Developing an Eco-friendly formulation is essential to reducing the use of traditional pesticides. Halloysite nanotubes were added as a stabilizing or emulsifying agent, neem oil was utilized to create Pickering emulsions, and acephate was added to evaluate the pesticidal effectiveness. Microscopic images show that the interfacial tension and droplet size decrease with increasing HNT levels. The contact angle affects the pesticide formulations’ capacity to stick, moisten, and disperse on plant leaves. The majority of produced emulsions exhibit good wettability at contact angles below 60˚. HNTs were efficiently adsorbed at droplet interfaces, as confirmed by EDS, SEM, and FTIR, ensuring the stability of the emulsion. Escherichia coli , Pseudomonas aeruginosa , Bacillus cereus , and Staphylococcus aureus were the bacterial strains employed to test the biosafety. Using Spodoptera frugiperda as a pest model and maize as a plant model, insecticidal tests were conducted. It is neem oil-based emulsions that have the highest fatality rate. These results show that HNT-stabilized Neem oil emulsions provide a reliable, environmentally friendly, and biosafe platform for pest control.
Wei, H., Wang, H., Chu, H. and Li, J. (2019) Preparation and Characterization of Slow-Release and Water-Retention Fertilizer Based on Starch and Halloysite. International Journal of Biological Macromolecules , 133, 1210-1218. https://doi.org/10.1016/j.ijbiomac.2019.04.183
Shen, Y., Wang, H., Li, W., Liu, Z., Liu, Y., Wei, H., et al . (2020) Synthesis and Characterization of Double-Network Hydrogels Based on Sodium Alginate and Halloysite for Slow Release Fertilizers. International Journal of Biological Macromolecules , 164, 557-565. https://doi.org/10.1016/j.ijbiomac.2020.07.154
Wang, C., He, Z., Liu, Y., Zhou, C., Jiao, J., Li, P., et al . (2020) Chitosan-Modified Halloysite Nanotubes as a Controlled-Release Nanocarrier for Nitrogen Delivery. Applied Clay Science , 198, Article 105802. https://doi.org/10.1016/j.clay.2020.105802
El Assimi, T., Chaib, M., Raihane, M., El Meziane, A., Khouloud, M., Benhida, R., et al . (2020) Poly(ε-Caprolactone)-G-Guar Gum and Poly(ε-Caprolactone)-G-Halloysite Nanotubes as Coatings for Slow-Release DAP Fertilizer. Journal of Polymers and the Environment , 28, 2078-2090. https://doi.org/10.1007/s10924-020-01750-7
Masoudniaragh, A., Oraei, M., Gohari, G., Akbari, A. and Faramarzi, A. (2021) Using Halloysite Nanotubes as Carrier for Proline to Alleviate Salt Stress Effects in Sweet Basil ( Ocimum basilicum L.). Scientia Horticulturae , 285, Article 110202. https://doi.org/10.1016/j.scienta.2021.110202
Yaakov, N., Ananth Mani, K., Felfbaum, R., Lahat, M., Da Costa, N., Belausov, E., et al . (2018) Single Cell Encapsulation via Pickering Emulsion for Biopesticide Applications. ACS Omega , 3, 14294-14301. https://doi.org/10.1021/acsomega.8b02225
Li, J., Cheng, M., Yang, C., Zhang, Y. and Li, D. (2022) Regenerated Cellulose-Stabilized Pickering Emulsion for Sustained Release of Imidacloprid. Colloid and Polymer Science , 300, 1169-1177. https://doi.org/10.1007/s00396-022-05017-6
Ramadhany, P., Witono, J.R.B. and Rosaria, R. (2021) Neem-Based Oil-in-Water (O/W) Emulsion as a Biopesticide. IOP Conference Series : Materials Sci ence and Engineering , 1053, Article 012047. https://doi.org/10.1088/1757-899x/1053/1/012047
Chen, L., Huang, J., Chen, J., Shi, Q., Chen, T., Qi, G., et al . (2022) Halloysite Nanotube-Based Pesticide Formulations with Enhanced Rain Erosion Resistance, Foliar Adhesion, and Insecticidal Effect. ACS Applied Materials & Interfaces , 14, 41605-41617. https://doi.org/10.1021/acsami.2c11234
Yuan, P., Tan, D. and Annabi-Bergaya, F. (2015) Properties and Applications of Halloysite Nanotubes: Recent Research Advances and Future Prospects. Applied Clay Science , 112, 75-93. https://doi.org/10.1016/j.clay.2015.05.001
Lisuzzo, L., Cavallaro, G., Milioto, S. and Lazzara, G. (2022) Pickering Emulsions Stabilized by Halloysite Nanotubes: From General Aspects to Technological Applications. Advanced Materials Interfaces , 9, Article 2102346. https://doi.org/10.1002/admi.202102346
Cui, Y., Threlfall, M. and van Duijneveldt, J.S. (2011) Optimizing Organoclay Stabilized Pickering Emulsions. Journal of Colloid and Interface Science , 356, 665-671. https://doi.org/10.1016/j.jcis.2011.01.046
Zhong, B., Wang, S., Dong, H., Luo, Y., Jia, Z., Zhou, X., et al . (2017) Halloysite Tubes as Nanocontainers for Herbicide and Its Controlled Release in Biodegradable Poly(Vinyl Alcohol)/Starch Film. Journal of Agricultural and Food Chemistry , 65, 10445-10451. https://doi.org/10.1021/acs.jafc.7b04220
Wang, S., Jia, Z., Zhou, X., Zhou, D., Chen, M., Xie, D., et al . (2017) Preparation of a Biodegradable Poly(Vinyl Alcohol)-Starch Composite Film and Its Application in Pesticide Controlled Release. Journal of Applied Polymer Science , 134, Article 45051. https://doi.org/10.1002/app.45051
Yang, J., Zang, W., Zhang, Z., Wang, P. and Yang, Q. (2019) The Enhanced and Tunable Sustained Release of Pesticides Using Activated Carbon as a Carrier. Materials , 12, Article 4019. https://doi.org/10.3390/ma12234019
Tan, D., Yuan, P., Annabi-Bergaya, F., Liu, D. and He, H. (2015) Methoxy-Modified Kaolinite as a Novel Carrier for High-Capacity Loading and Controlled-Release of the Herbicide Amitrole. Scientific Reports , 5, Article 8870. https://doi.org/10.1038/srep08870
Tan, D., Yuan, P., Annabi-Bergaya, F., Dong, F., Liu, D. and He, H. (2015) A Comparative Study of Tubular Halloysite and Platy Kaolinite as Carriers for the Loading and Release of the Herbicide Amitrole. Applied Clay Science , 114, 190-196. https://doi.org/10.1016/j.clay.2015.05.024
Wang, X., Hou, X., Zou, P., Huang, A., Zhang, M. and Ma, L. (2022) Cationic Starch Modified Bentonite-Alginate Nanocomposites for Highly Controlled Diffusion Release of Pesticides. International Journal of Biological Macromolecules , 213, 123-133. https://doi.org/10.1016/j.ijbiomac.2022.05.148
Wang, K., Sun, X., Long, B., Li, F., Yang, C., Chen, J., et al . (2021) Green Production of Biodegradable Mulch Films for Effective Weed Control. ACS Omega , 6, 32327-32333. https://doi.org/10.1021/acsomega.1c05725
Zeng, X., Zhong, B., Jia, Z., Zhang, Q., Chen, Y. and Jia, D. (2019) Halloysite Nanotubes as Nanocarriers for Plant Herbicide and Its Controlled Release in Biodegradable Polymers Composite Film. Applied Clay Science , 171, 20-28. https://doi.org/10.1016/j.clay.2019.01.021
Meyer, W.L., Gurman, P., Stelinski, L.L. and Elman, N.M. (2015) Functional Nano-Dispensers (FNDs) for Delivery of Insecticides against Phytopathogen Vectors. Green Chemistry , 17, 4173-4177. https://doi.org/10.1039/c5gc00717h
Seven, S.A., Tastan, Ö.F., Tas, C.E., Ünal, H., Ince, İ.A. and Menceloglu, Y.Z. (2019) Insecticide-releasing LLDPE Films as Greenhouse Cover Materials. Materials Today Communications , 19, 170-176. https://doi.org/10.1016/j.mtcomm.2019.01.015
Qin, Y., An, T., Cheng, H., Su, W., Meng, G., Wu, J., et al . (2022) Functionalized Halloysite Nanotubes as Chlorpyrifos Carriers with High Adhesion and Temperature Response for Controlling of Beet Armyworm. Applied Clay Science , 222, Article 106488. https://doi.org/10.1016/j.clay.2022.106488
El Assimi, T., Lakbita, O., El Meziane, A., Khouloud, M., Dahchour, A., Beniazza, R., et al . (2020) Sustainable Coating Material Based on Chitosan-Clay Composite and Paraffin Wax for Slow-Release DAP Fertilizer. International Journal of Biological Macromolecules , 161, 492-502. https://doi.org/10.1016/j.ijbiomac.2020.06.074
Saki, H., Alemayehu, E., Schomburg, J. and Lennartz, B. (2019) Halloysite Nanotubes as Adsorptive Material for Phosphate Removal from Aqueous Solution. Water , 11, Article 203. https://doi.org/10.3390/w11020203
Vo, P.T., Nguyen, H.T., Trinh, H.T., Nguyen, V.M., Le, A., Tran, H.Q., et al . (2021) The Nitrogen Slow-Release Fertilizer Based on Urea Incorporating Chitosan and Poly(Vinyl Alcohol) Blend. Environmental Technology & Innovation , 22, Article 101528. https://doi.org/10.1016/j.eti.2021.101528
Wang, C., Song, S., Yang, Z., Liu, Y., He, Z., Zhou, C., et al . (2022) Hydrophobic Modification of Castor Oil-Based Polyurethane Coated Fertilizer to Improve the Controlled Release of Nutrient with Polysiloxane and Halloysite. Progress in Organic Coatings , 165, Article 106756. https://doi.org/10.1016/j.porgcoat.2022.106756
Chen, L., Guo, Z., Lao, B., Li, C., Zhu, J., Yu, R., et al . (2021) Phytotoxicity of Halloysite Nanotubes Using Wheat as a Model: Seed Germination and Growth. Environmental Science : Nano , 8, 3015-3027. https://doi.org/10.1039/d1en00507c
Yang, Y., Fang, Z., Chen, X., Zhang, W., Xie, Y., Chen, Y., et al . (2017) An Overview of Pickering Emulsions: Solid-Particle Materials, Classification, Morphology, and Applications. Frontiers in Pharmacology , 8, Article ID: 235054. https://doi.org/10.3389/fphar.2017.00287
Pang, Y., Wang, S., Qiu, X., Luo, Y., Lou, H. and Huang, J. (2017) Preparation of Lignin/Sodium Dodecyl Sulfate Composite Nanoparticles and Their Application in Pickering Emulsion Template-Based Microencapsulation. Journal of Agricultural and Food Chemistry , 65, 11011-11019. https://doi.org/10.1021/acs.jafc.7b03784
Wu, J. and Ma, G. (2016) Recent Studies of Pickering Emulsions: Particles Make the Difference. Small , 12, 4633-4648. https://doi.org/10.1002/smll.201600877
Shorey, R. and Mekonnen, T.H. (2023) Esterification of Lignin with Long Chain Fatty Acids for the Stabilization of Oil-in-Water Pickering Emulsions. International Journal of Biological Macromolecules , 230, Article 123143. https://doi.org/10.1016/j.ijbiomac.2023.123143
Wang, Y., Li, X., Shen, C., Mao, Z., Xu, H., Zhong, Y., et al . (2020) Lignin Assisted Pickering Emulsion Polymerization to Microencapsulate 1-Tetradecanol for Thermal Management. International Journal of Biological Macromolecules , 146, 1-8. https://doi.org/10.1016/j.ijbiomac.2019.12.175
Van Hooghten, R., Blair, V.E., Vananroye, A., Schofield, A.B., Vermant, J. and Thijssen, J.H.J. (2017) Interfacial Rheology of Sterically Stabilized Colloids at Liquid Interfaces and Its Effect on the Stability of Pickering Emulsions. Langmuir , 33, 4107-4118. https://doi.org/10.1021/acs.langmuir.6b04365
Kpogbemabou, D., Lecomte-Nana, G., Aimable, A., Bienia, M., Niknam, V. and Carrion, C. (2014) Oil-in-Water Pickering Emulsions Stabilized by Phyllosilicates at High Solid Content. Colloids and Surfaces A : Physicochemical and Engineering Aspects , 463, 85-92. https://doi.org/10.1016/j.colsurfa.2014.09.037
Cai, X., Li, C., Tang, Q., Zhen, B., Xie, X., Zhu, W., et al . (2019) Assembling Kaolinite Nanotube at Water/Oil Interface for Enhancing Pickering Emulsion Stability. Applied Clay Science , 172, 115-122. https://doi.org/10.1016/j.clay.2019.02.021
Cavallaro, G., Milioto, S., Nigamatzyanova, L., Akhatova, F., Fakhrullin, R. and Lazzara, G. (2019) Pickering Emulsion Gels Based on Halloysite Nanotubes and Ionic Biopolymers: Properties and Cleaning Action on Marble Surface. ACS Applied Nano Materials , 2, 3169-3176. https://doi.org/10.1021/acsanm.9b00487
Yu, B., Cheng, J., Fang, Y., Xie, Z., Xiong, Q., Zhang, H., et al . (2024) Multi-Stimuli-responsive, Topology-Regulated, and Lignin-Based Nano/Microcapsules from Pickering Emulsion Templates for Bidirectional Delivery of Pesticides. ACS Nano , 18, 10031-10044. https://doi.org/10.1021/acsnano.3c11621
Yu, X., Li, X., Ma, S., Wang, Y., Zhu, W. and Wang, H. (2023) Biomass-Based, Interface Tunable, and Dual-Responsive Pickering Emulsions for Smart Release of Pesticides. Advanced Functional Materials , 33, Article 2214911. https://doi.org/10.1002/adfm.202214911
Yang, C., Li, J., Zhang, Y., Wu, C. and Li, D. (2023) A Pesticide Sustained‐Release Microcapsule from Cellulose Nanocrystal Stabilized Pickering Emulsion Template. Journal of Applied Polymer Science , 140, e53716. https://doi.org/10.1002/app.53716
Tang, C., Li, Y., Pun, J., Mohamed Osman, A.S. and Tam, K.C. (2019) Polydopamine Microcapsules from Cellulose Nanocrystal Stabilized Pickering Emulsions for Essential Oil and Pesticide Encapsulation. Colloids and Surfaces A : Physicochemical and Engineering Aspects , 570, 403-413. https://doi.org/10.1016/j.colsurfa.2019.03.049
Pang, Y., Li, X., Wang, S., Qiu, X., Yang, D. and Lou, H. (2018) Lignin-Polyurea Microcapsules with Anti-Photolysis and Sustained-Release Performances Synthesized via Pickering Emulsion Template. Reactive and Functional Polymers , 123, 115-121. https://doi.org/10.1016/j.reactfunctpolym.2017.12.018
Kotliarevski, L., Cohen, R., Ramakrishnan, J., Wu, S., Mani, K.A., Amar-Feldbaum, R., et al . (2022) Individual Coating of Entomopathogenic Nematodes with Titania (tio 2 ) Nanoparticles Based on Oil-in-Water Pickering Emulsion: A New Formulation for Biopesticides. Journal of Agricultural and Food Chemistry , 70, 13518-13527. https://doi.org/10.1021/acs.jafc.2c04424
Zou, W., Zhao, Y., Deng, Y., Zhang, H., Mao, Z., Xiong, Y., et al . (2022) Preparation of Layered Beta-Cypermethrin-Carrying Microcapsules from Pickering Emulsion of Hollow Mesoporous Silica Nanoparticles. Materials Today Communications , 31, Article 103695. https://doi.org/10.1016/j.mtcomm.2022.103695
Zheng, L., Cheng, X., Cao, L., Chen, Z., Huang, Q. and Song, B. (2022) Enhancing Pesticide Droplet Deposition through O/W Pickering Emulsion: Synergistic Stabilization by Flower-Like ZnO Particles and Polymer Emulsifier. Chemical Engin eering Journal , 434, 134761. https://doi.org/10.1016/j.cej.2022.134761
Tian, J., Xie, J., Hao, L., Chen, H., Zhou, X. and Zhou, H. (2024) Zein/Sodium Abietate Complex Stabilized Pickering Emulsion as a Delivery System for Controlled Release of Hydrophobic Photosensitive Pesticide. Industrial Crops and Products , 212, Article 118347. https://doi.org/10.1016/j.indcrop.2024.118347
Yaakov, N., Kottakota, C., Mani, K.A., Naftali, S.M., Zelinger, E., Davidovitz, M., et al . (2022) Encapsulation of Bacillus Thuringiensis in an Inverse Pickering Emulsion for Pest Control Applications. Colloids and Surfaces B : Biointerfaces , 213, Article 112427. https://doi.org/10.1016/j.colsurfb.2022.112427
Ma, Y., Gao, Y., Zhao, X., Zhu, Y., Du, F. and Hu, J. (2018) A Natural Triterpene Saponin‐Based Pickering Emulsion. Chemistry — A European Journal , 24, 11703-11710. https://doi.org/10.1002/chem.201801619
Gan, M., Pan, J., Zhang, Y., Dai, X., Yin, Y., Qu, Q., et al . (2014) Molecularly Imprinted Polymers Derived from Lignin-Based Pickering Emulsions and Their Selectively Adsorption of Lambda-Cyhalothrin. Chemical Engineering Journal , 257, 317-327. https://doi.org/10.1016/j.cej.2014.06.110
Zhang, X., Sun, X., Wang, M., Wang, Y., Wu, Q., Ji, L., et al . (2020) Dummy Molecularly Imprinted Microspheres Prepared by Pickering Emulsion Polymerization for Matrix Solid-Phase Dispersion Extraction of Three Azole Fungicides from Fish Samples. Journal of Chromatography A , 1620, Article 461013. https://doi.org/10.1016/j.chroma.2020.461013
Yu, X., Chen, S., Wang, W., Deng, T. and Wang, H. (2022) Empowering Alkali Lignin with High Performance in Pickering Emulsion by Selective Phenolation for the Protection and Controlled-Release of Agrochemical. Journal of Cleaner Production , 339, Article 130769. https://doi.org/10.1016/j.jclepro.2022.130769
Zhou, C., Li, H., Zhou, H., Wang, H., Yang, P. and Zhong, S. (2015) Water-Compatible Halloysite-Imprinted Polymer by Pickering Emulsion Polymerization for the Selective Recognition of Herbicides. Journal of Separation Science , 38, 1365-1371. https://doi.org/10.1002/jssc.201401469
Yin, R., Chen, L. and Ma, L. (2019) Extraction of Matrine from Soil with Matrix Solid‐phase Dispersion by Molecularly Imprinted Polymers Derived from Lignin-Based Pickering Emulsions. Journal of Separation Science , 42, 3563-3570. https://doi.org/10.1002/jssc.201900803