Feather keratin-functionalized nanomesoporous silica enhances the control effect of indoxacarb on Solenopsis invicta

Feather keratin-functionalized nanomesoporous silica enhances the control effect of indoxacarb on Solenopsis invicta | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Feather keratin-functionalized nanomesoporous silica enhances the control effect of indoxacarb on Solenopsis invicta Su-qing Huang, Xiao-feng Xie, Jiao Ding, Nanhe Huang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3377780/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Herein, a pesticide-controlled release system (IDC-loaded FK-HMS) with pH and reduced glutathione (GSH) response characteristics was designed and prepared, in which the carboxyl group of feather keratin (FK) was coupled with aminated hollow mesoporous silica (HMS), and indoxacarb (IDC) was loaded into HMS. The composite system was characterized by scanning electron microscopy, Fourier transform spectroscopy, X-ray diffraction, and high-performance liquid chromatography. FK-HMS showed a high loading ratio (23.22%, w/w) on IDC while exhibiting dual sensitivity to pH value and reduction response. Compared with the same dose of the original IDC drug, IDC-loaded FK-HMS showed better killing activity against invasive species of Solenopsis invicta , which was because nanoscale FK-HMS was easily absorbed by Solenopsis invicta and entered midgut cells, reducing the effect of detoxification enzymes. Furthermore, low-dose IDC@FK-HMS effectively inhibited the actions of Solenopsis invicta , indicating that the insecticide-controlled release system based on FK-modified HMS nanoparticles is capable of sustained and long-term control of Solenopsis invicta . Hollow mesoporous silica Feather keratin Indoxacarb Solenopsis invicta Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Pesticides are an important means of preventing and controlling diseases, pests, and weeds, which can ensure the growth process of crops and make significant contributions to modern agricultural production (Mechado et al. 2022; Frizen et al. 2021 ). Pesticides improve crop yields and land use efficiency to a certain extent and meet the food needs of the growing global population. However, traditional formulations of pesticides have drawbacks such as poor dispersion and adhesion. Their large-scale abuse not only leads to low pesticide utilization and environmental pollution but also enhances resistance to diseases, pests, and weeds, resulting in resource waste (Liang et al. 2017 ; Zhao et al. 2018 ). At present, types of traditional pesticides are no longer able to meet the requirements of green and sustainable development. To meet the growing food demand without damaging the environment, researchers are looking for feasible solutions to the current agricultural problems through innovative nanotechnology and nanomaterials, aiming to realize green agricultural production and overcome the limitations of traditional agriculture (Yang et al. 2017 ; Scott et al. 2018 ; Bartolucci et al. 2020 ;). Researchers have found that compared with other nanomaterials, hollow mesoporous silica (HMS) has highly structured mesoporous channels and large internal cavities and has the advantages of excellent biocompatibility, good stability and large drug load (Chakravarty et al. 2015 ). The types of loaded drugs are not limited, and the surface of HMS is easy to modify so that it can be endowed with various response functions. Response functions, such as light, pH, temperature, redox, and enzyme, are therefore widely used in controlled drug release systems (Aznar et al. 2009 ; Du et al. 2013 ; Fan et al. 2017 ; Liang et al. 2018 ; Gao et al. 2019 ). In recent years, agricultural researchers have also been committed to studying the preparation of nanopesticide controlled release systems by HMS, using the excellent performance of HMS to improve the utilization rate of pesticides and reduce environmental pollution. Tang (2017) et al. reported that a large number of HMS molecules were cross-linked with carboxylated β-cyclodextrin, and their Si-OH bonds were modified by -COOH and -NH 2 to form Si-NH 2 bonds, making β-cyclodextrin the "gatekeeper" of HMS. Yang (2021) et al. prepared carboxylated β-cyclodextrin-modified HMS loaded with IDC, which had pH and enzyme trigger reaction characteristics and showed excellent toxicity to armyworms, reducing the toxicity of IDC to zebrafish by more than 5 times. Yang (2022) et al. synthesized a pH and glutathione (GSH) dual-stimulatory response pesticide delivery system with disulfide bond-modified chitosan blocking HMS for the prevention and control of cucumber downy mildew, and its toxicity to zebrafish was significantly reduced. The pesticides encapsulated in HMS enter the insect body through insect ingestion, and then their release is controlled through pH value, digestive enzymes, and redox stimulation in the insect body to prevent and control insects. Alternatively, the release of pesticides in HMS can be controlled through plant lesions caused by diseases, such as the pH value of the lesion site and redox stimulation, to prevent and control diseases (Kaziem et al. 2017 ; He et al. 2021 ). In addition to HMS and other nanomaterials that are favored by researchers, biological polymers have attracted the attention of researchers because of their excellent biocompatibility and biodegradability. With the deepening of structural analysis and the understanding of nanotechnology, the research and utilization of proteins have also rapidly increased in recent years (Wamel et al. 2016 ; Villanueva et al. 2018 ). Keratin (FK), a structural protein widely existing in waste feathers, is rich in functional groups (such as amino, carboxyl, and sulfhydryl groups), as well as disulfide, hydrogen, and ionic bonds, showing a wealth of modification sites and groups or key positions for material functionalization. Therefore, FK has also been widely used in nanotechnology in recent years (O’Connell and Hedges 1999 ; Saucedo-Rivalcoba et al. 2011 ; Fass and Thorpe 2018 ). As a bond widely used in functional nanomaterials, the high sensitivity of bonds endows nanomaterials with excellent redox response characteristics (O’Connell and Hedges 1999 ). Li (2017) et al. prepared mercaptocarboxymethylated keratin-chlorhexidine nanoparticles with a pH value and GSH double response through electrostatic interactions, showing excellent antibacterial activity but slight cytotoxicity at a low dose. Sun (2017) et al. prepared nanogels with pH value and reduction sensitivity by crosslinking keratin to sodium alginate through sulfhydryl groups, which had certain targeting functions and produced certain toxicity to related cancer cells. In the medical field, researchers have designed many nanomaterials with pH and redox characteristics by using the characteristics of keratin to produce more GSH and pH changes near cancer cells (Li et al. 2017 ; Sun et al. 2018 ; Yi et al. 2018 ). At present, there are few studies on the use of keratin in agriculture. GSH is an important biomolecule in the second stage of insect detoxification, and the use of keratin has a certain application potential in pest control. Solenopsis invicta , one of the most dangerous in the world, can seriously destroy the local natural ecological balance and threaten people's lives (Cheng et al. 2015 ). Moreover, red fire ants are highly vigilant against insecticides. When solid- or liquid-containing insecticides are carried back to the ant nest by workers, they are decomposed into liquid food by the larvae and eaten by other members. Once the insecticides take effect too early, the workers quickly release warning signals to remind the whole ant colony, which makes the insecticides fail to achieve a good killing effect (David and Faith 2006 ; Xiong et al. 2019 ). Therefore, an effective method for ant colony control is to ensure that most ant colony members are exposed to insecticides. However, most chemical insecticides currently take effect quickly and have difficulty achieving the expected effect. Responsive drug delivery systems can be an effective way to spread pesticides throughout red fire ants. In this study, FK was used as a functional molecule to cover HMS, enabling HMS to have the ability of GSH response to sustainably release IDC. The ability of HMS to release IDC at different pH values was explored, with or without FK modification and with or without GSH. The toxicity of IDC@FK-HMS to red fire ants and the effect of low concentrations of IDC@FK-HMS on red fire ants were determined, and the enhancement effect of FK-HMS on the photostability of IDC was systematically evaluated. The results of this study contribute to research on nanointelligent drug delivery systems for controlling agricultural pests and reducing environmental damage caused by pesticides. Materials and Insects Feather keratin (FK) was proposed in the laboratory from waste chicken feathers; Peracetic acid was provided by Guangzhou Chemical Group Co., Ltd. 2,2'-Azobis (2-methylpropylamine) dihydrochloride (V-50, > 97.0%), 1-(3-dimethylaminopropyl)-N' -ethylcarbon diimide hydrochloride (EDC, 98%), n-hydroxysuccinimide (NHS, 98%), cetyltrimethyl ammonium bromide (CTAB, > 97.0%), sodium hydride (60%),N, N-dimethylformamide (99.5%), and polyvinyl alcohol pirrodanone (K-30, > 99.5%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. China. Tetrasilone orthosilicate (TEOS, 98%), styrene (99%), (3-amino-propyl) triethoxysilane (APTS, 98%), urea (AR, 99%), and isothiocyanate (FITC) were obtained from Shanghai Maclin Biochemical Co., Ltd. Acryloxyethyl trimethyl ammonium chloride (80%) was provided from Tianjin Zhongnuo Biochemical Technology Co., Ltd. Ammonia (28%) and sodium hydroxide (96%) were obtained from China Silong Technology Co., Ltd. Toluene (99.5%) and acetone (99.5%) were bought from Guangzhou Chemical Reagent Factory in China. Acetonitrile (> 99.9%), methanol, and ethanol (> 99.9%) were purchased (> 99.5%) from ANPEL Scientific Instruments (Shanghai). IDC (95%) was provided by the Chinese Academy of Agricultural Sciences. All the chemicals were not additionally purified. The blank bait was provided by Key Laboratory of Natural Pesticide and Chemical Biology, Ministry of Education, South China Agricultural University, Guangzhou, China. Solenopsis invicta came from a farm in Tianhe District, Guangzhou, China (E113.46, N23.38). Based on the method documented by Banks (Banks et al. 1981), red fire ants were collected, screened, and reared in containers coated with Teflon emulsion on the top walls. A test tube filled with 10% bee water or water was used and covered with a cotton swab to provide water, and ham sausage and mealworms served as food sources. The ant nests were kept in a suitable environment of 25 ± 2 ℃ and 70 ± 10% relative humidity (RH) for two weeks. 2.2. Preparation of mesoporous silica and functionalization of feather keratin FK was extracted from waste feathers by the oxidation method (Weston 1955 ), as follows. Liquids A and B of peracetic acid were mixed at 1:1, stirred evenly, and allowed to stand for 24 h. Feather powder and peracetic acid solution were weighed and mixed in a solid‒liquid ratio of 1:15. The mixture was stirred in a 60 ℃ water bath for 90 min, centrifuged in a 4500 rpm centrifuge for 5 min, and filtered with 200 mesh gauze to remove unreacted solid particles. The filtered liquid was placed in a dialysis bag (Oso-t 8280, with an interception molecular weight of 8000–14000 Da) for dialysis for 4 d. The deionized water was changed every 12 h, and the feather keratin solids were extracted and filtered. Then, the solid was precooled in an ice well at -60 ℃ for 6 h and dried in a freeze-dryer for 5 d. Finally, a light-yellow solid was obtained, ground into powder, and placed in a dry environment for use. HMSs were prepared by an improved template method (Kaziem et al. 2018 ). Then, 2.5 mL K-30 was added to a three-necked flask containing 200 mL water, 100 mL styrene was slowly added while continuing to drain N 2 , and the mixture was stirred magnetically at room temperature for 30 min. Then, 25 mL V-50 aqueous solution was added to the system, which was placed in an oil bath at a constant temperature of 90 ℃ and stirred magnetically for 24 h to form polystyrene latex (PSL). In a 500 mL round-bottomed flask, 6.4 g CTAB was dissolved in 224 mL water, and 96 mL ethanol, 8 mL ammonium hydroxide, and 80 g PSL solution were added in turn. 36 g of TEOS was slowly dripped into the system and subjected to 48 hours of magnetic stirring in an oil bath at a constant temperature of 40°C. The reaction solution was centrifuged at 5000 rpm for 10 min, and the precipitates were cleaned with ethanol three times. The precipitates were dried in an oven at 60 ℃ for 12 h. The PSL template was removed by calcination at 600 ℃ in a muffle furnace for 8 h, obtaining HMS. HMS was aminated to achieve its functionalization. HMS (2.5 g) was dissolved ultrasonically into 250 mL anhydrous toluene and placed in a constant temperature oil bath at 110°C with magnetic stirring. Then, 12.5 mL of APTS was slowly dropped and refluxed under continuous N 2 flow for 24 h. The reaction solution was centrifuged at 4500 rpm for 5 min, and the precipitates were cleaned with ethanol three times. The precipitates were dried in an oven at 60 ℃ for 12 h. 10 g of FK was dissolved in an 8 M urea solution, followed by the addition of 2.5 g of EDC to activate the -COOH group of the FK solution. After 30 min, 5 g HMS-NH 2 phosphate buffer solution (PBS) was added to the ultrasonic solution, followed by 2.5 g NHS. The solution was then placed in the dark for 24 h with magnetic stirring. The samples were centrifuged (4500 rpm) for 5 min, washed 3 times, and dried in a 60°C oven for 24 h to obtain FK-HMS 3 g of IDC and 1 g of NH 2 -HMS were dissolved in acetone solution in turn, stirred magnetically for 24 h, and dried by vacuum rotary evaporation, and IDC@NH 2 -HMS was collected. Then, IDC@NH 2 -HMS was dissolved in a phosphate buffer solution (PBS) by ultrasound. Then, 0.5 g EDC-activated 2 g FK solution and 0.5 g NHS were added successively, stirred in the dark for 24 h, centrifuged (4500 rpm) for 5 min, washed 3 times, and dried in an oven at 60°C for 24 h to obtain IDC@FK-HMS. 2.3. Characterization The structure and morphology of the samples were observed by a Verios 460 (Thermo Fisher, USA) field emission scanning electron microscope (SEM) and a Talos F200S (Thermo Fisher, USA) field emission transmission electron microscope (TEM) equipped with energy dispersive scanning (EDS). The zeta potential of the sample was measured using a Zetasizer Nanosizer (Malvern Instruments, Worcestershire, UK). The Fourier transform infrared spectra of the samples were analysed using a Spectrum100 instrument (Perkin-Elmer, USA) with a resolution of 4 cm − 1 , a scanning range of 500–4000 cm − 1 , and 16 repeated scans. Thermogravimetric analysis (TGA) was performed using TGA 2 (Mettler Toledo, Switzerland) at a heating rate of 10 ℃/min and a temperature range of 35–800℃. The N 2 isothermal elution attachment of the sample was determined by a Gemini VII 2390 instrument (Micromeritics Instruments, USA). The Brunauer‒Emmett‒Teller (BET) method was employed to calculate the specific surface area. The loading efficiency of IDC was measured by high-performance liquid chromatography (HPLC, 20A, Shimazu Scientific Instruments, Japan) (Wang et al. 2020 ). The determination was performed on an AgilentZORBAX Eclipse XDB-C18 (4.6 mm × 250 mm, 5 µm) column with a detection wavelength of 244 nm and a column temperature of 30 ℃. The mobile phase used in this experiment was methanol/water (70:30, v/v), the flow rate was 1 mL/min, and the sample volume was 10 µL. 2.4. UV stabilization determination Photolysis is one of the main reasons for the degradation of active components of pesticides under field conditions, and resistance to photolysis testing is an important means to evaluate the synergistic effect of materials on pesticides. The IDC active drug with an IDC concentration of 100 mg/L and the acetonitrile-water solution of IDC@FK-HMS (30: 70, v/v) were combined, placed under a 36 W UV lamp (244 nm), and stirred at 25 ℃ with magnetic force to test the UV shielding properties of IDC and IDC@FK-HMS. The light source was located 10 cm above the surface of the solution, and 3 mL of solution was collected regularly for HPLC analysis to determine the remaining concentration of IDC. 2.5. Release in vitro The release of IDC@FK-HMS at pH = 7.4 and pH = 4.5 was studied, with or without FK functionalization, and with or without glutathione (reduced). IDC@FK-HMS or IDC@HMS (100 mg) was dissolved sonically into 500 mL acetonitrile-water solution (30:70, v/v) and then stirred at 200 rpm. At different time intervals, 3 mL of solution was removed from the release medium, and the same volume of release medium was added. The collected solution was centrifuged at a speed of 15000 rpm for 3 min, and the supernatant was collected and analysed by HPLC. The experiment was repeated 3 times for each treatment. The formula for calculating the IDC cumulative release is as follows: V 1 is the total volume of solution (500 mL), V 2 is the volume of solution taken out (3 mL), C t is the measured concentration, and M is the amount of IDC actually contained in the sample. Zero-order and first-order release dynamic equations were used to model the in vitro release dynamic data. The release mechanism of IDC from HMS and FK-HMS was determined by simple and useful mathematical models, including the Korsmeyer-Peppas model (Korsmeyer et al. 1983 ), Hixson-Crowel model (Hixson and Crowell 1931), and Higuchi model (Higuchi 2010 ; Patel et al. 2010 ). The n values in the Korsmeyer-Peppas model were then used to characterize the different release mechanisms, as shown in Table 1 . Table 1 Explanation of the diffusion release mechanism. Release index (n) Drug release mechanism n ≤ 0.5 Fickian release 0.5 < n < 0.8 non-Fickian release n ≥ 0.8 Case II release When n ≤ 0.5, the diffusion rate is less than the relaxation rate, and the release rate is mainly controlled by the Fickian diffusion process. Non-Fickian diffusion occurs when n is in the range of 0.5–0.8. In this case, diffusion and relaxation rates are comparable, and drug release depends on swelling diffusion and matrix erosion. When n ≥ 0.8, the main mechanism of drug release is Case II diffusion, indicating that the release is mainly controlled by the polymer relaxation process; that is, the matrix also causes erosion when the drug is released over time (Singh et al. 2018 ). 2.6. Biological activity determination 2.6.1. Toxicity determination IDC acetone solution, IDC@FK-HMS acetone suspension, and FK-HMS acetone suspension were diluted with 0.5% Triton X-100 water in accordance with the liquid‒solid ratio of 1:10 (mL: g). IDC acetone solution, IDC@FK-HMS suspension, and FK-HMS suspension at different concentrations were added to the blank bait, and the samples required for the biological activity test were obtained by stirring evenly. After the red fire ants were driven out of the soil with water for 12 h, 5 g of different bait and 1.5 centrifuge tubes containing 1 mL distilled water were placed at the bottom of a 250 mL pancake (the top wall was coated with Teflon emulsion), and the control group was blank bait with 0.5% Triton X-100 + 0.5% acetone water. All treatments were repeated 3 times, and each group contained 30 red fire ants. Bait and water were replaced every 12 hours. The experiment was conducted at 25 ± 2 ℃ and 70 ± 10% relative humidity (Zheng et al. 2020 ). The number of deaths of red fire ants was recorded at a predetermined time, and the death rate was calculated according to Formula 2–2: Mortality rate = number of dead ants/total number of ants×100% (2–2) 2.6.2. Observation of aggressive behavior On the basis of the toxicity test, red fire ants were fed acetone, FK-HMS, and IDC@FK-HMS at an IDC concentration of 2 mg/L to analyse the changes in their aggressive behavior. The control group was fed a blank diet supplemented with 0.5% Triton X-100 + 0.5% acetone water, with 50 red fire ants of similar size in each group. The experiment was carried out according to Step 2.6.1. After 24 h, the bait was replaced with 1 cm mealworms, and the number of red fire ants that touched and attacked it within 30 min was recorded. In addition, the time of suspended animation and death of the mealworms were recorded. The inability of powder insects to move after being stimulated by needles was defined as death. Then, the mealworms were removed and replaced with the corresponding bait, and observations were performed at 24 h, 48 h and 72 h (Zheng et al. 2022 ). 2.6.3. Determination of detoxification enzyme activity Red fire ants (1.5 g) were randomly selected and fed IDC bait, IDC@FK-HMS bait, and FK-HMS bait at a dose of 2 mg/L. Blank bait with 0.5% Triton X-100 + 0.5% acetone water was used as the control group. Glutathione S-transferase (GST), acetylcholinesterase (AchE), and carboxylesterase (CarE) were extracted from red fire ants at different time points (24 h, 48 h and 72 h), and their activities were measured using GST, AchE, and CarE activity assay kits according to the experimental protocol recommended by Beijing Box Science & Technology Co., Ltd. 100 mg of red fire ants with different treatments was weighed and placed in a 5 mL centrifuge tube. Then, 1.0 mL of enzyme extract was added, placed on ice for homogenization, and centrifuged at 8000 rpm for 10 min at 4°C. The supernatant was collected as the enzyme source. LabServ K3 TOUCH (Thermo Fisher Scientific, USA) was used to determine absorbance, and all treatments were repeated three times. 2.7. Study on the intestinal structure of red fire ants 2.7.1. Changes in midgut cells observed by He staining Some red fire ants were randomly selected and fed the 2 mg/L IDC diet, IDC@FK-HMS diet, and FK-HMS diet. Red fire ants with a blank diet of 0.5% Triton X-100 + 0.5% acetone water were used as the control group. After 72 hours of feeding, red fire ants were placed in PBS, and the midgut was separated from the abdomen of red fire ants with tweezers. The midguts were transferred to a glass tube containing 4 mL of paraformaldehyde fixator, fixed at 4°C for 24 h, and then transferred to 70% ethanol solution for dehydration. The samples were embedded in paraffin, cut into sections of 3–4 µm, fixed on slides, stained with hematoxylin and eosin, and observed under a microscope (Nikon, Japan). 2.7.2. The migration of drug-carrying materials in the midgut observed with fluorescence microscope FK-HMS (300 mg) was ultrasonically dispersed in PBS (pH = 8.0), 50 mg FITC was then added, and the reaction was kept in the dark for 24 h. The reaction solution was transferred to a dialysis bag (Oso-t 8280, with an intercepted molecular weight of 8000–14000 Da) for dialysis until the solution was clear and colorless. Then, FITC-FK-HMS was added to the diet to feed red fire ants for 72 h. Red fire ants fed a blank diet of 0.5% Triton X-100 + 0.5% acetone water were employed as the control group. The midintestine of red fire ants was treated according to 2.7.1. Fluorescence images were collected using an inverted fluorescence microscope (Nikon, Japan) at a maximum wavelength of 490–495 nm for absorption and 525–530 nm for emission. 2.8. Statistical analysis All data were calculated and analysed using SPSS 25.0 software and Microsoft Office Excel 2019. Data are reported as the mean ± SD (standard deviation). Origin 2021 was employed to draw and fit drug release kinetics models. A graphic summary was drawn using Powerpoint 2019. An independent sample t test was used to analyse the difference between the two treatment groups, and (*) indicates a statistically significant difference between the two treatment groups (P < 0.05). Duncan's test was used to analyse the differences among the four treatment groups. The same letter indicates no significant difference, while different letters represent significant differences (P < 0.05). Preparation of IDC@FK-HMS The synthesis route from IDC loading to FK-functionalized HMS was shown in Fig. 1 . First, HMSs were prepared by the hard template method. To enable FK to successfully perform functional modification on HMS, the surface of HMS was modified by APTS to achieve amination. Then, the IDC dissolved in acetone solution was loaded into the HMS by vacuum spin steaming. IDC-loaded NH 2 -HMS was obtained, and the functional modification of NH 2 -HMS by FK was realized through the coupling reaction of amino and carboxyl groups, generating the final result, namely, IDC@FK-HMS. 3.2. SEM, TEM and EDS The morphological characteristics of HMS, NH 2 -HMS, FK-HMS, and IDC@FK-HMS were observed by SEM and TEM, the particle size distribution statistics of HMS and IDC@FK-HMS were determined, and energy dispersion spectrum (EDS) mapping of IDC@FK-HMS was performed (Fig. 2 ). As shown in SEM micrographs (Fig. 2 a, b), HMS and FK-HMS of loaded IDC exhibited relatively uniform nanospheres in size. The particle size of HMS (Fig. 2 c) reached approximately 155 nm, while that of IDC@FK-HMS (Fig. 2 d) was approximately 178 nm, which was due to the encapsulation of HMS by FK. Figure 3 a showed that HMS possessed an obvious cavity structure, with many pores on the surface directly entering the cavity. The particle size of HMS obtained by TEM was consistent with that obtained by SEM. By observing Fig. 3 b and Fig. 3 c, it could be found that neither amination nor FK modification will damage the cavity structure inside HMS, and FK modification could seal the pores on the surface. Figure 3 d showed that the cavity size of IDC@FK-HMS was much smaller than that of NH 2 -HMS and FK-HMS, which proved the successful loading of IDC on HMS. In Fig. 3 e, the EDS results showed that C, O, Si, N, F, Cl, S and other elements all present sphericity consistent with IDC@FK-HMS, indicating that IDC@FK-HMS contained IDC, which was consistent with the results observed by TEM. 3.3. Structural characterization The functional groups of HMS, NH 2 -HMS, FK-HMS, IDC, FK and IDC@FK-HMS were characterized by FTIR. Compared with FK, NH 2 -HMS, HMS and FK-HMS (Fig. 4 a), the characteristic absorption peak of the amidogen was centered at 1668 cm − 1 and 1489 cm − 1 (i.e., the bending vibration peak of N-H), indicating that the surface hydroxyl group of HMS successfully reacted with phenylamino silane group of APTS. The characteristic absorption peak of the polypeptide (-CO-NH-) from feather keratin was centered at 2924 cm − 1 in the FK-HMS spectrum (Eslahi et al. 2013 ). The peaks at 1637 cm − 1 , 1523 cm − 1 , and 1452 cm − 1 were the amide Ⅰ band (i.e., the tensile vibration peak of C = O), Ⅱ band (i.e., the bending vibration peak of N-H and the tensile vibration peak of C-N), and Ⅲ band (i.e., the bending vibration peak of C = O and the tensile vibration peak of C-N) (Eslahi et al. 2013 ). The tensile vibration peak caused by Si-O-Si was located at 1080 cm − 1 (Ha et al. 2005 ), and the vibration peak caused by Si-O was concentrated at 798 cm − 1 , indicating that HMS was successfully modified by FK. By comparing the FTIR spectral lines of FK-HMS, IDC, and IDC@FK-HMS (Fig. 4 b), the peak at 1746 cm − 1 and 1694 cm − 1 corresponded to the asymmetric stretching vibration of the carbonyl group (-C = O) in IDC. The stretching vibration peak of CF 3 and O = C-N was located at 546 cm − 1 (Memarizadeh et al. 2014 ), without obvious movement, which was ascribed to the successful loading of IDC into HMS without causing chemical changes. The zeta potentials of HMS, NH 2 -HMS, FK-HMS, and IDC@FK-HMS were analysed using a Zetasizer Nanosizer. The ζ potentials of HMS, NH 2 -HMS, FK-HMS, and IDC@FK-HMS were − 3.05 mV, 28.50 mV, 23.97 mV, and 6.47 mV, respectively (Fig. 4 c). HMS exhibited a negative ζ potential in the presence of the -OH group, while NH 2 -HMS demonstrated a positive ζ potential due to protonation following the introduction of the amino group. Compared with that of NH 2 -HMS, the ζ potential of FK-HMS decreased, which was related to the coupling between the carboxyl group of FK and an amino group. However, there were certain amino groups in FK, and the ζ potential of FK only slightly decreased, which proved that FK successfully modified HMS. In addition, IDC was loaded into HMS, and the hydrogen bond force or intermolecular force between IDC and FK led to a large drop in ζ potential. The thermal stability of HMS, NH 2 -HMS, FK-HMS, FK, IDC and IDC@FK-HMS was analysed by TGA (Fig. 4 d, e, g and h). The TGA and DTG curves showed that HMS was equipped with good thermal stability and maintained a stable weight over a long temperature range. The TGA curves (Fig. 4 d) showed that the total weight losses of HMS, NH 2 -HMS, FK-HMS and FK were 6.62%, 20.39%, 39.41% and 93.98%. And the DTG curves (Fig. 4 e) showed that FK-HMS, NH 2 -HMS and FK had same moss loss peak at 316 ℃ and 546 ℃, indicating that HMS was successfully aminated and modified by FK. The TGA curves (Fig. 4 g) showed that the total weight losses of IDC and IDC@FK-HMS were 99.84% and 62.56%. And the DTG curves (Fig. 4 h) showed that IDC and IDC@FK-HMS had same moss loss peak at 318℃. Comparing with the weight loss of FK-HMS and IDC@FK-HMS, the weight loss rete was 23.14%, and the load rate of IDC measured by HPLC was 23.22%. The test results of both were consistent, which further proved that IDC was successfully loaded into HMS. The mesoporous structures of HMS and IDC@FK-HMS were determined by BET specific surface area analysis. The N 2 isothermal adsorption and desorption curves of HMS and IDC@FK-HMS were shown in Fig. 4 f. HMS and IDC@FK-HMS showed obvious type IV isotherms, with clear hysteric loops caused by mesoporous structures. Through BET specific surface area calculations, IDC@FK-HMS significantly decreased from 271.21 m 2 /g to 64.77 m 2 /g compared to HMS, which was due to the successful loading of IDC and the modification of FK. Both HMS and IDC@FK-HMS only possessed a single wide peak in Fig. 4 i, achieving the maximum peak value at 22°. HMS and IDCFK-HMS appeared as amorphous states, without crystal sequence reflection throughout the entire spectrum or IDC crystal peaks, which indicated that the IDC was loaded in the HMS. 3.4. In vitro release and light stabilization Table 2 Regression coefficient values and release index (n) corresponding to kinetic model fitting Sample Release condition Zero-order First-order Higuchi Hixson– Crowel Korsmeyer–Peppas R 2 R 2 R 2 R 2 R 2 n IDC@FK-HMS pH 4.5 0.7633 0.9614 0.9347 0.6779 0.9730 0.3389 pH 7.4 0.8859 0.9791 0.9936 0.7855 0.9936 0.4622 GSH,pH7.4 0.9249 0.9879 0.9971 0.8081 0.9959 0.5428 IDC@HMS pH 7.4 0.8531 0.9468 0.9811 0.7611 0.9944 0.3900 Figure 5 a showed the cumulative release of IDC from IDC@FK-HMS at 25 ℃ at different pH values (4.5 and 7.4). The cumulative release of IDC@FK-HMS at pH 4.5 was greater than that at pH 7.4. The amide bond (-CONH-) was broken under acidic conditions, and the outer layer of FK dissolved in acidic conditions and presented a straight chain state, exposing the pores of HMS and synergistically accelerating the release of IDC. The initial release was fast, showing a slow rate over time, which was similar to previous studies (Xu et al. 2018 ; Gao et al. 2019 ). The experiment showed that IDC@FK-HMS could be released quickly in the red formic acid intestines. Figure 5 b showed the cumulative release of IDC@FK-HMS with GSH (reduced prototype) at 25 ℃ and a pH of 7.4. In the absence of GSH (reduced prototype), the cumulative release of IDC@FK-HMS was small, only 4.89% at 1 d and 16.24% at 15 d. In contrast, the cumulative release of IDC@FK-HMS in the presence of GSH (reduced prototype) was relatively high, with only 13.40% at 1 d and 55.82% after 15 d (Yang et al. 2022 ). The disulfide bond (-S-S-) of FK was destroyed under GSH (reduced type), generating a straight chain state of FK, increasing dissolution, and exposing HMS channels. As an important detoxifying raw material of glutathione S-transferase in insects (Smith et al. 2019 ), GSH is widely found in insects and very beneficial to intelligent drug delivery. Figure 5 c displayed the effect of FK modification on HMS at 25 ℃ and a pH of 7.4. The release rate of IDC@HMS was faster, and its cumulative release rate reached 28.88% in 1 d and 80.24% in 15 d. The release rate of IDC@FK-HMS was relatively slow, and its cumulative release amount from 1 d to 15 d was 4.89% and 16.24%, respectively, which indicated that the covering of FK on the surface of HMS effectively prevented the release of IDC (Yang et al. 2021 ; Wu et al. 2022 ). Under ultraviolet irradiation, the IDC decomposition amount reached 31.48%, while only 3.24% of the 24 h released part was decomposed in IDC@FK-HMS, as shown in Fig. 5 d. The energy in OH − , H + , and UV in water was absorbed by molecules or atoms in the IDC structure, resulting in the breaking of IDC molecular bonds (Wen et al. 2021; Xu et al. 2018 ). The experimental results showed that FK-HMS effectively improved the optical stability of IDC and exhibited good UV-shielding performance. According to the fitting results in Table 2 , the regression coefficients R 2 of the first-order dynamic models of IDC@FK-HMS and IDC@HMS were larger than those of the zero-order dynamic model under any in vitro release conditions, indicating that the release curve of IDC followed the first-order dynamic model. In addition, IDC@FK-HMS and IDC@HMS conformed to the Higuchi model rather than the Hixson-Crowel model under all in vitro release conditions, suggesting that most IDCs in FK-HMS and HMS were released by diffusion. The n values of IDC@FK-HMS and IDC@HMS obtained by the Korsmeyer-Peppas model were both less than 0.5 under acidic and neutral conditions, and the diffusion mechanism of IDC belongs to Fickian diffusion, namely, the diffusion of drugs from the pore. The diffusion index n value of IDC@FK-HMS was greater than 0.5, and the diffusion mechanism of IDC followed a non-Fickian diffusion mechanism, which was due to the certain dissolution effect of GSH on FK covering the surface. From the above experimental results, IDC@FK-HMS was released in response to both acid and GSH. 3.5. Biologicalactivity observation The death rates of red fire ants treated with IDC, FK-HMS, and IDC@FK-HMS at different concentrations after different periods were analysed. In Fig. 6 a, the death rate of red fire ants treated with IDC for 24 h was significantly higher than that of red fire ants treated with IDC@FK-HMS (P < 0.05). IDC@FK-HMS had a slow-release function, and IDC was not released completely from FK-HMS. However, IDC directly acted on red fire ants, which caused them to be alert and reduced feeding (Wen et al. 2021). There was no significant difference in the mortality rate of red fire ants treated with IDC and IDC@FK-HMS for 48 h (Fig. 6 b), while the mortality rate of IDC@FK-HMS after 48 h was significantly higher than that before 24 h (P < 0.05). IDC@FK-HMS was under the action of red fire formic acid in the intestinal tract and internal GSH. IDC was released from IDC@FK-HMS, which increased the death rate of red fire ants. After 72 h (Fig. 6 c), the mortality rate of the IDC@FK-HMS group was significantly higher than that of the IDC group (P < 0.05), indicating that IDC was enhanced when loaded into FK-HMS nanoparticles. IDC@FK-HMS had good shielding ability, which reduced the hydrolysis of IDC by the insect intestinal environment. The half-life of IDC was effectively enhanced, and the service life of the active ingredients of pesticides was significantly enhanced. In addition, the fast release of IDC@FK-HMS was triggered conditionally, which weakened the harm of IDC to nontarget organisms and made the ecological environment safer. As shown in Fig. 6 d, the contact recognition of attacking mealworms in the IDC and IDC@FK-HMS treatment groups was significantly lower than that in the FK-HMS and control groups. The function of the nerve cells of red fire ants was lost by blocking sodium ion channels in nerve cells, resulting in red fire ant movement disorder and reducing the recognition and attack on mealworms (Silver and Soderlund 2005 ). However, the contact recognition of attacking mealworms in the IDC treatment group was significantly higher than that in the IDC@FK-HMS group at 48 h and 72 h. At this point, IDC triggered the attack instinct and alert recognition of red fire ants (Wen et al. 2021), enabling them to quickly identify the attacking mealworms. As shown in Fig. 6 e, there was no significant difference in the suspended death time of mealworms under different treatments at 24 h. After 48 h and 72 h, the suspended death time of mealworms in the IDC and IDC@FK-HMS treatment groups was significantly higher than that in the FK-HMS and control groups. Notably, the IDC@HMS treatment group had a significantly higher suspended death time than the IDC treatment group. FK-HMS exhibited a certain shielding effect on the warning and recognition of red fire ants against IDC, allowing more red fire ants to feed on food. More red fire ants exhibited motion disorders due to the toxicity of the slowly released IDC. This phenomenon was consistent with the previous relevant test results. The results in Fig. 6 f showed that red fire ants in all treatment groups killed mealworms, while red fire ants treated with IDC@FK-HMS took a longer time to kill mealworms. The toxic effect of IDC released slowly from FK-HMS confused the metabolism level of red fire ants in whole-body tissues, thus reducing the attacking ability of red fire ants. Many studies found that the activity of detoxifying enzymes is an important index to test the influence of exogenous substances on insect enzymes and insect resistance (Chen et al. 2020 ). Figure 6 g showed that the activity of GST in the IDC treatment group was significantly higher than that in the other treatment groups at 24 h, 48 h and 72 h, which proved that the detoxification ability of red fire ants against IDC was enhanced. IDC@FK-HMS treatment group showed no significantly different from FK-HMS and CK treatment group at 24 h, 48 h and 72 h, but it was significantly lower than IDC treatment group, indicating that FK-HMS weakened the activity of GST and enhanced the virulence effect of IDC. Figure 6 h and i showed that the CarE and AchE activities of IDC and IDC@FK-HMS at 24 h, 48 h and 72 h were significantly lower than those of the other treatment groups, which was attributed to IDC significantly inhibiting the CarE and AchE activities of red fire ants. The experiment showed that FK-HMS nanoparticles enhanced the effect of IDC on red fire ants and significantly reduced the attack instinct of red fire ants, thus affecting their survival ability in the wild. 3.6. Study on the effect on intestinal structure of red fire ants Fluorescence microscopy was used to observe the location of the midgut labelled with fluorescent nanomaterials and the midgut changes in the red fire ants treated with IDC, FK-HMS, and IDC@FK-HMS at low concentrations for 72 h. As observed in Fig. 7 b, there was no significant difference between the midgut cells of red fire ants treated with FK-HMS and those of the blank control group, with normal cell membranes, which proved that FK-HMS had high biocompatibility and nontoxic effects on cells. The midgut treated with IDC showed obvious shrinkage and cell decay, which was similar to the toxicological effect of IDC and restricted the activities of red fire ants. The same shrinking cell decay occurred in IDC@FK-HMS-treated midgut cells as in IDC-treated midgut cells, showing a slight effect in the presence of the slow release of IDC from FK-HMS. According to Fig. 7 c, there were many small bright green spots in the midgut of the red fire ants fed FITC-FK-HMS, and the bright green spots should be FK-HMS labelled by FITC. Cross-sectional fluorescence intensity analysis was conducted on the midgut to further analyse the position of FITC-FK-HMS. Figure 7 d showed that the peak height of the cross-sectional fluorescence intensity in the FITC-FK-HMS treatment group was generally higher than that in the blank control group. The fluorescence intensity of bright green spots in the FITC-HMS treatment group possessed an obvious prominent peak. The nanoscale FK-HMS was easily absorbed by red fire ants and entered the midgut cells, which was conducive to promoting the toxic effect of IDC on red fire ants. Summary In this study, the functional modification of NH 2 -HMS by FK was realized through the coupling reaction of the -NH 2 group and -COOH group. FK-HMS nanoparticles loaded with IDC were synthesized, and the control effect of FK-HMS on red fire ants was investigated. FK-HMS exhibited good controlled-release ability and quickly responded to acidic pH and GSH, effectively shielding the effects of light on drugs. Biological toxicity experiments showed that FK-HMS loaded with IDC had a lasting insecticidal effect. Even a low dose of IDC@FK-HMS significantly weakened the attacking ability of red fire ants and enhanced the virulence of IDC. In addition, nanoscale FK-HMS was easily absorbed by the red fire ant and entered the midgut cells. Comparing IDC, IDC@FK-HMS reduced the action of detoxification enzymes of the red fire ant. Therefore, IDC@FK-HMS with dual response characteristics has strong potential in effectively limiting the growth of red fire ant populations and even in controlling other agricultural pests. Declarations CRediT authorship contribution statement Su-qing Huang: Conceptualization, Methodology, Data curation, Writing review and editing, Project administration, Fund acquisition. Xiao-feng Xie: Conceptualization, Methodology, Data curation, Experiment, Writing review and editing. Jiao Ding: Conceptualization, Methodology, Data curation. Nan-he Huang: Experiment. 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 Date will be made available on request. Acknowledgements Partial experiments in this work were supported by Key Laboratory of Natural Pesticide and Chemical Biology, Ministry of Education, South China Agricultural University, Guangzhou, China. Thanks to Dr. Zhi-xiang Zhang for his guidance and help in this work. Fund This work was supported by Modern agricultural industrial technology System of Guangdong Province (The task of Innovation team building of key generic technologies in agricultural resources and environment) (2023KJ118). References Aznar E, Marcos MD, Máñez RM, Sancenón F, Soto J, Amorós P, Guillem C (2009) pH- and photo-switched release of guest molecules from mesoporous silica supports. J. Am. Chem. 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Food Chem. 66 (26): 6504-6512 https://doi.org/10.1021/acs.jafc.7b02004 Zheng Q, Qin D, Wang R, Yan W, Zhao W, Shen S, Huang S, Cheng D, Zhao C, Zhang Z (2022) Novel application of biodegradable chitosan in agriculture: Using green nanopesticides to control Solenopsis invicta. Int. J. Biol. Macromol. 220: 193-203 https://doi.org/10.1016/j.ijbiomac.2022.08.066 Zheng Q, Yang L, Lin S, Ma Q, Qin D, Zhang Z (2020) Insecticidal Activity of the Leaf and Stem Water Extract of Gelsemium elegans against Solenopsis invicta . Sociobiology, 67 (2): 232 https://doi.org/10.13102/sociobiology.v67i2.4517 Additional Declarations No competing interests reported. Supplementary Files GraphicalAbstract.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3377780","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":235424069,"identity":"0fe3d2bc-2f28-457c-a8f3-bde086286a5a","order_by":0,"name":"Su-qing Huang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAuUlEQVRIiWNgGAWjYBACAxCRwMAgx8befIA0LcZ8PMcSSNACBInzJHIUiNNizn/G8MbDHbXpbQw5DAw/KrYR1mI5I8fYIvHM8dw2hrMHGHvO3CbCYTd4zCQS247ltjH2JTAzthGj5fwZsJZ0NmYeAyK1HMgBaalJYGMjWsuNtGKLxLYDhm08bAkHifPL+cMbb/5sq5OXn//44IMfFURoAQEJBobDYMYB4tRDtNQRrXgUjIJRMApGIAAAabk8H0taLpUAAAAASUVORK5CYII=","orcid":"","institution":"Zhongkai University of Agriculture and Engineering College of Chemistry and Chemical Engineering","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Su-qing","middleName":"","lastName":"Huang","suffix":""},{"id":235424070,"identity":"2a042378-bdeb-48b9-9a24-1caf290cac98","order_by":1,"name":"Xiao-feng Xie","email":"","orcid":"","institution":"Zhongkai University of Agriculture and Engineering College of Chemistry and Chemical Engineering","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Xiao-feng","middleName":"","lastName":"Xie","suffix":""},{"id":235424071,"identity":"72440f20-6281-434f-a86a-bcf72d11211d","order_by":2,"name":"Jiao Ding","email":"","orcid":"","institution":"Zhongkai University of Agriculture and Engineering College of Chemistry and Chemical Engineering","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Jiao","middleName":"","lastName":"Ding","suffix":""},{"id":235424072,"identity":"6908857b-494a-47ad-8222-f4c4fd30ac69","order_by":3,"name":"Nanhe Huang","email":"","orcid":"","institution":"Zhongkai University of Agriculture and Engineering College of Chemistry and Chemical Engineering","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Nanhe","middleName":"","lastName":"Huang","suffix":""}],"badges":[],"createdAt":"2023-09-22 18:29:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3377780/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3377780/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":43781482,"identity":"e3b227eb-afca-40a9-822e-ccb806a50868","added_by":"auto","created_at":"2023-09-27 16:40:24","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":330513,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic illustration of the preparation of IDC@FK-HMS\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/e5a717d0b00b8aa1b1946230.png"},{"id":43782060,"identity":"c8ee7ce3-b656-4578-b015-af897d141a80","added_by":"auto","created_at":"2023-09-27 16:48:24","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":487534,"visible":true,"origin":"","legend":"\u003cp\u003eSEM of HMS (a) and IDC@FK-HMS (b). Particle size distribution diagram of HMS (c) and IDC@FK-HMS (d).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/b243e41e80880653ccf92412.png"},{"id":43781486,"identity":"dee77f54-2d70-47f1-914c-e675e5c537ea","added_by":"auto","created_at":"2023-09-27 16:40:24","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":957852,"visible":true,"origin":"","legend":"\u003cp\u003eTEM of HMS (a), NH\u003csub\u003e2\u003c/sub\u003e-HMS (b), FK-HMS (c) and IDC@FK-HMS (d). EDS of IDC@FK-HMS (e).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/4ca9a2b378eb25edf5770329.png"},{"id":43781487,"identity":"59ed84ab-855e-41b9-be01-ac595a0dcec4","added_by":"auto","created_at":"2023-09-27 16:40:25","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":257984,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra (a) of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS and FK, FTIR spectra (b) of IDC, IDC@FK-HMS and FK-HMS. Zeta potential (c) of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS and IDC@FK-HMS. TGA (d) and DTG curves (e) of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS and FK. Nitrogen adsorption-desorption isotherms (f) for HMS and IDC@FK-HMS. TGA (g) and DTG curves (h) of FK-HMS, IDC@FK-HMS and IDC. XRD (i) of HMS and IDC@FK-HMS.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/bb722f370ebfbfdcb9a952ad.png"},{"id":43782062,"identity":"4f01b2f9-e5cd-4ecd-b2be-d3ea5b7c495c","added_by":"auto","created_at":"2023-09-27 16:48:25","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":162914,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of GSH (a), pH value (b) and FK (c) on the release behaviors of IDC from HMS, The stability of IDC and IDC@FKHMS UV irradiation (d).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/19526432fa0a4f5d1e64d7a1.png"},{"id":43782061,"identity":"ea55827c-0121-48d7-9b03-78f571dd9d62","added_by":"auto","created_at":"2023-09-27 16:48:24","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":219859,"visible":true,"origin":"","legend":"\u003cp\u003eInsecticidal activity of IDC, IDC@FK-HMS and FK-HMS against ants at different times (a) 24h, (b) 48h, (c) 72h. Effects of 2mg/L IDC, IDC@FK-HMS and FK-HMS on the attack behavior of ants. (d) Number of red fire ants attacking the mealworms. (e) False death time of mealworms. (f) Death time of mealworms. Effects of 2mg/L IDC, IDC@FK-HMS and FK-HMS on GST (g), CarE (h) and AchE (i) activities. All date are presented as the mean ±SE. Different letters represent significant differences (p\u0026lt; 0.05).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/eda8915562c3d4ea9936db90.png"},{"id":43781483,"identity":"d810a40e-6515-4575-9b42-688dd47110a3","added_by":"auto","created_at":"2023-09-27 16:40:24","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":401126,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Schematic of dissected ants. (b) Effects of 2 mg/L IDC, FK-HMS and IDC@FK-HMS on the intestinal cells of ants. (c) Fluorescence photograph of the cross-section of the midgut of ants. (d) Fluorescence intensity analysis results.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/5128f8c03aa33ab9704ec886.png"},{"id":44132162,"identity":"09b2687d-be2c-4cc8-b395-3b8f3acfb35e","added_by":"auto","created_at":"2023-10-05 12:22:31","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2980405,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/73213197-cdad-4e9a-952a-2d41f59cd3a4.pdf"},{"id":43781489,"identity":"b5f82715-f84d-43cb-abe5-ca98409e2de8","added_by":"auto","created_at":"2023-09-27 16:40:25","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":9861616,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstract.docx","url":"https://assets-eu.researchsquare.com/files/rs-3377780/v1/9f21473172c1f4cc46274586.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Feather keratin-functionalized nanomesoporous silica enhances the control effect of indoxacarb on Solenopsis invicta","fulltext":[{"header":"Introduction","content":"\u003cp\u003ePesticides are an important means of preventing and controlling diseases, pests, and weeds, which can ensure the growth process of crops and make significant contributions to modern agricultural production (Mechado et al. 2022; Frizen et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Pesticides improve crop yields and land use efficiency to a certain extent and meet the food needs of the growing global population. However, traditional formulations of pesticides have drawbacks such as poor dispersion and adhesion. Their large-scale abuse not only leads to low pesticide utilization and environmental pollution but also enhances resistance to diseases, pests, and weeds, resulting in resource waste (Liang et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Zhao et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). At present, types of traditional pesticides are no longer able to meet the requirements of green and sustainable development. To meet the growing food demand without damaging the environment, researchers are looking for feasible solutions to the current agricultural problems through innovative nanotechnology and nanomaterials, aiming to realize green agricultural production and overcome the limitations of traditional agriculture (Yang et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Scott et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Bartolucci et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2020\u003c/span\u003e;).\u003c/p\u003e \u003cp\u003eResearchers have found that compared with other nanomaterials, hollow mesoporous silica (HMS) has highly structured mesoporous channels and large internal cavities and has the advantages of excellent biocompatibility, good stability and large drug load (Chakravarty et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). The types of loaded drugs are not limited, and the surface of HMS is easy to modify so that it can be endowed with various response functions. Response functions, such as light, pH, temperature, redox, and enzyme, are therefore widely used in controlled drug release systems (Aznar et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Du et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Fan et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Liang et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Gao et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). In recent years, agricultural researchers have also been committed to studying the preparation of nanopesticide controlled release systems by HMS, using the excellent performance of HMS to improve the utilization rate of pesticides and reduce environmental pollution. Tang (2017) et al. reported that a large number of HMS molecules were cross-linked with carboxylated β-cyclodextrin, and their Si-OH bonds were modified by -COOH and -NH\u003csub\u003e2\u003c/sub\u003e to form Si-NH\u003csub\u003e2\u003c/sub\u003e bonds, making β-cyclodextrin the \"gatekeeper\" of HMS. Yang (2021) et al. prepared carboxylated β-cyclodextrin-modified HMS loaded with IDC, which had pH and enzyme trigger reaction characteristics and showed excellent toxicity to armyworms, reducing the toxicity of IDC to zebrafish by more than 5 times. Yang (2022) et al. synthesized a pH and glutathione (GSH) dual-stimulatory response pesticide delivery system with disulfide bond-modified chitosan blocking HMS for the prevention and control of cucumber downy mildew, and its toxicity to zebrafish was significantly reduced. The pesticides encapsulated in HMS enter the insect body through insect ingestion, and then their release is controlled through pH value, digestive enzymes, and redox stimulation in the insect body to prevent and control insects. Alternatively, the release of pesticides in HMS can be controlled through plant lesions caused by diseases, such as the pH value of the lesion site and redox stimulation, to prevent and control diseases (Kaziem et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; He et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn addition to HMS and other nanomaterials that are favored by researchers, biological polymers have attracted the attention of researchers because of their excellent biocompatibility and biodegradability. With the deepening of structural analysis and the understanding of nanotechnology, the research and utilization of proteins have also rapidly increased in recent years (Wamel et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Villanueva et al. \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Keratin (FK), a structural protein widely existing in waste feathers, is rich in functional groups (such as amino, carboxyl, and sulfhydryl groups), as well as disulfide, hydrogen, and ionic bonds, showing a wealth of modification sites and groups or key positions for material functionalization. Therefore, FK has also been widely used in nanotechnology in recent years (O\u0026rsquo;Connell and Hedges \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e1999\u003c/span\u003e; Saucedo-Rivalcoba et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Fass and Thorpe \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). As a bond widely used in functional nanomaterials, the high sensitivity of bonds endows nanomaterials with excellent redox response characteristics (O\u0026rsquo;Connell and Hedges \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e1999\u003c/span\u003e). Li (2017) et al. prepared mercaptocarboxymethylated keratin-chlorhexidine nanoparticles with a pH value and GSH double response through electrostatic interactions, showing excellent antibacterial activity but slight cytotoxicity at a low dose. Sun (2017) et al. prepared nanogels with pH value and reduction sensitivity by crosslinking keratin to sodium alginate through sulfhydryl groups, which had certain targeting functions and produced certain toxicity to related cancer cells. In the medical field, researchers have designed many nanomaterials with pH and redox characteristics by using the characteristics of keratin to produce more GSH and pH changes near cancer cells (Li et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Sun et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Yi et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). At present, there are few studies on the use of keratin in agriculture. GSH is an important biomolecule in the second stage of insect detoxification, and the use of keratin has a certain application potential in pest control.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSolenopsis invicta\u003c/em\u003e, one of the most dangerous in the world, can seriously destroy the local natural ecological balance and threaten people's lives (Cheng et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). Moreover, red fire ants are highly vigilant against insecticides. When solid- or liquid-containing insecticides are carried back to the ant nest by workers, they are decomposed into liquid food by the larvae and eaten by other members. Once the insecticides take effect too early, the workers quickly release warning signals to remind the whole ant colony, which makes the insecticides fail to achieve a good killing effect (David and Faith \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Xiong et al. \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Therefore, an effective method for ant colony control is to ensure that most ant colony members are exposed to insecticides. However, most chemical insecticides currently take effect quickly and have difficulty achieving the expected effect. Responsive drug delivery systems can be an effective way to spread pesticides throughout red fire ants.\u003c/p\u003e \u003cp\u003eIn this study, FK was used as a functional molecule to cover HMS, enabling HMS to have the ability of GSH response to sustainably release IDC. The ability of HMS to release IDC at different pH values was explored, with or without FK modification and with or without GSH. The toxicity of IDC@FK-HMS to red fire ants and the effect of low concentrations of IDC@FK-HMS on red fire ants were determined, and the enhancement effect of FK-HMS on the photostability of IDC was systematically evaluated. The results of this study contribute to research on nanointelligent drug delivery systems for controlling agricultural pests and reducing environmental damage caused by pesticides.\u003c/p\u003e "},{"header":"Materials and Insects","content":"\u003cdiv id=\"Sec2\" class=\"Section2\"\u003e\u003cp\u003eFeather keratin (FK) was proposed in the laboratory from waste chicken feathers; Peracetic acid was provided by Guangzhou Chemical Group Co., Ltd. 2,2'-Azobis (2-methylpropylamine) dihydrochloride (V-50, \u0026gt;\u0026thinsp;97.0%), 1-(3-dimethylaminopropyl)-N' -ethylcarbon diimide hydrochloride (EDC, 98%), n-hydroxysuccinimide (NHS, 98%), cetyltrimethyl ammonium bromide (CTAB, \u0026gt;\u0026thinsp;97.0%), sodium hydride (60%),N, N-dimethylformamide (99.5%), and polyvinyl alcohol pirrodanone (K-30, \u0026gt;\u0026thinsp;99.5%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. China. Tetrasilone orthosilicate (TEOS, 98%), styrene (99%), (3-amino-propyl) triethoxysilane (APTS, 98%), urea (AR, 99%), and isothiocyanate (FITC) were obtained from Shanghai Maclin Biochemical Co., Ltd. Acryloxyethyl trimethyl ammonium chloride (80%) was provided from Tianjin Zhongnuo Biochemical Technology Co., Ltd. Ammonia (28%) and sodium hydroxide (96%) were obtained from China Silong Technology Co., Ltd. Toluene (99.5%) and acetone (99.5%) were bought from Guangzhou Chemical Reagent Factory in China. Acetonitrile (\u0026gt;\u0026thinsp;99.9%), methanol, and ethanol (\u0026gt;\u0026thinsp;99.9%) were purchased (\u0026gt;\u0026thinsp;99.5%) from ANPEL Scientific Instruments (Shanghai). IDC (95%) was provided by the Chinese Academy of Agricultural Sciences. All the chemicals were not additionally purified. The blank bait was provided by Key Laboratory of Natural Pesticide and Chemical Biology, Ministry of Education, South China Agricultural University, Guangzhou, China.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSolenopsis invicta\u003c/em\u003e came from a farm in Tianhe District, Guangzhou, China (E113.46, N23.38). Based on the method documented by Banks (Banks et al. 1981), red fire ants were collected, screened, and reared in containers coated with Teflon emulsion on the top walls. A test tube filled with 10% bee water or water was used and covered with a cotton swab to provide water, and ham sausage and mealworms served as food sources. The ant nests were kept in a suitable environment of 25\u0026thinsp;\u0026plusmn;\u0026thinsp;2 ℃ and 70\u0026thinsp;\u0026plusmn;\u0026thinsp;10% relative humidity (RH) for two weeks.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Preparation of mesoporous silica and functionalization of feather keratin\u003c/h2\u003e \u003cp\u003eFK was extracted from waste feathers by the oxidation method (Weston \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e1955\u003c/span\u003e), as follows. Liquids A and B of peracetic acid were mixed at 1:1, stirred evenly, and allowed to stand for 24 h. Feather powder and peracetic acid solution were weighed and mixed in a solid‒liquid ratio of 1:15. The mixture was stirred in a 60 ℃ water bath for 90 min, centrifuged in a 4500 rpm centrifuge for 5 min, and filtered with 200 mesh gauze to remove unreacted solid particles. The filtered liquid was placed in a dialysis bag (Oso-t 8280, with an interception molecular weight of 8000\u0026ndash;14000 Da) for dialysis for 4 d. The deionized water was changed every 12 h, and the feather keratin solids were extracted and filtered. Then, the solid was precooled in an ice well at -60 ℃ for 6 h and dried in a freeze-dryer for 5 d. Finally, a light-yellow solid was obtained, ground into powder, and placed in a dry environment for use.\u003c/p\u003e \u003cp\u003eHMSs were prepared by an improved template method (Kaziem et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Then, 2.5 mL K-30 was added to a three-necked flask containing 200 mL water, 100 mL styrene was slowly added while continuing to drain N\u003csub\u003e2\u003c/sub\u003e, and the mixture was stirred magnetically at room temperature for 30 min. Then, 25 mL V-50 aqueous solution was added to the system, which was placed in an oil bath at a constant temperature of 90 ℃ and stirred magnetically for 24 h to form polystyrene latex (PSL). In a 500 mL round-bottomed flask, 6.4 g CTAB was dissolved in 224 mL water, and 96 mL ethanol, 8 mL ammonium hydroxide, and 80 g PSL solution were added in turn. 36 g of TEOS was slowly dripped into the system and subjected to 48 hours of magnetic stirring in an oil bath at a constant temperature of 40\u0026deg;C. The reaction solution was centrifuged at 5000 rpm for 10 min, and the precipitates were cleaned with ethanol three times. The precipitates were dried in an oven at 60 ℃ for 12 h. The PSL template was removed by calcination at 600 ℃ in a muffle furnace for 8 h, obtaining HMS. HMS was aminated to achieve its functionalization. HMS (2.5 g) was dissolved ultrasonically into 250 mL anhydrous toluene and placed in a constant temperature oil bath at 110\u0026deg;C with magnetic stirring. Then, 12.5 mL of APTS was slowly dropped and refluxed under continuous N\u003csub\u003e2\u003c/sub\u003e flow for 24 h. The reaction solution was centrifuged at 4500 rpm for 5 min, and the precipitates were cleaned with ethanol three times. The precipitates were dried in an oven at 60 ℃ for 12 h.\u003c/p\u003e \u003cp\u003e10 g of FK was dissolved in an 8 M urea solution, followed by the addition of 2.5 g of EDC to activate the -COOH group of the FK solution. After 30 min, 5 g HMS-NH\u003csub\u003e2\u003c/sub\u003e phosphate buffer solution (PBS) was added to the ultrasonic solution, followed by 2.5 g NHS. The solution was then placed in the dark for 24 h with magnetic stirring. The samples were centrifuged (4500 rpm) for 5 min, washed 3 times, and dried in a 60\u0026deg;C oven for 24 h to obtain FK-HMS 3 g of IDC and 1 g of NH\u003csub\u003e2\u003c/sub\u003e-HMS were dissolved in acetone solution in turn, stirred magnetically for 24 h, and dried by vacuum rotary evaporation, and IDC@NH\u003csub\u003e2\u003c/sub\u003e-HMS was collected. Then, IDC@NH\u003csub\u003e2\u003c/sub\u003e-HMS was dissolved in a phosphate buffer solution (PBS) by ultrasound. Then, 0.5 g EDC-activated 2 g FK solution and 0.5 g NHS were added successively, stirred in the dark for 24 h, centrifuged (4500 rpm) for 5 min, washed 3 times, and dried in an oven at 60\u0026deg;C for 24 h to obtain IDC@FK-HMS.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Characterization\u003c/h2\u003e \u003cp\u003eThe structure and morphology of the samples were observed by a Verios 460 (Thermo Fisher, USA) field emission scanning electron microscope (SEM) and a Talos F200S (Thermo Fisher, USA) field emission transmission electron microscope (TEM) equipped with energy dispersive scanning (EDS). The zeta potential of the sample was measured using a Zetasizer Nanosizer (Malvern Instruments, Worcestershire, UK). The Fourier transform infrared spectra of the samples were analysed using a Spectrum100 instrument (Perkin-Elmer, USA) with a resolution of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, a scanning range of 500\u0026ndash;4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 16 repeated scans. Thermogravimetric analysis (TGA) was performed using TGA 2 (Mettler Toledo, Switzerland) at a heating rate of 10 ℃/min and a temperature range of 35\u0026ndash;800℃. The N\u003csub\u003e2\u003c/sub\u003e isothermal elution attachment of the sample was determined by a Gemini VII 2390 instrument (Micromeritics Instruments, USA). The Brunauer‒Emmett‒Teller (BET) method was employed to calculate the specific surface area. The loading efficiency of IDC was measured by high-performance liquid chromatography (HPLC, 20A, Shimazu Scientific Instruments, Japan) (Wang et al. \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). The determination was performed on an AgilentZORBAX Eclipse XDB-C18 (4.6 mm \u0026times; 250 mm, 5 \u0026micro;m) column with a detection wavelength of 244 nm and a column temperature of 30 ℃. The mobile phase used in this experiment was methanol/water (70:30, v/v), the flow rate was 1 mL/min, and the sample volume was 10 \u0026micro;L.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.4. UV stabilization determination\u003c/h2\u003e \u003cp\u003ePhotolysis is one of the main reasons for the degradation of active components of pesticides under field conditions, and resistance to photolysis testing is an important means to evaluate the synergistic effect of materials on pesticides. The IDC active drug with an IDC concentration of 100 mg/L and the acetonitrile-water solution of IDC@FK-HMS (30: 70, v/v) were combined, placed under a 36 W UV lamp (244 nm), and stirred at 25 ℃ with magnetic force to test the UV shielding properties of IDC and IDC@FK-HMS. The light source was located 10 cm above the surface of the solution, and 3 mL of solution was collected regularly for HPLC analysis to determine the remaining concentration of IDC.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.5. Release in vitro\u003c/h2\u003e \u003cp\u003eThe release of IDC@FK-HMS at pH\u0026thinsp;=\u0026thinsp;7.4 and pH\u0026thinsp;=\u0026thinsp;4.5 was studied, with or without FK functionalization, and with or without glutathione (reduced). IDC@FK-HMS or IDC@HMS (100 mg) was dissolved sonically into 500 mL acetonitrile-water solution (30:70, v/v) and then stirred at 200 rpm. At different time intervals, 3 mL of solution was removed from the release medium, and the same volume of release medium was added. The collected solution was centrifuged at a speed of 15000 rpm for 3 min, and the supernatant was collected and analysed by HPLC. The experiment was repeated 3 times for each treatment. The formula for calculating the IDC cumulative release is as follows:\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\" height=\"44\" width=\"382\"\u003e\u003c/p\u003e\n\u003cp\u003eV\u003csub\u003e1\u003c/sub\u003e is the total volume of solution (500 mL), V\u003csub\u003e2\u003c/sub\u003e is the volume of solution taken out (3 mL), C\u003csub\u003et\u003c/sub\u003e is the measured concentration, and M is the amount of IDC actually contained in the sample.\u003c/p\u003e \u003cp\u003eZero-order and first-order release dynamic equations were used to model the in vitro release dynamic data. The release mechanism of IDC from HMS and FK-HMS was determined by simple and useful mathematical models, including the Korsmeyer-Peppas model (Korsmeyer et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e1983\u003c/span\u003e), Hixson-Crowel model (Hixson and Crowell 1931), and Higuchi model (Higuchi \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Patel et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). The n values in the Korsmeyer-Peppas model were then used to characterize the different release mechanisms, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eExplanation of the diffusion release mechanism.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"2\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eRelease index (n)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eDrug release mechanism\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003en\u0026thinsp;\u0026le;\u0026thinsp;0.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFickian release\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e0.5 \u003c n \u003c 0.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003enon-Fickian release\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003en\u0026thinsp;\u0026ge;\u0026thinsp;0.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCase II release\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eWhen n\u0026thinsp;\u0026le;\u0026thinsp;0.5, the diffusion rate is less than the relaxation rate, and the release rate is mainly controlled by the Fickian diffusion process. Non-Fickian diffusion occurs when n is in the range of 0.5\u0026ndash;0.8. In this case, diffusion and relaxation rates are comparable, and drug release depends on swelling diffusion and matrix erosion. When n\u0026thinsp;\u0026ge;\u0026thinsp;0.8, the main mechanism of drug release is Case II diffusion, indicating that the release is mainly controlled by the polymer relaxation process; that is, the matrix also causes erosion when the drug is released over time (Singh et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.6. Biological activity determination\u003c/h2\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.6.1. Toxicity determination\u003c/h2\u003e \u003cp\u003eIDC acetone solution, IDC@FK-HMS acetone suspension, and FK-HMS acetone suspension were diluted with 0.5% Triton X-100 water in accordance with the liquid‒solid ratio of 1:10 (mL: g). IDC acetone solution, IDC@FK-HMS suspension, and FK-HMS suspension at different concentrations were added to the blank bait, and the samples required for the biological activity test were obtained by stirring evenly. After the red fire ants were driven out of the soil with water for 12 h, 5 g of different bait and 1.5 centrifuge tubes containing 1 mL distilled water were placed at the bottom of a 250 mL pancake (the top wall was coated with Teflon emulsion), and the control group was blank bait with 0.5% Triton X-100\u0026thinsp;+\u0026thinsp;0.5% acetone water. All treatments were repeated 3 times, and each group contained 30 red fire ants. Bait and water were replaced every 12 hours. The experiment was conducted at 25\u0026thinsp;\u0026plusmn;\u0026thinsp;2 ℃ and 70\u0026thinsp;\u0026plusmn;\u0026thinsp;10% relative humidity (Zheng et al. \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). The number of deaths of red fire ants was recorded at a predetermined time, and the death rate was calculated according to Formula 2\u0026ndash;2:\u003c/p\u003e \u003cp\u003eMortality rate\u0026thinsp;=\u0026thinsp;number of dead ants/total number of ants\u0026times;100% (2\u0026ndash;2)\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.6.2. Observation of aggressive behavior\u003c/h2\u003e \u003cp\u003eOn the basis of the toxicity test, red fire ants were fed acetone, FK-HMS, and IDC@FK-HMS at an IDC concentration of 2 mg/L to analyse the changes in their aggressive behavior. The control group was fed a blank diet supplemented with 0.5% Triton X-100\u0026thinsp;+\u0026thinsp;0.5% acetone water, with 50 red fire ants of similar size in each group. The experiment was carried out according to Step 2.6.1. After 24 h, the bait was replaced with 1 cm mealworms, and the number of red fire ants that touched and attacked it within 30 min was recorded. In addition, the time of suspended animation and death of the mealworms were recorded. The inability of powder insects to move after being stimulated by needles was defined as death. Then, the mealworms were removed and replaced with the corresponding bait, and observations were performed at 24 h, 48 h and 72 h (Zheng et al. \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e2.6.3. Determination of detoxification enzyme activity\u003c/h2\u003e \u003cp\u003eRed fire ants (1.5 g) were randomly selected and fed IDC bait, IDC@FK-HMS bait, and FK-HMS bait at a dose of 2 mg/L. Blank bait with 0.5% Triton X-100\u0026thinsp;+\u0026thinsp;0.5% acetone water was used as the control group. Glutathione S-transferase (GST), acetylcholinesterase (AchE), and carboxylesterase (CarE) were extracted from red fire ants at different time points (24 h, 48 h and 72 h), and their activities were measured using GST, AchE, and CarE activity assay kits according to the experimental protocol recommended by Beijing Box Science \u0026amp; Technology Co., Ltd. 100 mg of red fire ants with different treatments was weighed and placed in a 5 mL centrifuge tube. Then, 1.0 mL of enzyme extract was added, placed on ice for homogenization, and centrifuged at 8000 rpm for 10 min at 4\u0026deg;C. The supernatant was collected as the enzyme source. LabServ K3 TOUCH (Thermo Fisher Scientific, USA) was used to determine absorbance, and all treatments were repeated three times.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e2.7. Study on the intestinal structure of red fire ants\u003c/h2\u003e \u003cdiv id=\"Sec12\" class=\"Section3\"\u003e \u003ch2\u003e2.7.1. Changes in midgut cells observed by He staining\u003c/h2\u003e \u003cp\u003eSome red fire ants were randomly selected and fed the 2 mg/L IDC diet, IDC@FK-HMS diet, and FK-HMS diet. Red fire ants with a blank diet of 0.5% Triton X-100\u0026thinsp;+\u0026thinsp;0.5% acetone water were used as the control group. After 72 hours of feeding, red fire ants were placed in PBS, and the midgut was separated from the abdomen of red fire ants with tweezers. The midguts were transferred to a glass tube containing 4 mL of paraformaldehyde fixator, fixed at 4\u0026deg;C for 24 h, and then transferred to 70% ethanol solution for dehydration. The samples were embedded in paraffin, cut into sections of 3\u0026ndash;4 \u0026micro;m, fixed on slides, stained with hematoxylin and eosin, and observed under a microscope (Nikon, Japan).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section3\"\u003e \u003ch2\u003e2.7.2. The migration of drug-carrying materials in the midgut observed with fluorescence microscope\u003c/h2\u003e \u003cp\u003eFK-HMS (300 mg) was ultrasonically dispersed in PBS (pH\u0026thinsp;=\u0026thinsp;8.0), 50 mg FITC was then added, and the reaction was kept in the dark for 24 h. The reaction solution was transferred to a dialysis bag (Oso-t 8280, with an intercepted molecular weight of 8000\u0026ndash;14000 Da) for dialysis until the solution was clear and colorless. Then, FITC-FK-HMS was added to the diet to feed red fire ants for 72 h. Red fire ants fed a blank diet of 0.5% Triton X-100\u0026thinsp;+\u0026thinsp;0.5% acetone water were employed as the control group. The midintestine of red fire ants was treated according to 2.7.1. Fluorescence images were collected using an inverted fluorescence microscope (Nikon, Japan) at a maximum wavelength of 490\u0026ndash;495 nm for absorption and 525\u0026ndash;530 nm for emission.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e2.8. Statistical analysis\u003c/h2\u003e \u003cp\u003eAll data were calculated and analysed using SPSS 25.0 software and Microsoft Office Excel 2019. Data are reported as the mean\u0026thinsp;\u0026plusmn;\u0026thinsp;SD (standard deviation). Origin 2021 was employed to draw and fit drug release kinetics models. A graphic summary was drawn using Powerpoint 2019. An independent sample t test was used to analyse the difference between the two treatment groups, and (*) indicates a statistically significant difference between the two treatment groups (P\u0026thinsp;\u0026lt;\u0026thinsp;0.05). Duncan's test was used to analyse the differences among the four treatment groups. The same letter indicates no significant difference, while different letters represent significant differences (P\u0026thinsp;\u0026lt;\u0026thinsp;0.05).\u003c/p\u003e \u003c/div\u003e "},{"header":"Preparation of IDC@FK-HMS","content":"\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\u003cp\u003eThe synthesis route from IDC loading to FK-functionalized HMS was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. First, HMSs were prepared by the hard template method. To enable FK to successfully perform functional modification on HMS, the surface of HMS was modified by APTS to achieve amination. Then, the IDC dissolved in acetone solution was loaded into the HMS by vacuum spin steaming. IDC-loaded NH\u003csub\u003e2\u003c/sub\u003e-HMS was obtained, and the functional modification of NH\u003csub\u003e2\u003c/sub\u003e-HMS by FK was realized through the coupling reaction of amino and carboxyl groups, generating the final result, namely, IDC@FK-HMS.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003e3.2. SEM, TEM and EDS\u003c/h2\u003e \u003cp\u003eThe morphological characteristics of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS, and IDC@FK-HMS were observed by SEM and TEM, the particle size distribution statistics of HMS and IDC@FK-HMS were determined, and energy dispersion spectrum (EDS) mapping of IDC@FK-HMS was performed (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). As shown in SEM micrographs (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, b), HMS and FK-HMS of loaded IDC exhibited relatively uniform nanospheres in size. The particle size of HMS (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec) reached approximately 155 nm, while that of IDC@FK-HMS (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed) was approximately 178 nm, which was due to the encapsulation of HMS by FK. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea showed that HMS possessed an obvious cavity structure, with many pores on the surface directly entering the cavity. The particle size of HMS obtained by TEM was consistent with that obtained by SEM. By observing Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec, it could be found that neither amination nor FK modification will damage the cavity structure inside HMS, and FK modification could seal the pores on the surface. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed showed that the cavity size of IDC@FK-HMS was much smaller than that of NH\u003csub\u003e2\u003c/sub\u003e-HMS and FK-HMS, which proved the successful loading of IDC on HMS. In Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee, the EDS results showed that C, O, Si, N, F, Cl, S and other elements all present sphericity consistent with IDC@FK-HMS, indicating that IDC@FK-HMS contained IDC, which was consistent with the results observed by TEM.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Structural characterization\u003c/h2\u003e \u003cp\u003eThe functional groups of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS, IDC, FK and IDC@FK-HMS were characterized by FTIR. Compared with FK, NH\u003csub\u003e2\u003c/sub\u003e-HMS, HMS and FK-HMS (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea), the characteristic absorption peak of the amidogen was centered at 1668 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1489 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (i.e., the bending vibration peak of N-H), indicating that the surface hydroxyl group of HMS successfully reacted with phenylamino silane group of APTS. The characteristic absorption peak of the polypeptide (-CO-NH-) from feather keratin was centered at 2924 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in the FK-HMS spectrum (Eslahi et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). The peaks at 1637 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1523 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 1452 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were the amide Ⅰ band (i.e., the tensile vibration peak of C\u0026thinsp;=\u0026thinsp;O), Ⅱ band (i.e., the bending vibration peak of N-H and the tensile vibration peak of C-N), and Ⅲ band (i.e., the bending vibration peak of C\u0026thinsp;=\u0026thinsp;O and the tensile vibration peak of C-N) (Eslahi et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). The tensile vibration peak caused by Si-O-Si was located at 1080 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Ha et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2005\u003c/span\u003e), and the vibration peak caused by Si-O was concentrated at 798 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating that HMS was successfully modified by FK. By comparing the FTIR spectral lines of FK-HMS, IDC, and IDC@FK-HMS (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), the peak at 1746 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1694 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponded to the asymmetric stretching vibration of the carbonyl group (-C\u0026thinsp;=\u0026thinsp;O) in IDC. The stretching vibration peak of CF\u003csub\u003e3\u003c/sub\u003e and O\u0026thinsp;=\u0026thinsp;C-N was located at 546 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Memarizadeh et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2014\u003c/span\u003e), without obvious movement, which was ascribed to the successful loading of IDC into HMS without causing chemical changes. The zeta potentials of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS, and IDC@FK-HMS were analysed using a Zetasizer Nanosizer. The ζ potentials of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS, and IDC@FK-HMS were \u0026minus;\u0026thinsp;3.05 mV, 28.50 mV, 23.97 mV, and 6.47 mV, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec). HMS exhibited a negative ζ potential in the presence of the -OH group, while NH\u003csub\u003e2\u003c/sub\u003e-HMS demonstrated a positive ζ potential due to protonation following the introduction of the amino group. Compared with that of NH\u003csub\u003e2\u003c/sub\u003e-HMS, the ζ potential of FK-HMS decreased, which was related to the coupling between the carboxyl group of FK and an amino group. However, there were certain amino groups in FK, and the ζ potential of FK only slightly decreased, which proved that FK successfully modified HMS. In addition, IDC was loaded into HMS, and the hydrogen bond force or intermolecular force between IDC and FK led to a large drop in ζ potential.\u003c/p\u003e \u003cp\u003eThe thermal stability of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS, FK, IDC and IDC@FK-HMS was analysed by TGA (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed, e, g and h). The TGA and DTG curves showed that HMS was equipped with good thermal stability and maintained a stable weight over a long temperature range. The TGA curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed) showed that the total weight losses of HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS, FK-HMS and FK were 6.62%, 20.39%, 39.41% and 93.98%. And the DTG curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee) showed that FK-HMS, NH\u003csub\u003e2\u003c/sub\u003e-HMS and FK had same moss loss peak at 316 ℃ and 546 ℃, indicating that HMS was successfully aminated and modified by FK. The TGA curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg) showed that the total weight losses of IDC and IDC@FK-HMS were 99.84% and 62.56%. And the DTG curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eh) showed that IDC and IDC@FK-HMS had same moss loss peak at 318℃. Comparing with the weight loss of FK-HMS and IDC@FK-HMS, the weight loss rete was 23.14%, and the load rate of IDC measured by HPLC was 23.22%. The test results of both were consistent, which further proved that IDC was successfully loaded into HMS.\u003c/p\u003e \u003cp\u003eThe mesoporous structures of HMS and IDC@FK-HMS were determined by BET specific surface area analysis. The N\u003csub\u003e2\u003c/sub\u003e isothermal adsorption and desorption curves of HMS and IDC@FK-HMS were shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef. HMS and IDC@FK-HMS showed obvious type IV isotherms, with clear hysteric loops caused by mesoporous structures. Through BET specific surface area calculations, IDC@FK-HMS significantly decreased from 271.21 m\u003csup\u003e2\u003c/sup\u003e/g to 64.77 m\u003csup\u003e2\u003c/sup\u003e/g compared to HMS, which was due to the successful loading of IDC and the modification of FK. Both HMS and IDC@FK-HMS only possessed a single wide peak in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ei, achieving the maximum peak value at 22\u0026deg;. HMS and IDCFK-HMS appeared as amorphous states, without crystal sequence reflection throughout the entire spectrum or IDC crystal peaks, which indicated that the IDC was loaded in the HMS.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section2\"\u003e \u003ch2\u003e3.4. In vitro release and light stabilization\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eRegression coefficient values and release index (n) corresponding to kinetic model fitting\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eRelease condition\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZero-order\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eFirst-order\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eHiguchi\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eHixson\u0026ndash;\u003c/p\u003e \u003cp\u003eCrowel\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eKorsmeyer\u0026ndash;Peppas\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003en\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"2\" rowspan=\"3\"\u003e \u003cp\u003eIDC@FK-HMS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003epH 4.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.7633\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.9614\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.9347\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.6779\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.9730\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.3389\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003epH 7.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.8859\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.9791\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.9936\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.7855\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.9936\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.4622\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eGSH,pH7.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.9249\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.9879\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.9971\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.8081\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.9959\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.5428\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eIDC@HMS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003epH 7.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.8531\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.9468\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.9811\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.7611\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.9944\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e0.3900\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea showed the cumulative release of IDC from IDC@FK-HMS at 25 ℃ at different pH values (4.5 and 7.4). The cumulative release of IDC@FK-HMS at pH 4.5 was greater than that at pH 7.4. The amide bond (-CONH-) was broken under acidic conditions, and the outer layer of FK dissolved in acidic conditions and presented a straight chain state, exposing the pores of HMS and synergistically accelerating the release of IDC. The initial release was fast, showing a slow rate over time, which was similar to previous studies (Xu et al. \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Gao et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). The experiment showed that IDC@FK-HMS could be released quickly in the red formic acid intestines.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb showed the cumulative release of IDC@FK-HMS with GSH (reduced prototype) at 25 ℃ and a pH of 7.4. In the absence of GSH (reduced prototype), the cumulative release of IDC@FK-HMS was small, only 4.89% at 1 d and 16.24% at 15 d. In contrast, the cumulative release of IDC@FK-HMS in the presence of GSH (reduced prototype) was relatively high, with only 13.40% at 1 d and 55.82% after 15 d (Yang et al. \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The disulfide bond (-S-S-) of FK was destroyed under GSH (reduced type), generating a straight chain state of FK, increasing dissolution, and exposing HMS channels. As an important detoxifying raw material of glutathione S-transferase in insects (Smith et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), GSH is widely found in insects and very beneficial to intelligent drug delivery.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec displayed the effect of FK modification on HMS at 25 ℃ and a pH of 7.4. The release rate of IDC@HMS was faster, and its cumulative release rate reached 28.88% in 1 d and 80.24% in 15 d. The release rate of IDC@FK-HMS was relatively slow, and its cumulative release amount from 1 d to 15 d was 4.89% and 16.24%, respectively, which indicated that the covering of FK on the surface of HMS effectively prevented the release of IDC (Yang et al. \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Wu et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Under ultraviolet irradiation, the IDC decomposition amount reached 31.48%, while only 3.24% of the 24 h released part was decomposed in IDC@FK-HMS, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed. The energy in OH\u003csup\u003e\u0026minus;\u003c/sup\u003e, H\u003csup\u003e+\u003c/sup\u003e, and UV in water was absorbed by molecules or atoms in the IDC structure, resulting in the breaking of IDC molecular bonds (Wen et al. 2021; Xu et al. \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The experimental results showed that FK-HMS effectively improved the optical stability of IDC and exhibited good UV-shielding performance.\u003c/p\u003e \u003cp\u003eAccording to the fitting results in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, the regression coefficients R\u003csup\u003e2\u003c/sup\u003e of the first-order dynamic models of IDC@FK-HMS and IDC@HMS were larger than those of the zero-order dynamic model under any in vitro release conditions, indicating that the release curve of IDC followed the first-order dynamic model. In addition, IDC@FK-HMS and IDC@HMS conformed to the Higuchi model rather than the Hixson-Crowel model under all in vitro release conditions, suggesting that most IDCs in FK-HMS and HMS were released by diffusion. The n values of IDC@FK-HMS and IDC@HMS obtained by the Korsmeyer-Peppas model were both less than 0.5 under acidic and neutral conditions, and the diffusion mechanism of IDC belongs to Fickian diffusion, namely, the diffusion of drugs from the pore. The diffusion index n value of IDC@FK-HMS was greater than 0.5, and the diffusion mechanism of IDC followed a non-Fickian diffusion mechanism, which was due to the certain dissolution effect of GSH on FK covering the surface. From the above experimental results, IDC@FK-HMS was released in response to both acid and GSH.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Biologicalactivity observation\u003c/h2\u003e \u003cp\u003eThe death rates of red fire ants treated with IDC, FK-HMS, and IDC@FK-HMS at different concentrations after different periods were analysed. In Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea, the death rate of red fire ants treated with IDC for 24 h was significantly higher than that of red fire ants treated with IDC@FK-HMS (P\u0026thinsp;\u0026lt;\u0026thinsp;0.05). IDC@FK-HMS had a slow-release function, and IDC was not released completely from FK-HMS. However, IDC directly acted on red fire ants, which caused them to be alert and reduced feeding (Wen et al. 2021). There was no significant difference in the mortality rate of red fire ants treated with IDC and IDC@FK-HMS for 48 h (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb), while the mortality rate of IDC@FK-HMS after 48 h was significantly higher than that before 24 h (P\u0026thinsp;\u0026lt;\u0026thinsp;0.05). IDC@FK-HMS was under the action of red fire formic acid in the intestinal tract and internal GSH. IDC was released from IDC@FK-HMS, which increased the death rate of red fire ants. After 72 h (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec), the mortality rate of the IDC@FK-HMS group was significantly higher than that of the IDC group (P\u0026thinsp;\u0026lt;\u0026thinsp;0.05), indicating that IDC was enhanced when loaded into FK-HMS nanoparticles. IDC@FK-HMS had good shielding ability, which reduced the hydrolysis of IDC by the insect intestinal environment. The half-life of IDC was effectively enhanced, and the service life of the active ingredients of pesticides was significantly enhanced. In addition, the fast release of IDC@FK-HMS was triggered conditionally, which weakened the harm of IDC to nontarget organisms and made the ecological environment safer.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed, the contact recognition of attacking mealworms in the IDC and IDC@FK-HMS treatment groups was significantly lower than that in the FK-HMS and control groups. The function of the nerve cells of red fire ants was lost by blocking sodium ion channels in nerve cells, resulting in red fire ant movement disorder and reducing the recognition and attack on mealworms (Silver and Soderlund \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). However, the contact recognition of attacking mealworms in the IDC treatment group was significantly higher than that in the IDC@FK-HMS group at 48 h and 72 h. At this point, IDC triggered the attack instinct and alert recognition of red fire ants (Wen et al. 2021), enabling them to quickly identify the attacking mealworms. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee, there was no significant difference in the suspended death time of mealworms under different treatments at 24 h. After 48 h and 72 h, the suspended death time of mealworms in the IDC and IDC@FK-HMS treatment groups was significantly higher than that in the FK-HMS and control groups. Notably, the IDC@HMS treatment group had a significantly higher suspended death time than the IDC treatment group. FK-HMS exhibited a certain shielding effect on the warning and recognition of red fire ants against IDC, allowing more red fire ants to feed on food. More red fire ants exhibited motion disorders due to the toxicity of the slowly released IDC. This phenomenon was consistent with the previous relevant test results. The results in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef showed that red fire ants in all treatment groups killed mealworms, while red fire ants treated with IDC@FK-HMS took a longer time to kill mealworms. The toxic effect of IDC released slowly from FK-HMS confused the metabolism level of red fire ants in whole-body tissues, thus reducing the attacking ability of red fire ants.\u003c/p\u003e \u003cp\u003eMany studies found that the activity of detoxifying enzymes is an important index to test the influence of exogenous substances on insect enzymes and insect resistance (Chen et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eg showed that the activity of GST in the IDC treatment group was significantly higher than that in the other treatment groups at 24 h, 48 h and 72 h, which proved that the detoxification ability of red fire ants against IDC was enhanced. IDC@FK-HMS treatment group showed no significantly different from FK-HMS and CK treatment group at 24 h, 48 h and 72 h, but it was significantly lower than IDC treatment group, indicating that FK-HMS weakened the activity of GST and enhanced the virulence effect of IDC. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eh and i showed that the CarE and AchE activities of IDC and IDC@FK-HMS at 24 h, 48 h and 72 h were significantly lower than those of the other treatment groups, which was attributed to IDC significantly inhibiting the CarE and AchE activities of red fire ants. The experiment showed that FK-HMS nanoparticles enhanced the effect of IDC on red fire ants and significantly reduced the attack instinct of red fire ants, thus affecting their survival ability in the wild.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section2\"\u003e \u003ch2\u003e3.6. Study on the effect on intestinal structure of red fire ants\u003c/h2\u003e\u003cp\u003eFluorescence microscopy was used to observe the location of the midgut labelled with fluorescent nanomaterials and the midgut changes in the red fire ants treated with IDC, FK-HMS, and IDC@FK-HMS at low concentrations for 72 h. As observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb, there was no significant difference between the midgut cells of red fire ants treated with FK-HMS and those of the blank control group, with normal cell membranes, which proved that FK-HMS had high biocompatibility and nontoxic effects on cells. The midgut treated with IDC showed obvious shrinkage and cell decay, which was similar to the toxicological effect of IDC and restricted the activities of red fire ants. The same shrinking cell decay occurred in IDC@FK-HMS-treated midgut cells as in IDC-treated midgut cells, showing a slight effect in the presence of the slow release of IDC from FK-HMS. According to Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec, there were many small bright green spots in the midgut of the red fire ants fed FITC-FK-HMS, and the bright green spots should be FK-HMS labelled by FITC. Cross-sectional fluorescence intensity analysis was conducted on the midgut to further analyse the position of FITC-FK-HMS. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed showed that the peak height of the cross-sectional fluorescence intensity in the FITC-FK-HMS treatment group was generally higher than that in the blank control group. The fluorescence intensity of bright green spots in the FITC-HMS treatment group possessed an obvious prominent peak. The nanoscale FK-HMS was easily absorbed by red fire ants and entered the midgut cells, which was conducive to promoting the toxic effect of IDC on red fire ants.\u003c/p\u003e \u003c/div\u003e"},{"header":"Summary","content":"\u003cp\u003eIn this study, the functional modification of NH\u003csub\u003e2\u003c/sub\u003e-HMS by FK was realized through the coupling reaction of the -NH\u003csub\u003e2\u003c/sub\u003e group and -COOH group. FK-HMS nanoparticles loaded with IDC were synthesized, and the control effect of FK-HMS on red fire ants was investigated. FK-HMS exhibited good controlled-release ability and quickly responded to acidic pH and GSH, effectively shielding the effects of light on drugs. Biological toxicity experiments showed that FK-HMS loaded with IDC had a lasting insecticidal effect. Even a low dose of IDC@FK-HMS significantly weakened the attacking ability of red fire ants and enhanced the virulence of IDC. In addition, nanoscale FK-HMS was easily absorbed by the red fire ant and entered the midgut cells. Comparing IDC, IDC@FK-HMS reduced the action of detoxification enzymes of the red fire ant. Therefore, IDC@FK-HMS with dual response characteristics has strong potential in effectively limiting the growth of red fire ant populations and even in controlling other agricultural pests.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSu-qing Huang: Conceptualization, Methodology, Data curation, Writing review and editing, Project administration, Fund acquisition. Xiao-feng Xie: Conceptualization, Methodology, Data curation, Experiment, Writing review and editing. Jiao Ding: Conceptualization, Methodology, Data curation. Nan-he Huang: Experiment.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe 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.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eDate will be made available on request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePartial experiments in this work were supported by Key Laboratory of Natural Pesticide and Chemical Biology, Ministry of Education, South China Agricultural University, Guangzhou, China. Thanks to Dr. Zhi-xiang Zhang for his guidance and help in this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFund\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by Modern agricultural industrial technology System of Guangdong Province (The task of Innovation team building of key generic technologies in agricultural resources and environment) (2023KJ118).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eAznar E, Marcos MD, M\u0026aacute;\u0026ntilde;ez RM, Sancen\u0026oacute;n F, Soto J, Amor\u0026oacute;s P, Guillem C (2009) pH- and photo-switched release of guest molecules from mesoporous silica supports. J. Am. Chem. Soc. 131 (19): 6833-43 https://doi.org/10.1021/ja810011p\u003c/li\u003e\n \u003cli\u003eBanks WA, Lofgren CS, P JD (1981) in: Techniques for Collecting, Rearing and Handing Imported Fire ants, U. S. 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Sociobiology, 67 (2): 232 https://doi.org/10.13102/sociobiology.v67i2.4517\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Hollow mesoporous silica, Feather keratin, Indoxacarb, Solenopsis invicta","lastPublishedDoi":"10.21203/rs.3.rs-3377780/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3377780/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eHerein, a pesticide-controlled release system (IDC-loaded FK-HMS) with pH and reduced glutathione (GSH) response characteristics was designed and prepared, in which the carboxyl group of feather keratin (FK) was coupled with aminated hollow mesoporous silica (HMS), and indoxacarb (IDC) was loaded into HMS. The composite system was characterized by scanning electron microscopy, Fourier transform spectroscopy, X-ray diffraction, and high-performance liquid chromatography. FK-HMS showed a high loading ratio (23.22%, w/w) on IDC while exhibiting dual sensitivity to pH value and reduction response. Compared with the same dose of the original IDC drug, IDC-loaded FK-HMS showed better killing activity against invasive species of \u003cem\u003eSolenopsis invicta\u003c/em\u003e, which was because nanoscale FK-HMS was easily absorbed by \u003cem\u003eSolenopsis invicta\u003c/em\u003e and entered midgut cells, reducing the effect of detoxification enzymes. Furthermore, low-dose IDC@FK-HMS effectively inhibited the actions of \u003cem\u003eSolenopsis invicta\u003c/em\u003e, indicating that the insecticide-controlled release system based on FK-modified HMS nanoparticles is capable of sustained and long-term control of \u003cem\u003eSolenopsis invicta\u003c/em\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Feather keratin-functionalized nanomesoporous silica enhances the control effect of indoxacarb on Solenopsis invicta","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-09-27 16:40:20","doi":"10.21203/rs.3.rs-3377780/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"dbfe8a87-c9cd-44aa-b822-2631a44ef871","owner":[],"postedDate":"September 27th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2023-10-05T12:14:23+00:00","versionOfRecord":[],"versionCreatedAt":"2023-09-27 16:40:20","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3377780","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3377780","identity":"rs-3377780","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}