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Electrospinning and nanofibers Building drug delivery systems and potential in pesticide delivery Materials Today Communications 33 (2022) 104399 Available online 8 September 2022 2352 4928/© 2022 Els[.]

Materials Today Communications 33 (2022) 104399 Contents lists available at ScienceDirect Materials Today Communications journal homepage: www.elsevier.com/locate/mtcomm Electrospinning and nanofibers: Building drug delivery systems and potential in pesticide delivery Wenjie Shangguan a, b, Shuqi Li a, Lidong Cao b, Min Wei c, Zishi Wang a, *, Hongliang Xu a, * a Engineering Research Center of Pesticide of Heilongjiang Province, College of Advanced Agriculture and Ecological Environment, Heilongjiang University, 150080 Harbin, China b Key Laboratory of Integrated Pest Management in Crops, Ministry of Agriculture, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, 100193 Beijing, China c Heilongjiang Plant Quarantine and Protection Station, 150080 Harbin, China A R T I C L E I N F O A B S T R A C T Keywords: Electrospinning Nanofiber Drug release system Nanoformulation processing Controlled release Flexible and efficient electrospinning technology is favored in pharmaceutical processing Nanocarriers obtained in this way have high drug loading capacity, encapsulation, and excellent mechanical properties, thus enriching the equipment library of drug delivery systems It is also noteworthy that the superior performance of nanofiber carriers has attracted the attention of the pesticide nanoformulation field, this technology is gradually promoting pesticide delivery systems moving to the nanoscale, which will increase the application scenarios and safety of traditional pesticides It is a mainstream trend to obtain multi-structured fiber carriers at the microscopic level through needle modification of electrospinning equipment In this paper, electrospinning technology and elec­ trospun nanofiber are introduced in detail, included drug nanocarriers and multiple electrospinning methods, these are necessary and comprehensive for the expansion and translation of nanotechnology applications More importantly, the development and challenges of electrospinning in pesticide micro/nano formulation are reviewed, and prospects were also prospected from the perspective of nanoscale pesticide formulation processing and application, all to improve the combination of electrospinning nanotechnology and plant protection Introduction Drug delivery systems can solve the traditional drug dilemma [1–5] The use of polymers as drug delivery vehicles can provide practical properties such as controlled and sustained release, enhancement and protection of drug activity, safety, and others, besides studies have shown that these composite systems can be effective in clinical treat­ ment [6] The development of carrier materials down to the nanoscale further enhances the targeting and intracellular penetration of the complexes and allows for continuous circulation in the body, improving the overall therapeutic effect of the enhanced delivery mechanism [7,8] Stimulus-responsive nanocarriers can also make drug delivery systems more intelligent and flexible for different therapeutic scenarios, and nanocarrier-assisted drug delivery systems are rapidly becoming a research hotspot [9] Initially, a template method based on "membrane synthesis" allowed for size-controlled nanofiber carriers to be obtained [10] Nanofibers have the advantages of small diameter, high porosity, large specific surface area, and mechanical properties compared to conventional fibrous materials [11] Thus, these properties allow nanofibers to be used with a wide range of drugs and in novel drug delivery systems However, the question of how to improve the prepa­ ration efficiency and average product quality of nanocarriers to reach the standard of scale-up and industrialization has been one of the most pressing problems for researchers and nano companies Electrospinning is a flexible, efficient, homogeneous uniform nano­ fiber preparation technology that has largely improved the productivity of the nano-pharmaceutical industry [12] In fact, in the last two de­ cades, more and more researchers have been focusing on the preparation of drug nanocarriers by electrospinning technology and have achieved remarkable results Electrospinning compounding of pure drug mole­ cules with polymers results in drug delivery systems with a sustained release effect [13] The electrospun fibers of artemisinin complexes with core-shell structures for effective transdermal drug delivery systems [14] Improved triaxial electrospinning provides a more optimal de­ livery mode for aspirin drugs [15] Unconventional air-jet electro­ spinning technology enables efficient access to protein carrier-based * Corresponding authors E-mail addresses: shanggwj@126.com (W Shangguan), caolidong@caas.cn (L Cao), 2016048@hlju.edu.cn (Z Wang), xuhongliang@hlju.edu.cn (H Xu) https://doi.org/10.1016/j.mtcomm.2022.104399 Received 12 May 2022; Received in revised form 18 August 2022; Accepted September 2022 Available online September 2022 2352-4928/© 2022 Elsevier Ltd All rights reserved W Shangguan et al Materials Today Communications 33 (2022) 104399 increasingly different applications are being developed In the middle of the 20th century, the use of nanotechnology began to explode, and na­ tional research institutes were established to develop nanotechnology [31] In the same period, the advances in biopharmaceutics and phar­ macokinetics focused the attention of researchers on the controlled and sustained release of drugs [32] The first nanocapsules for drug delivery were developed in the 1970 s and this work succeeded in prolonging the release time of drugs [33] Since then, drug nanocarriers have officially entered the limelight Nanocarriers often refer to new carriers with a particle size between 10 and 1000 nm, and the materials of nanocarriers are inorganic nanomaterials (carbon, fullerene derivatives, metals, and metallic ox­ ides, porous materials) and organic nanomaterials (natural bio­ molecules, synthetic polymers, semi-synthetic polymers) [28,34] These materials can be processed for use in exogenous stimuli-responsive drug delivery (temperature, magnetic, ultrasound, light, and electrical sensing) and endogenous stimuli-responsive drug delivery (pH, redox, enzymes) as well as multi-stimuli-responsive drug delivery [35,36] In addition, drug delivery systems are often expected to have the following characteristics to adapt to different therapeutic conditions or environ­ ments [7,37]: (1) long-term cycle; (2) targeted drug delivery through multiple mechanisms of action; (3) stimulation in response to patho­ logical location; (4) enhanced drug delivery through the intracellular movement of drug molecules; (5) provided real-time information on drug biodistribution and target accumulation These characteristics are strongly associated with cellular internalization mechanisms [38] When engineered nanocarriers of the appropriate size class are designed, delivery of sustained-release drugs can be achieved in a va­ riety of situations [39–41] The methods typically used to prepare nanomedicine carriers: pre-polymerization, monomer polymerization, and ionic gelation [28,42–44] The conventional carriers prepare by pre-polymerization method suffers from poor encapsulation and low drug loading, while solvents and additives in the preparation process are difficult to handle completely, which can have an impact on later drug toxicity and therapeutic effects When preparing drug nanocarriers by monomer polymerization, most samples suffer from poor mechanical and thermal properties The ionic gelation process is highly restrictive and difficult to put into large-scale industrial production However, the research has shown that nanofibers prepared by electrospinning have a nanofiber meshes [16] These studies have shown the limitless value of this technology in the preparation of drug nanocarriers To be sure, it is also a technology worthy of continuous development Today, applica­ tions relating to electrospinning technology have been involved in a wide range of fields, such as medicine, food, clothing, and others [17–19] (Fig 1) It is also worth noting that traditional agriculture is facing the double challenges of inadequate supply and serious pollution therefore the agricultural sector must undergo a comprehensive energy transition and structural optimization [20] Likewise, the world is focusing on the impact of pesticides as a guarantee of agricultural production on the future of sustainable agriculture [21] As nanotechnology and nano­ materials enter agricultural production, they will largely contribute to the overall transformation of green pesticides, of which electrospinning has attracted the interest of some researchers with its superior perfor­ mance [22–25] In this review, the purpose is to gain insight into the development and integration of electrospinning technology with drug nanocarriers and to further explore the impediments and future of this technology in the preparation of pesticide carriers, which we hope will stimulate the reader’s thinking Nanocarriers Nanoparticles are often defined as ultrafine particles with a particle diameter between and 100 nm Nanomaterials are materials with di­ mensions up to nanometer size in at least one dimension of threedimensional space, and can usually be divided into three categories: [10,26–28] (1) the first category is in the form of nanoparticles, nano­ wires, or nanotubes; (2) the second category is nanolayers or nanofilms; (3) the third category is nanospheres or nanoflowers A set of different tests have shown that these materials on the nanoscale possess unique electrical, optical, mechanical, and magnetic properties [29] Chitin and chitosan are very popular drug carrier materials in recent years Their variation on this nanoscale is very surprising, as their various biological properties are enhanced with the increase in effective surface area, and material properties such as antibacterial, antioxidant, thermal, and mechanical properties become more prominent, with the consequent benefit of a wider range of applicability [30] As the recognition of nanoparticles and nanotechnology increases, Fig Electrospinning technology for different applications W Shangguan et al Materials Today Communications 33 (2022) 104399 high drug loading capacity with low toxicity, excellent thermodynamic properties, better industrial value, and powerful encapsulation capa­ bilities, so electrospinning technology is emerging as an excellent alternative technology [45–49] process parameters of the spinning machine, and environmental con­ ditions [56,61,62] In Table 1, the effect of process parameters, solution parameters, ambient parameters on fiber morphology were summarized As understanding of the nature of drug carriers and the principles of the electrospinning process grows, more drugs are using electrospun fiber as carriers which are used in different therapeutic scenarios For example, gentamicin sulfide [70], doxycycline [71], curcumin [72], ciprofloxacin [73], hyaluronic acid [74], moxifloxacin [75], silver nanoparticles [76], etc are used in fiber-based treatments Typically, idealized electrospinning produces continuous nanofibers of uniform diameter, defect-free morphology, and individually collectible fibers [77] However, the properties of different drugs can affect the overall compounding system and the electrospinning process The physico­ chemical properties of nanofibers will have an important impact on the drug delivery system as can be seen from numerous research reports [78–80] Among them, it has been shown that the selection of the right type of carrier material, electrospinning method, and additives will optimize the mechanical properties, hydrophilic, antimicrobial proper­ ties, and other key physicochemical properties of nanofibers [81–83] The superiority of nanofibers in terms of physicochemical properties is illustrated by the results of some of the studies listed in Table Electrospinning and nanofibers Electrospinning was officially born in the 1930 s, Anton [50] suc­ cessfully applied for a patent for electrospinning, after which nanofiber preparation, a symbol of efficiency and convenience, was officially introduced into human society After then Childs et al [51] improved the processing apparatus of electrospinning, effectively solving the problems of extrusion of polymers and their derivatives, continuous extrusion, and extrusion efficiency In 1969, Taylor et al [52] analyzed in detail the process of cone formation (Taylor cone) of droplets at the end of the needle and the ejection process of the fiber stream, which helped further understanding of how electrospinning machines work Subsequently, HOW et al [53] used electrospinning to synthesize polymeric materials into artificial vascular grafts Gilding et al [54] used electrospinning to produce homogeneous porous nonwoven fiber mats Hence, the application of electrospinning technology has been extended to drug delivery systems in the medical field {{{Fig 2}}} Electrospinning technology works by using a high voltage power supply to bring a charge of a certain polarity into the polymer solution or melt After the charge has been accelerated into the collector at the opposite electrode it is subject to electrostatic attraction and internal repulsion of the solution When the electric field force is greater than the surface force, the semi-circular tip becomes a cone, and the fibers stream is then ejected from the cone tip Finally, passing through the atmo­ sphere where the solvent evaporates and is eventually deposited on the grounded collector [56] After mathematical analysis of the motion of a single fiber in a uniform and non-uniform electric field, it was found that the output of an electrostatic spinning machine was more than 20 times higher than that of a traditional spinning machine by a staggering margin [57] When comparing electrospray and electrospun, which are polymer processing processes, obvious differences in sample properties and processing parameters were found After the preparation of micro­ spheres and fibers containing different concentrations of caffeine by both methods, the electrospun produced better yields and morphology, and the in vitro drug release of nanofibers was found to be better than that of nanospheres [58,59] When drug nanocarriers are prepared by electrospinning, the morphology of the nanofibers is often a combination of different ele­ ments [60] The crucial elements are the feedstock properties, the Diversified electrospun fibers The release mechanism of nanofiber drug delivery systems prepared by electrospinning can be divided into three controlled phases, in order of diffusion due to fiber swelling, release through the membrane, and polymer degradation, with significant differences in the rates of the Table Table of parameters affecting fiber morphology Category Parameter Effect on fiber Reference processing applied voltage flow rate/feed rate tip to collector distance orifice diameter types of collectors concentration viscosity surface tension conductivity solvent dielectric constant temperature humidity diameter; morphology size; porosity; shape diameter; morphology diameter; morphology structure diameter; morphology diameter; morphology shape diameter diameter diameter; morphology porosity [63] [64] [65] [61] [62] [56] [66] [61] [67] [68] [69] [69] feedstock ambient Fig A brief Schematic representation of the electrospinning process and its relevant parameters Adapted with permission from [55] Copyright 2014 American Chemical Society W Shangguan et al Materials Today Communications 33 (2022) 104399 Table Physicochemical properties of nanofibres obtained by electrospinning Physicochemical properties Carrier material Additive Combination method Optimized performance and data Application Mechanical performance PLA/GO Silver nanoparticle Blend electrospinning PLGA /ALG Ciprofloxacin Blend electrospinning Tissue-engineering scaffolds Wound dressing PLA PVA/PLGA Doxycycline Gentamicin/ Methylprednisolone Wound dressing Ophthalmic drug delivery [71] [84] PVA/ HPβCD Hyaluronic acid/ Naproxen Blend electrospinning Blend/ Double-jet/ Coaxial electrospinning Blend electrospinning Tensile stiffness and strength (1211.05 MPa and 5.46 MPa) Young’s modulus and tensile strength (approx 150 MPa and 4.5 MPa) Ultimate tensile strength (5.57 ± 0.43 MPa) Folding endurance (142–430 times) Tissue-engineering scaffolds [74] PVP Metronidazole Blend electrospinning Norfloxacin/ Montmorillonite Pluronic F127/ Prodigiosin Blend electrospinning Vaginal drug delivery Tissue-engineering scaffolds Tissue-engineering scaffolds [85] Chitosan /CS/PUL Young’s modulus in dry state (609 ± 360 MPa), Strain at fracture in the water state (127 ± 11 %) Work of mucoadhesion (4830–1560 mJ/ m2) Elongation in the dry state (approx 49%) PBAT Fish gelatin Gentamicin Caffeine Blend electrospinning Blend electrospinning [88] [89] PLA/PU Chitosan /PVA/GO Chitosan /Gel/ PEO Tannic acid/ Silver nanoparticles Allicin Hyaluronic acid PCL/PEO Doxycycline Blend electrospinning/ LBL self-assembly Blend electrospinning Double-jet electrospinning/ Water vapor treatment Blend electrospinning Wound dressing Fast-disintegrating drug delivery systems Antibacterial dressing Wound dressing Wound dressing PEO/CS Moxifloxacin Blend electrospinning PVA/CH Tetracycline hydrochloride Blend electrospinning PEO/ALG Vancomycin Blend electrospinning Starch/PEO Silver nanoparticles Blend electrospinning/ In situ reduction PEG/PCL Silver nanoparticles/ Hyaluronic acid/ Ibuprofen Cinnamon extract Coaxial electrospinning Allyl-TPU Quaternary ammonium compounds Multinozzle blend electrospinning Chitosan/ Polyethylene/5chloro-8-quinolinol Poly (hexamethylene biguanide) /Nylon6 Indocyanine green Coaxial electrospinning PLGA/Gel Hydrophilic Antimicrobial properties Chitosan /Gel Chitosan /PVA Blend electrospinning Blend electrospinning Blend electrospinning three phases [102] Specific drug delivery methods include (1) physical absorption of the drug by the nanofiber, with the drug mostly dispersed on the carrier surface; (2) chemical surface modification of the fibers; (3) mixing of the drug and polymer solution and spinning in emulsion form; (4) preparation of drug/nanofibers with core-shell or multilayer struc­ tures by coaxial or multi-axial electrospinning techniques [103] The most common methods for the preparation of drug carriers by the electrostatic spinning devices are mono-axial electrospinning and Young’s modulus and ultimate tensile strength (1.290 ± 0.617 kPa and 0.185 ± 0.480 kPa) Water contact angle (from 127◦ to 0◦ ) Disintegration time (1.5 seconds) Water contact angle (from 121◦ to 78.9◦ ) Water contact angle (from 65◦ to 53.4◦ ) Water contact angle (from 54◦ to 41◦ ) Water contact angle (from 115.35◦ to 0◦ ) The corresponding radius of the zone of inhibition (mean ± SD) Againsting S aureus, E coli, and P aeruginosa (32.33 ± 1.15 mm, 35.67 ± 1.53 mm, and 36.83 ± 2.56 mm) The corresponding radius of the zone of inhibition (mean ± SD) Againsting E coli, S epidermidis, S aureus (8.8 ± 0.4 mm, 15.6 ± 0.3 mm, and 19.6 ± 0.2 mm) The corresponding radius of the zone of inhibition (mean ± SD) Againsting MRSA (approx 13 mm) The corresponding radius of the zone of inhibition (mean ± SD) Againsting E coli and S aureus (more than 9.7 mm and more than 10.2 mm) Zone of inhibition measurements against E coli and S aureus (0.24 ± 0.07 cm2 and 0.18 ± 0.09 cm2) Antibacterial activity against E coli and S aureus (82 ± % and 90 ± %) After in contact with E coli and S aureus for 15 (UV-treated), approx 35% killing against E coli and approx 60% killing against S aureus The corresponding radius of the zone of inhibition (mean ± SD) Againsting S aureus and P aeruginosa (14.4 ± 0.7 mm and 9.9 ± 0.7 mm) Vlable Colony Count of Pseudomonas aeruginosa/Staphylococcus aureus (CFU/mL) Nanofiber: approx 7; Model: approx 8.3 Reference [76] [73] [86] [87] [90] [91] [92] Drug delivery system Tissue-engineering scaffolds [93] Topical delivery platform [94] Wound dressing [95] Wound dressing [96] Multifunctional barrier membrane [97] Medical material [98] Wound dressing [99] Surgical mesh surfaces [100] Wound dressing [101] [75] coaxial electrospinning, while coaxial electrospinning can produce nanofibers with a core-shell structure [104] In recent years, in order to meet the needs of new drug delivery systems, a multi-fluid electro­ spinning process has been obtained by changing the needle of the de­ vice, which enables more composition and spatial structure of the drug delivery systems [105] In addition, the use of side-by-side electro­ spinning to obtain Janus nanofibers with asymmetric properties has also attracted the attention of scientists [106] In recent years, scholars have W Shangguan et al Materials Today Communications 33 (2022) 104399 obtained many different fibers based on a processing-structure-property preparation concept and modifying the needle structure of electro­ spinning apparatus to obtain nanofiber carriers with different properties is almost certain to be one of the most common development directions in the field of carriers in the future {{{Fig 3}}} market [121,122] Solubilization ability of porous nanofibrous supports has been verified [123–125] In recent years, with the improvement of mono-axial electrospinning machines, the production speed has been greatly enhanced and the related downstream production lines have been intensively developed [126–129] Szabo et al [130] prepared electrospun tablets loaded with itraconazole and designed a continuous system to produce pharmaceutical formulations, drug testing, and product collection, this system provides a reference for tablet prepara­ tion of poorly soluble pesticides 4.1 Mono-axial electrospinning The use of single-needle electrospinning is the original method of electrospinning, which produces fibers with continuity, toughness, high porosity, and mechanical properties Surprisingly, it performs well in terms of productivity and drug delivery [107] In terms of obtaining a sustained release of the drug, the linezolid combination prepared by this technique has long-lasting antibacterial activity and can be obtained in a more stable drug form [108–110] The electrospun fiber mats had excellent encapsulation rates and mechanical properties [111] Drug carriers were able to perform the long-term treatment at low drug doses In subsequent studies, researchers found that different solvents and even different solvent ratios affected the spinnability of the solution in the process, so the resulting slow release of the drug was different [112] In another case, Bohm et al [113] postulated that viscosity-induced changes in spinnability might be due to chemical reactions or physical entanglements that form crosslinks in the feedstock The advantages of mono-axial electrospinning technology are also reflected in the high encapsulation and loading capacity For example, essential oil requires a closed environment for the delivery and the fiber structure provides an effective encapsulation for these drugs, thus extending their range of application [114–117] In the delivery system loaded with essential oils, the antimicrobial effect becomes more pro­ nounced over time and the essential oils are well protected, resulting in a surprisingly slow release [118,119] Comparing different preparation techniques for drug carriers, Karen et al [120] evaluated microcapsules and nanofiber films loaded with cinnamaldehyde and tested them spe­ cifically for their encapsulation and antifungal properties The results indicated that the fiber carrier prepared by the single-needle electro­ spinning technique was able to encapsulate about 0.4 g of cinnamalde­ hyde and had a wider area of inhibition against the grey mold fungus At the same time, low-cost single-needle electrospinning is also a very promising way to prepare fast-dissolving tablet formulations on the 4.2 Side-by-side electrospinning By adapting the needle structure of the electrospinning apparatus so that the solution enters the needle from both sides and is then electro­ spinning, it can obtain Janus nanofibers Drug carriers prepared by sideby-side electrospinning provide a stable two-stage drug release mecha­ nism, one stage leads to an accelerated release with increased drug dissolution and the other gives a sustained and controlled release for the drug in the polymer [131] Materials with opposite properties are widely used in side-by-side electrospinning to gain more functionality [132–137] In a study by Zheng et al [138], it seems possible that for water-soluble polymers, the crescent shape facilitated rapid release while the round shape facilitated the controlled and sustained release of the composite drug It is quite certain that the concept of functional nanomaterials design based on shape change will strike on future thinking about drug production Secondly, to ensure the formation of effective Janus nanofiber structures, the various spin fluids should have sufficient contact time and area before spinning [139] Compared to single-needle electrospinning fibers, fibers with two different sides offer more versatility in design and functionality in special scenarios [106] In addition, the beading of fibers caused by changes in the drug to polymer ratio during electrospinning has long been regarded as a sign of a defective product However, Li et al [140] obtained a Janus beads-on-a-string prepared by side-by-side electrospinning technique, and controlled the particle distribution and diameter range of the Janus beads-on-a-string nanostructures by polymer concentration, while the Janus beads-on-a-string obtained a better release than the Janus nano­ fiber (Fig 4) Fig Preparation of drug carriers and their fibrous morphology by electrospinning technology W Shangguan et al Materials Today Communications 33 (2022) 104399 Fig Preparation and morphology of Janus beads-on-a-string, and schematic diagram of the release mechanism Reprinted with permission from [140] Comply with Creative Commons Attribution 4.0 International License 4.3 Coaxial electrospinning coaxial electrospinning technology could effectively inhibit the side ef­ fects of sudden drug release [13,153] The core-shell structural response function can also be achieved by processing pH-sensitive materials [154] The coaxial electrospinning apparatus has two concentric nozzles that eject fibers with a core-shell structure under voltage This tech­ nology, which was first proposed in experiments with water encapsu­ lation, has surprisingly attracted a lot of attention and the encapsulation and protection offered by the core-shell fibers have unlimited potential in the field of drug delivery [141–143] The core is better protected by the shell material of the coaxial electrospun fibers, coaxial electrospinning technology have been proven to have outstanding drug release [144,145] Rafiei et al [146] combined wet electrospinning and coaxial electrospinning to produce a tissue-engineering scaffold with a three-dimensional “spongy” structure It has commonly been assumed that the porous structure of the nano­ fibers facilitates the proliferation of cells or the efficient release of active substances Environmentally responsive polymers could provide addi­ tional targeting capabilities when used as carrier material Wang et al [147] developed a multi-component nanofiber that could control drug release based on pH changes, thereby enabling multi-point drug release Indeed, the improved coaxial electrospinning apparatus also enables electrospinning of traditionally "non-spinnable" solutions and is one of the potential techniques for the formation of amorphous solid disper­ sions (Fig 5) [148–151] It has been reported that the stable Taylor cone could be a key factor in the formation of this core-shell structure [152] Finally, because of the encapsulation properties of the core-shell struc­ ture, the drug rarely appears on the surface of the fibers and thus the 4.4 Triaxial electrospinning The triaxial electrospinning technology changes the needle structure since the traditional electrospinning apparatus and introduces three fluids together for electrospinning, thus obtaining multi-layered nanofiber mats The fibers prepared by triaxial electrospinning can have more structural and hierarchical properties, triaxial electrospinning-based fi­ bers also play an important role in increasing drug dissolution, sustained release, and zero-order release kinetics, among other functions [155, 156] Chang et al prepared electrospun shell-Janus core nanostructures for drug delivery, which are capable of intelligent three-stage controlled drug release according to pH changes in the digestive system (Fig 6) [157] In the same way, Ding et al [15] modified the original "dynamic atomization process" by placing the outermost layer of the needle as a solvent layer, resulting in the same functional nanofibers with a core-shell mechanism Nanofibers obtained by triaxial electrospinning have a drug release profile that is closer to the zero-level release kinetics Wang et al [158] utilized cellulose acetate as the sole matrix to prepare drug composite fiber The drug/polymer composite structure of the interlayer allowed for optimization of the diffusion mechanism, which W Shangguan et al Materials Today Communications 33 (2022) 104399 Fig Core− shell nanodrug containers prepared by coaxial electrostatic spinning machine, which improved the sustained release of water-insoluble curcumin An Improved coaxial Electrospinning technique for the Preparation of rapid dissolution carriers for insoluble oral drugs Reprinted with permission from [148] Copyright 2021 American Chemical Society Reprinted with permission from [151] Comply with Creative Commons Attribution 4.0 International License in turn eliminated abrupt release and reduced the late tailing-off release Similarly, Huang et al [159] and Yang et al [160] also constructed core-shell nano depots based on triaxial electrospinning technology to optimize the release profile of drugs In order to respond to the needs of drug delivery in different contexts, electrospinning technology has been continuously optimized to obtain various functional drug carriers, these results would seem to suggest that the processing-structure-property based preparation concept has been more widely accepted Thus far, this thesis has argued that utilization of electrospinning for the preparation of drug carriers in the medical field already has some conditions to enter scale-up and industrialization, and the excellent properties of nanofibers provide a template for drug delivery that can be replicated Moreover, how to extend the technology of preparing drug carriers by electrospinning to pesticide delivery and to create value for pesticide industry remains one of the key issues for future researchers of this technology the agricultural sector, it offers an opportunity for revolutionary de­ velopments in the transformation of traditional agriculture and ecological management [163] In particular, the use of polymeric ma­ terials to encapsulate agrochemicals, allows them to be applied in a way that is permeable, rigid, biocompatible, and multifunctional in line with the requirements of future green pesticide [22,23,164] Green pesticide is an important topic worldwide, and its innovation requires new for­ mulations for synergy Electrospun nanofibers may make a strong contribution to it in the following aspects: (1) Natural polymer materials such as chitosan, cellulose, cyclodex­ trin, and synthetic polymer materials such as poly­ hydroxybutyrate and polycaprolactone have been successfully applied with electrospinning technology [30] These materials with good biodegradability are very friendly and green to the environment Electrospun nanofibers prepared from these mate­ rials will be more favored in the development of green carriers for pesticide In addition, this will increase the frequency of appli­ cation of biodegradable materials in green pesticides and reduce the burden on the environment from the use of pesticides (2) Electrospun nanofibers provide good mixing chambers for active ingredients, carrier materials, and other functional additives The electrospun carrier possesses high loading and encapsulation ef­ ficiency, as well as the large specific surface area brought by the loose porous structure, which can endow the pesticide delivery system with excellent slow and controlled release function [103] This will enhance the effectiveness of pesticides and reduce res­ idue problems caused by pesticide abuse (3) Electrospinning technology can be modified to obtain micro/ nanofibers with different structures, which provide more options for pesticide loading [105] Thus, the flexible electrospinning technology can be used as an application-scenario-oriented development process for pesticide formulations Functionalized chambers and abundant fiber interface modifications enable Electrospinning and pesticides As was pointed out in the introduction to this paper, the high dependence of traditional agriculture on fossil fuels and the overall lack of food supply is hindering the transition to sustainable agricultural development [20] Pesticides, which have been used for phytochemical protection since ancient times, are one of the main targets of these doubts The rapidly growing use of pesticides and the difficulty of sys­ tematically regulating the pesticide market have placed a serious burden on the environment and governments around the world [21] In addition to groundwater, soil, and food contamination caused by pesticide misuse, which is difficult to fully address, more and more plant patho­ gens, pests and weeds are showing varying degrees of resistance to traditional pesticides [161] Meanwhile, the development of new pes­ ticides faces multiple thresholds of toxicology, pathology, and signifi­ cant capital investment (Fig 7) [162] In recent years, as nanotechnology continues to be introduced into W Shangguan et al Materials Today Communications 33 (2022) 104399 Fig Morphological and internal structural features of sheath-separate-core nanofibers: (a) SEM images of the cross-sections, (b) TEM image of the inner complex nanostructures (c) Physical status of the components: XRD patterns (the raw polymers, drug and the sheath-separate-core nanofibers), PM image of drug substance particles (d) In vitro drug release profile of sthe sheath-separate-core nanofibers: A-stomach; B-small intestine; C-colon Reprinted with permission from [157] Comply with Creative Commons Attribution 4.0 International License Fig The dilemma facing pesticides around the world stimulus-responsive capabilities Such fibers can promote the precise targeting of pesticides and provide a more scientific and efficient platform for pesticide delivery (4) With the development of biotechnology, biopesticides have become an important part of green pesticides Due to the high requirements for biological activity of biopesticides, conven­ tional pesticide formulation processing methods cannot be well applied The microscopic arrangement of electrospun nanofibers is conducive to the growth of mycelium, and its activity and persistence are optimized and enhanced [165] The related technical achievements and crossover fields of electrospinning may lead the formulation innovation of green pesticide products The previous section has shown that electrospinning technology in the preparation of drug carriers has formed a certain scale of the research base and theoretical system Fortunately, the successes and lessons learned from this technology in medical drug delivery systems can be transferred to the construction of new pesticide delivery systems and address a number of these pressing issues [166] Nanofiber carriers have been attracted to the utilization of electrospinning technology for agricultural plant protection in the last decade because of their desirable properties such as high specific surface area, drug encapsulation rate, and loading capacity, and controlled and sustained release of drugs Insect pheromones, microbial pharmaceuticals, and some pesticides have been successfully combined with electrospun nanofibers and used W Shangguan et al Materials Today Communications 33 (2022) 104399 in pesticide delivery systems [24,25] pheromones to interfere with pest biology and to be used in conjunction with traps to kill pests over large areas [167] Hellmann et al [168] reported for the first time the electrospun fibers loaded with pheromone (Z)− 9-dodecyl acetate, which disrupted mating in insects, and showed that the carrier fibers could be loaded with large amounts of pheromone and extended the release effect to several months Following this, studies had been reported combining microcapsules with nanofibers to obtain 5.1 Insect pheromone Insect pheromones are regarded as a non-toxic, environmentally friendly, and species-specific compound and are fastly becoming an important part of agricultural pest management, enabling the use of Fig (A) Solution preparation and electrospinning process, characterization device and experimental materials (B) Interaction between composite membrane materials and biomolecules (C1-C3) Inhibitory potential regions of biocomposites against bacteria (M phaseolina; R solani; F oxysporum) (C4-C6) Inhibition of bacteria by biocomposites on different media (D4-D12) Morphology of the nanofibers of the biocomposite, and a close-up of the microbes in the fibers Reprinted with permission from [176] Copyright 2019 American Chemical Society W Shangguan et al Materials Today Communications 33 (2022) 104399 hydrophilic and stable pheromone carriers [169] At the time, such expositions are unsatisfactory because these works did not involve field trials and the exact model of delivery was still at the conceptual stage, so it was not known how well it would work in practice Bisotto-De-Oliveira et al [170] demonstrated that nanofibers loaded with Trimedlure could lure the male of Ceratitis capitata in field cage tests They also extracted and synthesized pheromones from Grapholita molesta and then loaded them onto electrospinning fibers, showing that the system was able to disrupt Grapholita molesta males for up to five weeks, and this work confirmed that fiber-loaded pheromones can assist in trapping pests under field conditions [171] Over time, the market for pheromones for plant protection has demanded more efficacy and sta­ bility Kikionis et al [172] created a pheromone release system capable of controlling the amount and rate of drug loading and ensuring the duration of release under different circumstances It has also been pro­ posed that electrospun fibers loaded with picaridin could be used as insect-proof clothing, which may provide a reference for the preparation of long-lasting and durable pheromone carriers [173] However, these are still some distance away from the real needs of pheromone release systems in different environments and there is a gap with commercial pheromones Additionally, they could not achieve the requirements of intelligent and environmentally friendly drug delivery systems electrospinning and solvent casting technique, respectively The microporous structure of electrospun films enables higher cumulative release rates of DCNA than in as-cast films, but the release profiles of the two drug-loaded films are not significantly different It is worth noting that in recent years, essential oils have received more and more atten­ tion in the field of pesticide applications because of their safety and antibacterial and anti-insect effects Stramarkou et al [182] used elec­ trospun nanofibers to effectively restrain the volatile and prolonged action time of rosemary essential oil This innovative strategy may be introduced into agricultural mulch films and greenhouse films, but field trials and more practical application scenarios need to be further ˜ eda et al [184] both utilized developed Farias et al [183] and Castan electrospinning technology to prepare nanofibers loaded with fungicides to coat plant seeds, which provided antibacterial throughout the seed development stage and did not cause negative effects Buchholz et al [185] produced an electrospun film of lianas that acted primarily on the pruning openings of the plants, forming a "wound dressing"-like film wrap that was effective in preventing the appearance of infection after antifungal agent loading Czarnobai et al [186] made a very interesting attempt, they used electrospun fibers to load both insecticides and pheromones and demonstrated that there were no side effects in this way Recent cases reported by Gao et al [187–189] also supports the technology that insoluble pesticide loading by electrospinning These efforts have succeeded in increasing the solubility of insoluble pesticides while maintaining concentration and bacterial inhibition, while signif­ icantly reducing the content of organic solvents and thus environmental pollution, providing a green and efficient solution for the preparation of traditional pesticide carriers (Fig 9) In summary, pesticide-loaded electrospun fibers enable the creation of multifunctional pesticide delivery systems and have industrial po­ tential as well as environmental friendliness In comparison with con­ ventional pesticide carriers, electrospinning technology has greatly developed the functionality of pesticide carriers, but there is still a lot of potentials to be explored in the preparation of pesticide nanocarriers via this technology Much of the research in the last decade has also been confined to the laboratory or semi-field state, and many of the results have not yet been deployed in large-scale production, depending of course on the synchronization of the associated downstream processes, as well as the gap compared to their commercial counterparts But it is almost certain there will be much room for discussion about the com­ bination of this technology with pesticide encapsulation in the fasci­ nating future research agendas 5.2 Microbial pesticide Nanofibers loaded with microorganisms are used as an effective alternative technology in biological formulations, and scholars in the field of plant protection are already practicing in this direction Spasova et.al [174] loaded Trichoderma viride spores into chitosan via electro­ spinning technique Spores maintained biological activity and repro­ duction while being able to effectively suppress bacteria after covering the plant Similarly, Damasceno et al [175] prepared a fiber carrier loaded with soybean rhizobia and the fiber was able to provide pro­ tection to these rhizobia under fungicide conditions Such approaches, however, have failed to involve illustrating the mechanism and process of bacterial inhibition by nanofiber loaded with microorganisms, which was a prerequisite and guarantee for biochemical products to enter the biocide market In some subsequent studies, the protective effect of biochemical agents prepared by electrospinning technology on plants or seeds has been emphasized, without stressing the potential systemic bactericidal effect of the composite fibers, which may, of course, be related to the unstable bactericidal capacity of the microorganisms themselves (Fig 8) [176,177] Recently De Cesare et.al [178] investi­ gated a soil-based three-dimensional porous fibrous scaffold The ability of the scaffold to provide better delivery assistance when biochemical agents were used for fungicidal or insecticidal purposes might excite more discussion on the mechanism and delivery of such compounded drugs 5.4 Potential research directions Finally, we note some interesting studies that may contribute to the development of the field in the future In the latest research on elec­ trospun films for the remediation of environmental pollution, porous fibrous mats are obtained by modifying the film structure and surface of nanofibrous films using porogenic agents, mesoporous materials, defective structures, etc., these super hydrophilic, highly loaded mats could carry a more rapid release pesticide carrier device and would result in a better release under vibration [190,191] It is likely to provide some reference for solving the current problem of dissolution and deposition of insoluble pesticides In the same way, Amorini et al [192] modified electrospun films to form a deep cavity structure on the surface that could accommodate solute molecules, and the cavity structure was freely regulated by pH to meet the renewable and recyclable nature of the films Up to now, not much attention has been paid to recyclable electrospinning carriers in the pesticide field, however, this concept is very attractive for green pesticides, particularly in the reuse of insect sex attractant loaded nanofiber mats in traps Additionally, with the development of melt electrospinning, new pesticide delivery systems based on bionic scaffolds have come into view The stent structure has the typical benefits of a drug delivery system, and the biocompatibility and protection offered by the bionic 5.3 Traditional pesticide Turning now to traditional pesticides, the processes for the prepa­ ration of electrospun fiber loaded with pesticides have emerged sporadically, but most work has focused on the sustained release of the delivery system, whereas in practical application scenarios more vari­ able and targeted delivery methods are needed to complement the treatment [179] In the construction of sustained and controlled release delivery of chemical pesticides by electrospinning, Roshani et al [180] used biodegradable Poly(L-Lactide) to prepare an electrospun mem­ brane loaded with thiram pesticide, and verified that the release mechanism of thiram pesticide in electrospun nanofibers was Fickian type Their study showed that fiber shrinkage caused by the annealing operation changes the release mechanism to Higuchi type, which may be one of the conventional methods for the modification of pesticide fiber formulations in the future Thitiwongsawet et al [181] prepared 2, 6-dichloro-4-nitroaniline (DCNA)-loaded film formulations by 10 W Shangguan et al Materials Today Communications 33 (2022) 104399 Fig (A) Mechanistic diagram of the process of hydroxypropyl-β-cyclodextrin (HPβCD) encapsulation of difenoconazole (DZ) (B) Docking modeling of HPβCD and DZ (C) Phase solubility diagram of the HPβCD/DZ inclusion complex system (D) Dissolution behavior of DZ in distilled water and (E) HPβCD/DZ nanofiber in distilled water Reprinted with permission from [188] Copyright 2021 American Chemical Society 11 W Shangguan et al Materials Today Communications 33 (2022) 104399 nanofibers could be of great help in the recovery of plant wounds [113] Notably, the novel hydrogel-nanofiber carrier obtained by electro­ spinning technology has unique properties such as hydrophilicity and flexibility, which makes the formulation more adaptable to different drug delivery systems [193] Its excellent mechanical properties make pharmaceutical manufacturers more expect its drug release in the field environment [194] Another significant aspect of nanocarriers is safety, more attention should be devoted to toxicity assessment and residue detection in the preparation of pesticides nanocarriers by electro­ spinning technology [195] {{{Fig 10}}} problem Researchers need to structurally analyse the phero­ mones and pair them with functional groups between different polymer molecules for the purpose of controlled release Here researchers can try to use materials with better photostability and biocompatibility as drug carriers, and where the field environ­ ment requires more diverse drug release mechanisms At the same time, the testing of release profiles needs to consider the application scenario, where electrospun membranes have different effects on the environment when they are in traps made of different materials Additionally, mechanical corrosion of traps and recycling of raw materials may be on the agenda for future research (2) Utilizing electrospinning to create pesticide carriers with different functions, of which environmentally responsive nano­ fibers are likely to be a future research hotspot in this field In combination with the previous point, the simultaneous loading of insecticide and sex pheromones into nanofibers is a potential and attractive insecticidal device and, as has now been tried by However, the mechanism of the synergistic effect of insecticides and sex pheromones has not been clearly explained and no very stable method to avoid the negative effects of synergy Electro­ spinning can be used as a binding medium for both, and the coreshell structure of coaxial electrospinning can avoid contact be­ tween pesticides and sex pheromones to a certain extent, which can reduce the adverse effects of mixing the two, but further research is needed on the release sequence and release capacity Environmentally responsive pesticide carrier devices can also be a fascinating challenge, as the complexity of the natural envi­ ronment can limit the choice of carrier materials (3) Fiber scaffold with bionic structure has excellent applications potential in phytoremediation and disease control Among these, melt electrospinning is a highly promising process for the prep­ aration of plant scaffolds, as it avoids the possible secondary damage to plants caused by harmful solvents during scaffold application and possesses an extremely high degree of mould­ ability For the practical application of this technology, specific model simulations and in vivo studies are necessary In addition, Conclusions and future perspective It has been shown from this review that electrospinning offers a number of advantages in the preparation of drug carriers The flexibility and simplicity of the device and process allow the technology to be applied to a variety of drug loading applications, and we believe that this work has both academic and industrial value Furthermore, all the ex­ periments with electrospinning technology in the preparation of phar­ maceutical carriers have laid some foundation for the future production of electrospinning pesticide carriers, which, in turn, could be a viable solution to the dilemma of conventional pesticide formulations Mean­ while, this technology certainly gives motive power to the development of novel green pesticide As was mentioned in the previous chapter, the following directions may be worth exploring and studying in the future: (1) Electrospun nanofibers loaded with insect pheromones in traps as an aid to pest control, which will greatly facilitate integrated pest management Sex pheromones can enhance the threat of traps to pests, and the slow-release effect of electrospun nanofibers can be the perfect partner for this control strategy Although attempts were made a few years ago, as far as we know, the industry has not been well industrialized The first must overcome the impact of UV, rain, wind on the delivery system in the field environment Although the pheromone market is well developed, the selection of suitable carrier materials for loading pheromones is still a Fig 10 Characterization of excellent mechanical properties of hydrogel fibers a) Manual fabrication of a hydrogel fiber from ultrastretchable hydrogel through a “Contact-Separation-Stretching” method, scanning electron microscopy (SEM) images of the b) external part and c) cross-section of the hydrogel fiber, the ability of hydrogel fiber to withstand d) twisting, e) bending, f) knotting, and g) lifting an ornament (11.9 g) using a single hydrogel fiber with a diameter of ≈ 50 µm, scale bar in inset g) is 100 µm Reprinted with permission from [193] Copyright 2022 John Wiley and Sons 12 W Shangguan et al Materials Today Communications 33 (2022) 104399 carrier materials used as scaffolds need to be further discussed as they may lead to adverse immunological and phycological consequences (4) In addtion, improved safety testing of nanocarriers is imminent in order to counter the permeability and toxicity of nanostructures that have emerged At the same time, residue rates and residue levels of nano-agents in soil or organisms have not been well addressed and further risk assessment is needed for nano-agents that significantly alter soil composition The researcher could monitor and characterise as much as possible around the path­ ways of exposure and the extent of involvement of nano-agents (5) The development of production processes for nanofibers as pesticide carriers and their downstream processes, optimization of drug release profiles by adjustment of process parameters In 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and composite layers, Solid State Ion 32–33 (1989) 771–782, https://doi.org/10.1016/0167-2738(89)90357-3 This review concentrates on the process of preparing drug carriers by electrospinning technology, focusing on a comprehensive discussion of its combination and application Finally, extending to the problems encountered in the development of this technology in the field of pes­ ticides and the prospect of producing pesticide nanocarriers by elec­ trospinning technology was discussed It is hoped that this review will stimulate the exploration of electrospinning techniques for the prepa­ ration of pesticide nanocarriers CRediT authorship contribution statement Wenjie Shangguan: Conceptualization, Visualization, Investiga­ tion, Formal analysis, Writing – original draft Shuqi Li: Investigation, Validation, Writing – review & editing Min Wei: Investigation, Writing – review & editing Lidong Cao: Writing – review & editing, Supervi­ sion Zishi Wang: Writing – review & editing, Supervision Hongliang Xu: Writing – review & editing, Project administration, Funding acquisition Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper Data Availability No data was used for the research described in the article Acknowledgment This work was supported by the Natural Science Foundation of Heilongjiang Province under Grant (grant number LH2019C055), the Innovative Research Projects for Graduate Students of Heilongjiang University (grant number YJSCX2022-100HLJU), the Project funded by China Postdoctoral Science Foundation under Grant (grant number 2019M651316), the Supported by the earmarked fund for China Agri­ culture Research System (grant numbers CARS-17-10B), the Hei­ longjiang Provincial Postdoctoral Science Foundation under Grant (grant number LBH-Z18261), and the Department of Education of Hei­ longjiang Province under Grant 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