Research Article
Nano-pesticide delivery system based on UiO-66 with pH sensitivity for precise control of Spodoptera frugiperda
Chaoqun Hou,
Nuo Wei,
Qianwei Liang,
Yifei Tan,
Xiang Li,
Jianguo Feng,
Chaoqun Hou
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorNuo Wei
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorQianwei Liang
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorYifei Tan
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorXiang Li
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorCorresponding Author
Jianguo Feng
College of Plant Protection, Yangzhou University, Yangzhou, China
Correspondence to: Jianguo Feng, College of Plant Protection, Yangzhou University, Yangzhou 225009, China. E-mail: [email protected]
Search for more papers by this authorChaoqun Hou,
Nuo Wei,
Qianwei Liang,
Yifei Tan,
Xiang Li,
Jianguo Feng,
Chaoqun Hou
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorNuo Wei
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorQianwei Liang
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorYifei Tan
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorXiang Li
College of Plant Protection, Yangzhou University, Yangzhou, China
Search for more papers by this authorCorresponding Author
Jianguo Feng
College of Plant Protection, Yangzhou University, Yangzhou, China
Correspondence to: Jianguo Feng, College of Plant Protection, Yangzhou University, Yangzhou 225009, China. E-mail: [email protected]
Search for more papers by this authorFirst published: 18 October 2024
Abstract
BACKGROUND
Metal–organic frameworks have the advantages of easy synthesis, high loading capacity and good biocompatibility, making them essential materials for constructing pesticide nano-delivery systems. In this study, a pH-responsive nano-controlled-release formulation Chl@UiO-66 was prepared using UiO-66 as the nano-scale carrier for adsorbing chlorantraniliprole (Chl).
RESULTS
The appearance, pesticide loading, release behaviour, insecticidal activity, long-term control efficacy and safety of Chl@UiO-66 for non-target organisms were extensively evaluated. The results showed that the prepared Chl@UiO-66 was a regular octahedron with a uniform particle size of 230 nm and pesticide loading of 15.62%. The release of pesticides under alkaline conditions was superior to that under acidic and neutral conditions, which showed pH-responsive performance. Chl@UiO-66 had an excellent ability to protect pesticides from ultraviolet degradation. Compared with chlorantraniliprole suspension concentrate, Chl@UiO-66 had a better control effect against Spodoptera frugiperda and long-term control efficacy. The prepared nano-controlled-release formulation had low toxicity to zebrafish, earthworms and human BEAS-2B cells.
CONCLUSION
Chl@UiO-66 is a new pesticide formulation with high efficacy and low toxicity that provides a smart controlled-release solution. © 2024 Society of Chemical Industry.
CONFLICT OF INTEREST
The authors claim that there is no conflict of interest.
Open Research
DATA AVAILABILITY STATEMENT
Data sharing is not applicable to this article as no datasets were generated or analysed during the current study.
REFERENCES
- 1Liang WL, Wang B, Cheng JL, Xiao D, Xie Z and Zhao J, 3D, eco-friendly metal-organic frameworks@carbon nanotube aerogels composite materials for removal of pesticides in water. J Hazard Mater 401:123718 (2021).
- 2Dong JT, Chen W, Feng JG, Liu X, Xu Y, Wang C et al., Facile, smart, and degradable metal-organic framework nanopesticides gated with Fe(III)-tannic acid networks in response to seven biological and environmental stimuli. ACS Appl Mater Interfaces 13: 19507–19520 (2021).
- 3Xiao D, Cheng J, Liang W, Sun L and Zhao J, Metal-phenolic coated and prochloraz-loaded calcium carbonate carriers with pH responsiveness for environmentally-safe fungicide delivery. Chem Eng J 418:129274 (2021).
- 4Feng P, Chen JL, Fan CR, Huang GH, Yu YZ et al., An eco-friendly MIL-101@CMCS double-coated dinotefuran for long-acting active release and sustainable pest control. J Clean Prod 265:121851 (2020).
- 5Shan Y, Cao L, Muhammad B, Xu B, Zhao P, Cao C et al., Iron-based porous metal-organic frameworks with crop nutritional function as carriers for controlled fungicide release. J Colloid Interface Sci 566: 383–393 (2020).
- 6Yang J, Dai D, Cai Z, Liu YQ, Qin JC, Wang Y et al., MOF-based multi-stimuli-responsive supramolecular nanoplatform equipped with macrocycle nanovalves for plant growth regulation. Acta Biomater 134: 664–673 (2021).
- 7Yu T, Ma H, Zhang H, Xiong M, Liu Y and Li F, Fabrication and characterization of purified esterase-embedded zeolitic imidazolate frameworks for the removal and remediation of herbicide pollution from soil. J Environ Manage 288:112450 (2021).
- 8Chen ML, Lu TH, Li SS, Wen L, Xu Z and Cheng YH, Photocatalytic degradation of imidacloprid by optimized Bi2WO6/NH2-MIL-88B(Fe) composite under visible light. Environ Sci Pollut Res 29: 19583–19593 (2022).
- 9Tang J, Ding G, Niu J, Zhang W, Tang G, Liang Y et al., Preparation and characterization of tebuconazole metal-organic framework-based microcapsules with dual-microbicidal activity. Chem Eng J 359: 225–232 (2019).
- 10Negro C, Martinez Perez-Cejuela H, Simo-Alfonso EF, Herrero-Martinez JM, Bruno R, Armentano D et al., Highly efficient removal of neonicotinoid insecticides by thioether-based (multivariate) metal-organic frameworks. ACS Appl Mater Interfaces 13: 28424–28432 (2021).
- 11Mejias FJR, Trasobares S, Varela RM, Molinillo JMG, Calvino JJ and Macias FA, One-step encapsulation of ortho-disulfides in functionalized zinc MOF. Enabling metal-organic frameworks in agriculture. ACS Appl Mater Interfaces 13: 7997–8005 (2021).
- 12Liang W, Xie Z, Cheng J, Xiao D, Xiong Q, Wang Q et al., A light-triggered pH-responsive metal-organic framework for smart delivery of fungicide to control Sclerotinia diseases of oilseed rape. ACS Nano 15: 6987–6997 (2021).
- 13Shadmehr J, Sedaghati F and Zeinali S, Efficient elimination of propiconazole fungicide from aqueous environments by nanoporous MIL-101(Cr): process optimization and assessment. Int J Environ Sci Technol 18: 2937–2954 (2021).
- 14Akpinar I and Yazaydin AO, Adsorption of atrazine from water in metal–organic framework materials. J Chem Eng Data 63: 2368–2375 (2018).
- 15Zhang P, Xu YY, Guo KL, Yin Y, Wang J and Zeng Y, Hierarchical-pore UiO-66 modified with Ag(+) for pi-complexation adsorption desulfurization. J Hazard Mater 418:126247 (2021).
- 16Bůžek D, Adamec S, Lang K and Demel J, Metal–organic frameworks vs. buffers: case study of UiO-66 stability. Inorg Chem Front 8: 720–734 (2021).
- 17Feng P, Huang GH, Fan CR, Li YM, Xu CH, Fu LH et al., A dual stimuli-responsive and safer controlled release platform of pesticide through constructing UiO-66-based alginate hydrogel. Polym Test 97:107152 (2021).
- 18Meng WY, Tian ZF, Yao PJ, Fang XL, Wu T, Cheng JG et al., Preparation of a novel sustained-release system for pyrethroids by using metal-organic frameworks (MOFs) nanoparticle. Colloids Surf A Physicochem Eng Asp 604:125266 (2020).
- 19Bird L, Miles M, Quade A and Spafford H, Insecticide resistance in Australian Spodoptera frugiperda (J.E. Smith) and development of testing procedures for resistance surveillance. PLoS One 17:e0263677 (2022).
- 20Xiao YW, Chen C, Wu YG, Wang J, Yin YT, Chen JB et al., Water-stable Al-TCPP MOF nanosheets with hierarchical porous structure for removal of chlorantraniliprole in water. Microporous Mesoporous Mater 324:111272 (2021).
- 21Ren H, Zhang H, Tan Y, Ni R, Shan Y, Li F et al., Sublethal effects of chlorantraniliprole on biological characteristics, detoxifying enzyme activity and gene expression profile in the Allium mongolicum regel leaf beetle Galeruca daurica (Coleoptera: Chrysomelidae). J Appl Entomol 148: 287–303 (2023).
10.1111/jen.13193 Google Scholar
- 22Yang LP, Song ZX, Li C, Huang SQ, Cheng DM and Zhang ZX, Fabricated chlorantraniliprole loaded chitosan/alginate hydrogel rings effectively control Spodoptera frugiperda in maize ears. Crop Prot 143:105539 (2021).
- 23Wang MY, Xu J, Li L, Shen HM, Ding ZY and Xie J, Development of packaging films based on UiO-66 MOF loaded melatonin with antioxidation functions for spinach preservation. Food Chem 440:138211 (2024).
- 24Javanbakht S, Shadi M, Mohammadian R, Shaabani A, Amini MM, Pooresmaeil M et al., Facile preparation of pH-responsive k-Carrageenan/tramadol loaded UiO-66 bio-nanocomposite hydrogel beads as a nontoxic oral delivery vehicle. J Drug Deliv Sci Technol 54:101311 (2019).
- 25Wang Y, Lin WX, Yu SJ, Huang XJ, Lang XR, He Q et al., A biocompatible Zr-based metal-organic framework UiO-66-PDC as an oral drug carrier for pH-response release. J Solid State Chem 293:121805 (2021).
- 26Zhou JW, Guo MM, Wu D, Shen MF, Liu DH and Ding T, Synthesis of UiO-66 loaded-caffeic acid and study of its antibacterial mechanism. Food Chem 402:134248 (2023).
- 27Gao YH, Xiao YN, Mao KK, Qin XY, Zhang Y, Li DL et al., Thermoresponsive polymer-encapsulated hollow mesoporous silica nanoparticles and their application in insecticide delivery. Chem Eng J 383:123169 (2020).
- 28Gao YH, Zhang YH, He S, Xiao YN, Qin XY, Zhang Y et al., Fabrication of a hollow mesoporous silica hybrid to improve the targeting of a pesticide. Chem Eng J 364: 361–369 (2019).
- 29Shan YP, Xu CL, Zhang HJ, Chen H, Bilal M, Niu S et al., Polydopamine-modified metal-organic frameworks, NH2-Fe-MIL-101, as pH-sensitive nanocarriers for controlled pesticide release. Nanomaterials (Basel) 10: 2000 (2020).
- 30Gao YH, Liang Y, Zhou ZY, Yang JL, Tian YY, Niu JF et al., Metal-organic framework nanohybrid carrier for precise pesticide delivery and pest management. Chem Eng J 422:130143 (2021).
- 31Meng WY, Gao YY, Tian ZF, Xu WJ, Cheng JG, Li SK et al., Fe3O4 magnetic cores coated with metal–organic framework shells as collectable composite nanoparticle vehicles for sustained release of the pesticide Imidacloprid. ACS Appl Nano Mater 4: 5864–5870 (2021).
- 32Ashouri V, Adib K and Rahimi Nasrabadi M, A new strategy for the adsorption and removal of fenitrothion from real samples by active-extruded MOF (AE-MOF UiO-66) as an adsorbent. New J Chem 45: 5029–5039 (2021).
- 33Farboudi A, Mahboobnia K, Chogan F, Karimi M, Askari A, Banihashem S et al., UiO-66 metal organic framework nanoparticles loaded carboxymethyl chitosan/poly ethylene oxide/polyurethane core-shell nanofibers for controlled release of doxorubicin and folic acid. Int J Biol Macromol 150: 178–188 (2020).
- 34Wu G, Ma J, Li S, Wang S, Jiang B, Luo S et al., Cationic metal-organic frameworks as an efficient adsorbent for the removal of 2,4-dichlorophenoxyacetic acid from aqueous solutions. Environ Res 186:109542 (2020).
- 35Du D, Liu PJ, Shi ZP, Ren GB, Qi MH, Li Z et al., Three solid forms of chlorantraniliprole: structure, characterization, and phase transformation. J Mol Struct 1171: 323–332 (2018).
- 36Yang LP, Wang SY, Wang RF, Zheng Q, Ma Q, Huang S et al., Floating chitosan-alginate microspheres loaded with chlorantraniliprole effectively control Chilo suppressalis (Walker) and Sesamia inferens (Walker) in rice fields. Sci Total Environ 783:147088 (2021).
- 37Kaziem AE, Gao Y, He S and Li J, Synthesis and insecticidal activity of enzyme-triggered functionalized hollow mesoporous silica for controlled release. J Agric Food Chem 65: 7854–7864 (2017).
- 38Athar M, Rzepka P, Thoeny D, Ranocchiari M and Anton Van Bokhoven J, Thermal degradation of defective high-surface-area UiO-66 in different gaseous environments. RSC Adv 11: 38849–38855 (2021).
- 39Ma YJ, Yu M, Wang YM, Pan S, Sun XL, Zhao R et al., A pH/cellulase dual stimuli-responsive cellulose-coated metal–organic framework for eco-friendly fungicide delivery. Chem Eng J 462:142190 (2023).
- 40Sung YS, Lin LY and Lin HY, Study of pH value effect on synthesizing UIO-66 and carbonized UIO-66 as active material for solid-state supercapacitors. J Taiwan Inst Chem Eng 116: 197–204 (2020).
- 41Kim JY, Kang J, Cha S, Kim H, Kim D, Kang H et al., Stability of Zr-based UiO-66 metal–organic frameworks in basic solutions. Nanomaterials 14: 2079–4991 (2024).
10.3390/nano14010110 Google Scholar
- 42Huang GH, Deng YF, Zhang YC, Feng P, Xu CH, Fu LH et al., Study on long-term pest control and stability of double-layer pesticide carrier in indoor and outdoor environment. Chem Eng J 403:126342 (2021).
- 43Chen HP, Shan YP, Cao LD, Zhao P, Cao C, Li F et al., Enhanced fungicidal efficacy by co-delivery of azoxystrobin and diniconazole with cauliflower-like metal-organic frameworks NH2-Al-MIL-101. Int J Mol Sci 22: 10412 (2021).
- 44Liang Y, Song JH, Dong HQ, Huo Z, Gao Y, Zhou Z et al., Fabrication of pH-responsive nanoparticles for high efficiency pyraclostrobin delivery and reducing environmental impact. Sci Total Environ 787:147422 (2021).
- 45Ren L, Zhao J, Li W, Li Q, Zhang D, Fang W et al., Site-specific controlled-release imidazolate framework-8 for dazomet smart delivery to improve the effective utilization rate and reduce biotoxicity. J Agric Food Chem 70: 5993–6005 (2022).
- 46Liang Y, Wang SJ, Jia HJ, Yao YJ, Song JH, Yang WC et al., pH/redox/α-amylase triple responsive metal-organic framework composites for pest management and plant growth promotion. Microporous Mesoporous Mater 344:112230 (2022).
- 47González L, Carmona FJ, Padial NM, Navarro JR, Barea E and Maldonado CR, Dual removal and selective recovery of phosphate and an organophosphorus pesticide from water by a Zr-based metal-organic framework. Mater Today Chem 22:100596 (2021).
- 48Ding XQ, Guo L, Du Q, Wang TY, Zeng Z, Wang Y et al., Preparation and comprehensive evaluation of the efficacy and safety of chlorantraniliprole nanosuspension. Toxics 12: 78 (2024).
- 49Ma YJ, Zhao R, Shang HY, Zhen S, Li LJ, Guo XY et al., pH-responsive ZIF-8-based metal–organic-framework nanoparticles for termite control. ACS Appl Nano Mater 5: 11864–11875 (2022).
- 50Meng ZY, Cui JJ, Liu L, Yang CM, Bao X, Wang JJ et al., Toxicity effects of chlorantraniliprole in zebrafish (Danio rerio) involving in liver function and metabolic phenotype. Pestic Biochem Physiol 187:105194 (2022).
- 51D'amora M, Schmidt TJN, Konstantinidou S, Raffa V, De Angelis F, Tantussi F et al., Effects of metal oxide nanoparticles in zebrafish. Oxid Med Cell Longev 2022: 1–37 (2022).
- 52Cao HC, Chen Y, Zhang DX, Jin Y, Zhang P, Li BX et al., Octaphenyl polyoxyethylene regulates the flexibility of pyraclostrobin-loaded soft microcapsules by interfacial polymerization for better foliar adhesion and pesticide utilization. Chem Eng J 439:135805 (2022).
- 53Yan WY, Fu X, Gao Y, Shi LY, Liu Q, Yang W et al., Synthesis, antibacterial evaluation, and safety assessment of CuS NPs against Pectobacterium carotovorum subsp. carotovorum. Pest Manag Sci 78: 733–742 (2022).
