Chemistry, Ulsan National

Institute of Science and Technology, Ulsan 44919, Republic of

Korea

Miyeon Kim − Department of Energy and Chemical

Engineering/Innovation Center for Chemical Engineering,

Incheon National University, Incheon 22012, Republic of

Korea

Joohan Nam − Department of Chemistry, Ulsan National

Institute of Science and Technology, Ulsan 44919, Republic of

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