Amphiphilic Cationic Carbon Dots for Efficient Delivery of Light-Dependent Herbicide.

The inefficient delivery of herbicides causes unpleasant side effects on the ecological environment. Protoporphyrinogen oxidase (PPO)-inhibiting herbicides rely on the presence of external light to exert the activities and thus their performance in the field is extremely susceptible to the light environment. Here, taking acifluorfen (ACI) as a model PPO-inhibiting herbicide to enhance efficacy by boosting the utilization rate of sunlight, amphiphilic cationic CDs (CPC-CDs) from cetylpyridinium chloride (CPC) as a precursor, is first prepared as a supplementary light source generator, and subsequently co-assembled with ACI through non-covalent bond interactions to obtain the stable fluorescent nanoparticles (ACI@CPC-CDs). ACI@CPC-CDs with fascinating physicochemical properties can penetrate the leaves of weeds through the stomata and undergo a long-distance transport in the cell intervals. Under low light intensity, CPC-CDs can be applied as the internal light source to promote the formation of more singlet oxygen to damage the leaf cell membrane, consequently improving the herbicidal activity of ACI. Moreover, the safety evaluation of ACI@CPC-CDs demonstrates no risk to non-target organisms and the environment. Therefore, this work offers a promising strategy for the efficient delivery of light-dependent PPO-inhibiting herbicides and opens new insights into the application of CDs in the development of sustainable agriculture.

Fabrication of ionic liquid self-assemblies based on dicamba with improved herbicidal activity and reduced environmental risks.

The off-target loss of pesticide formulations caused by volatilization and leaching has reduced effective utilization and increased risks to the ecological environment and human health. Self-assembly of pesticides has been widely concerned due to the improved bioactivity and environmental compatibility. Herbicidal ionic liquids (HILs) could effectively decrease off-target loss and increase efficacy and environmental safety by improving the physicochemical properties of herbicides. Herein, HILs were prepared by pairing dicamba with quaternary ammonium salts containing different alkyl chain lengths and aromatic groups and subsequently self-assembled into spherical nanoparticles (HIL NPs) via electrostatic interaction and hydrophobic effect. Compared with dicamba, the obtained HIL NPs with an average particle size of 6-55 nm exhibited improved physicochemical properties, including high zeta potential values (+20.3 to +27.8 mV), low volatilization rate (2.4-3.9 %) and surface tension (22.83-33.07 mN m-1), decreased contact angle (32.25-41.55°) and leaching potential (76.2-86.5 %), and high soil adsorption (12.1-23.8 %), suggesting low risks to the environment. The control efficacy against Amaranthus retroflexus of HIL3 NPs pairing dicamba with octadecyl-trimethyl ammonium chloride was better than that of dicamba sodium salt at different concentrations. Therefore, the ionic liquid self-assembly developed by a facile and green preparation approach to reduce the volatility and leaching of pesticides would have enormous potential in sustainable agriculture.

Carrier-free self-assembled nanoparticles based on prochloraz and fenhexamid for reducing toxicity to aquatic organism.

Nanoformulations of pesticides are an effective way to increase utilization efficiency and alleviate the adverse impacts on the environments caused by conventional pesticide formulations. However, the complex preparation process, high cost, and potential environmental risk of nanocarriers severely restricted practical applications of carrier-based pesticide nanoformulations in agriculture. Herein, carrier-free self-assembled nanoparticles (FHA-PRO NPs) based on fenhexamid (FHA) and prochloraz (PRO) were developed by a facile co-assembly strategy to improve utilization efficiency and reduce toxicity to aquatic organism of pesticides. The results showed that noncovalent interactions between negatively charged FHA and positively charged PRO led to core-shell structured nanoparticles arranged in an orderly manner dispersing in aqueous solution with a diameter of 256 nm. The prepared FHA-PRO NPs showed a typical pH-responsive release profile and exhibited excellent physicochemical properties including low surface tension and high max retention. The photostability of FHA-PRO NPs was improved 2.4 times compared with free PRO. The FHA-PRO NPs displayed superior fungicidal activity against Sclerotinia sclerotiorum and Botrytis cinerea and longer duration against Sclerotinia sclerotiorum on potted rapeseed plants. Additionally, the FHA-PRO NPs reduced the acute toxicity of PRO to zebrafish significantly. Therefore, this work provided a promising strategy to develop nanoformulations of pesticides with stimuli-responsive controlled release characteristics for precise pesticide delivery.

Making the Complicated Simple: A Minimizing Carrier Strategy on Innovative Nanopesticides.

The flourishing progress in nanotechnology offers boundless opportunities for agriculture, particularly in the realm of nanopesticides research and development. However, concerns have been raised regarding the human and environmental safety issues stemming from the unrestrained use of non-therapeutic nanomaterials in nanopesticides. It is also important to consider whether the current development strategy of nanopesticides based on nanocarriers can strike a balance between investment and return, and if the complex material composition genuinely improves the efficiency, safety, and circularity of nanopesticides. Herein, we introduced the concept of nanopesticides with minimizing carriers (NMC) prepared through prodrug design and molecular self-assembly emerging as practical tools to address the current limitations, and compared it with nanopesticides employing non-therapeutic nanomaterials as carriers (NNC). We further summarized the current development strategy of NMC and examined potential challenges in its preparation, performance, and production. Overall, we asserted that the development of NMC systems can serve as the innovative driving force catalyzing a green and efficient revolution in nanopesticides, offering a way out of the current predicament.

Fabrication of Enzyme-Responsive Prodrug Self-Assembly Based on Fluazinam for Reducing Toxicity to Aquatic Organisms.

Prodrug-based nanodrug delivery systems were drug formulations by covalently conjugating drugs with inversely polar groups via a cleavable bond to self-assemble into nanoparticles for efficient drug delivery. To improve the utilization efficiency of fluazinam (FZN), enzyme-responsive prodrugs were prepared by conjugating FZN with different alkyl aliphatic acids through a nucleophilic substitution reaction and subsequently self-assembled into nanoparticles (FZNP NPs) without using any harmful adjuvant. The obtained FZNP NPs exhibited excellent efficacies against Sclerotinia sclerotiorum as a result of improved physicochemical properties, including low surface tension, high retention, and enhanced photostability. The LC50 values of FZNP NPs toward zebrafish were 3-8 times that of FZN, which illustrated that the FZNP NPs reduced the detriments of FZN to the aquatic organisms while retaining good biological activity. Therefore, prodrug self-assembly technology would offer a potential method for improving the utilization efficiency of pesticides and lowering the risks to the ecological environment.

A high adhesion co-assembly based on myclobutanil and tannic acid for sustainable plant disease management.

BACKGROUND: Pesticides are irreplaceable inputs for protecting crops from pests and improving crop yield and quality. Self-assembly nanotechnology is a promising strategy by which to develop novel nano-formulations for pesticides. Nano-formulations improve the effective utilization of pesticides and reduce risks to the environment because of their eco-friendly preparation, high drug loading, and desirable physicochemical properties. Here, to enhance the utilization efficiency of myclobutanil (MYC) and develop a novel nano-formulation, carrier-free co-assembled nanoparticles (MT NPs) based on MYC and tannic acid (TA) were prepared by noncovalent molecular interactions using a green preparation process without any additives. RESULTS: The results showed that the prepared spherical nanoparticles had good stability in neutral and acidic aqueous solutions, low surface tension (40.53 mN m-1 ), high rainfastness, and good maximum retention values on plant leaves. Release of active ingredients from MT NPs could be regulated by altering the molar ratio of subassemblies in the co-assembly and the pH of the environment. Antifungal experiments demonstrated that MT NPs had better activities against Alternaria alternata and Fusarium graminearum [half-maximal effective concentration (EC50 ) = 6.40 and 77.08 mg/L] compared with free MYC (EC50 = 11.46 and 124.82 mg/L), TA (EC50 = 251.19 and 503.81 mg/L), and an MYC + TA mixture (EC50 = 9.62 and 136.21 mg/L). These results suggested that MYC and TA incorporated in the co-assembled nanoparticles had a synergistic antifungal activity. The results of a genotoxicity assessment indicated that MT NPs could reduce the genotoxicity of MYC to plant cells. CONCLUSION: Co-assembled MT NPs with synergistic antifungal activity have outstanding potential for the management of plant diseases. © 2023 Society of Chemical Industry.

Stable Fluorescent Nanoparticles Based on Co-assembly of Acifluorfen and Poly(salicylic acid) for Enhancing Herbicidal Activity and Reducing Environmental Risks.

Herbicides are widely used in modern agricultural production for their advantages of high efficiency, convenience, and speed. However, there have been many problems caused by herbicide formulations, such as volatilization, leaching, and rain-washing loss in the process of agricultural application. Self-assembled nanotechnology is a promising strategy to solve these existing problems due to the environmentally friendly preparation process and high delivery efficiency. In this study, the stable fluorescent nanoparticles (AP NPs) based on co-assembly of acifluorfen (ACI) and poly(salicylic acid) (PSA) are constructed by using non-covalent bond interactions. The results indicate that the obtained nanoparticles with a stable fluorescence characteristic show improved physiochemical properties, such as uniform morphology, good thermal stability, low surface tension, and high retention on plants. The co-assembly can produce singlet oxygen to enhance the herbicidal activity under irradiation of light and reduce the leaching property of ACI to minimize the adverse impact on the aquatic environment. The safety evaluation of soybean seedlings indicates that AP NPs have no damage to non-target plants. In summary, the co-assembled herbicidal nano-formulation composed of ACI and PSA has high bioactivity and low environmental risks, which can be widely used in agricultural production.

Prodrug Based on Ionic Liquids for Dual-Triggered Release of Thiabendazole.

The application of triggered release pesticides can provide active ingredient release at required environmental conditions, reduce environmental problems, and toxicity to nontarget organisms. In this work, a novel prodrug that responds to water and enzymes as release triggers for thiabendazole was prepared. The release behaviors under different conditions, bioactivity against Penicillium italicum, and acute toxicity to Danio rerio of prodrugs were investigated. The results showed that the prodrug had remarkable water- and enzyme-triggered release properties, and the correlation coefficients (r 2) fitted by the Weibull model were all >0.99. Meanwhile, the prodrug showed improved antifungal efficacy against Penicillium italicum and reduced toxicity to Danio rerio. Overall, the prodrug developed offers an efficient way to triggered release pesticides, control fungal, and reduce the risk of harm to aquatic organisms.

Pectin functionalized metal-organic frameworks as dual-stimuli-responsive carriers to improve the pesticide targeting and reduce environmental risks.

Encapsulation of active ingredients into intelligent response controlled release carriers has been recognized as a promising approach to enhance the utilization efficiency and reduce the environmental risks of pesticides. In this work, an intelligent redox and pectinase dual stimuli-responsive pesticide delivery system was constructed by bonding pectin with metal-organic frameworks (FeMOF nanoparticles) which were loaded with pyraclostrobin (PYR@FeMOF-pectin nanoparticles). The successful fabrication of PYR@FeMOF-pectin nanoparticles was proved by a series of physicochemical characterizations. The results indicated that the loading capacity of PYR@FeMOF-pectin nanoparticles for pyraclostrobin was approximately 20.6%. The pectin covered on the surface of PYR@FeMOF nanoparticles could protect pyraclostrobin from photolysis and improve their spreadability on rice blades effectively. Different biological stimuli associated with Magnaporthe oryzae could trigger the release of pyraclostrobin from the pesticide-loaded core-shell nanoparticles, resulting in the death of pathogens. The bioactivity survey determined that PYR@FeMOF-pectin nanoparticles had a superior fungicidal activity and a longer duration against Magnaporthe oryzae than pyraclostrobin suspension concentrate. In addition, the FeMOF-pectin nanocarriers showed no obvious phytotoxicity and could enhance the shoot length and root length of rice plants. More importantly, PYR@FeMOF-pectin nanoparticles had an 8-fold reduction in acute toxicity to zebrafish than that of pyraclostrobin suspension concentrate. Therefore, the dual-responsive FeMOF-pectin nanocarriers have great potential for realizing site-specific pesticide delivery and promoting plant growth.

Self-Assembled Nanoparticles of a Prodrug Conjugate Based on Pyrimethanil for Efficient Plant Disease Management.

Self-assembled nanotechnology is a promising strategy for improving the effective utilization of pesticides due to its distinct advantages. Herein, an amide-bonded prodrug conjugate based on pyrimethanil (PYR) and butyric acid (BA) was successfully synthesized by the nucleophilic substitution reaction and subsequently self-assembled into spherical nanoparticles (PB NPs) with an average size of 85 nm through the solvent exchange method without using any toxic adjuvant. The results showed that PB NPs based on PYR and BA had a synergistic antimicrobial activity against S. sclerotiorum on plant leaves due to good photostability, low volatilization, good surface activity, and improved retention. Additionally, PB NPs could be used by plant cells as nutrients to promote the growth of plants and thus reduced the toxicity of PYR to plant. Therefore, this prodrug conjugate self-assembly nanotechnology would provide a promising strategy for improving the effective utilization rates of pesticides and reducing their toxicities to plants.

Carrier-Free Small Molecular Self-Assembly Based on Berberine and Curcumin Incorporated in Submicron Particles for Improving Antimicrobial Activity.

Nanocarrier-based pesticide formulations have been severely restricted in agriculture practices due to their high-cost preparation process, poor loading capacity, and toxicity issues. To overcome these issues, carrier-free small molecular self-assembled submicron particles (SMPs) with an improved photoactivated antimicrobial activity based on two natural microbicides berberine hydrochloride (BBR) and curcumin (CM) are constructed by noncovalent interactions through a simple and fast preparation process (solvent exchange method) without using any adjuvant. The results show that the optimized molar ratio of BBR to CM is 2:1 at pH 5 and 25 °C in an aqueous solution for the formation of B-C SMPs. The obtained B-C SMPs exhibit excellent physicochemical properties, such as uniform morphology (407 nm), low polydispersity index (0.283), and strong ζ-potential (+24.4 mV). The antibacterial activities of B-C SMPs against Pseudomonas syringae pv. lachrymans, Clavibater michiganensis subsp. Michiganensis, and Sclerotinia sclerotiorum are 4, 2, and 1.5 times that of B + C MIX, respectively, suggesting a synergistic antimicrobial activity based on BBR and CM incorporation in the submicron particles. The genotoxicity evaluation results show that the self-assembled B-C SMPs are harmless to plant cells. Therefore, due to rational utilization of natural resources (natural microbicides, sunlight, and oxygen), carrier-free small molecular self-assembled B-C SMPs with synergistic photoactivated antimicrobial activity developed by a simple and fast preparation process would have great potential for sustainable plant disease management.

Supramolecular Self-Assembly of Herbicides with Reduced Risks to the Environment.

The side effects caused by some pesticides with high off-target movement have brought great risks to the environment and human health. Here, taking 2,4-dichlorophenoxyacetic acid (2,4-D) as a model herbicide to reduce its volatilization and leaching, a supramolecular self-assembly mediated by branched polyethylenimine (B-PEI) was constructed through noncovalent molecular recognition. The results showed that 2,4-D/B-PEI nanoparticles (NPs) with a mean particle size of 168 nm can be formed by electrostatic interaction, hydrophobic effect, and π-π stacking when the mass ratio of 2,4-D to B-PEI with the average molecular weight of 10 000 (B-PEI 10k) was 40:20, and their generation was not susceptible to common inorganic ions such as Ca2+, Na+, Cl-, and SO42-. Compared with 2,4-D, the self-assembled NPs with improved physicochemical properties including strong positive charges (+58.2 mV), reduced volatilization rate (2.50%), low surface tension (56.10 mN m-1), and decreased leaching potential could minimize the adverse impacts of this herbicide on the environment. The biological activity experiments in the greenhouse and field demonstrated that the control efficacy of NPs without using any surfactant against weeds was almost the same as that of the 2,4-D sodium salt form containing Tween 80. The safety tests showed that the self-assembled NPs had the same genotoxicity as 2,4-D to Vicia faba and little effect on the soil enzyme activities. Overall, the development of self-assembled herbicidal nanoformulations with desirable physicochemical properties and low risks to the environment would have potential application in agricultural production.

One-Pot Facile Synthesis of Double-Shelled Mesoporous Silica Microcapsules with an Improved Soft-Template Method for Sustainable Pest Management.

A controlled release formulation based on silica microcapsules is an ideal selection to improve both the effective utilization and duration of pesticides to decrease ecological damage. Herein, a simple and green method for preparing double-shelled microcapsules was developed using a newly prepared quaternary ammonium ionic liquid (IL) as the functional additive to entrap avermectin (Ave) in mesoporous silica nanospheres (MSNs) and tannic acid-Cu (TA-Cu) complex as the sealing agent to form the core-shell structure (Ave-IL@MSN@TA-Cu). The obtained microcapsules with an average size of 538 nm had pH-responsive release property and good stability in soil. The half-life of microcapsules (34.66 days) was 3 times that of Ave emulsifiable concentrate (EC) (11.55 days) in a test soil, which illustrated that microcapsules could protect Ave from rapid degradation by microorganisms by releasing TA, copper, and quaternary ammonium in the soil. Ave-IL@MSN@TA-Cu microcapsules had better nematicidal activity and antibacterial activity than Ave EC due to the synergistic effect of Ave, IL, and copper incorporated in the microcapsules. Pot experiments showed that the control efficacy of microcapsules was 87.10% against Meloidogyne incognita, which is better than that of Ave EC (41.94%) at the concentration of 1.0 mg/plant by the root-irrigation method after 60 days of treatment owing to the extended duration of Ave in microcapsules. The simple and green method for the preparation of double-shelled microcapsules based on natural quaternary ammonium IL would have tremendous potential for the extensive development of controlled release pesticide formulations.

Functionalized Silver Nanocapsules with Improved Antibacterial Activity Using Silica Shells Modified with Quaternary Ammonium Polyethyleneimine as a Bacterial Cell-Targeting Agent.

Silver nanoparticles (AgNPs) have remarkable and broad-spectrum antibacterial activities against Gram-positive (G+) and Gram-negative bacteria (G-). However, the negative surface potential of AgNPs limits their antibacterial activities due to the electrostatic repulsion with the negatively charged bacterial cell membrane. To address the limitation, AgNPs were loaded in the mesoporous silica nanoparticles by preparing silver core-mesoporous silica shell nanocapsules (Ag@MSNs), and then, a cationic antibacterial polymer, quaternary ammonium polyethyleneimine (QPEI), was used to modify Ag@MSNs for improving their surface potential and antibacterial activities. The results showed that the obtained Ag@MSN-QPEI exhibited a high positive surface potential (+39.6 mV) and a strong electrostatic attraction with Pseudomonas syringae pv. lachrymans cells in coculture, resulting in an excellent bacterial cell-targeting effect. At the same concentration, Ag@MSN-QPEI exhibited less silver content (reducing the silver content of Ag@MSNs by 19%), higher antibacterial activities, and longer effective duration against Clavibacter michiganensis subsp. michiganensis (G+) and P. syringae pv. lachrymans (G-) than Ag@MSNs and QPEI alone. The excellent bacterial cell-targeting effect and synergistic antibacterial action combined with QPEI accounted for the significantly enhanced antibacterial activities of Ag@MSN-QPEI. Therefore, using a cationic antibacterial polymer to confer the bacterial cell-targeting effect and synergistic antibacterial action would be extended to other antimicrobial materials.

Fabrication of pH-responsive nanoparticles for high efficiency pyraclostrobin delivery and reducing environmental impact.

In this work, a pH-responsive pesticide delivery system using mesoporous silica nanoparticles (MSNs) as the porous carriers and coordination complexes of Cu ions and tannic acid (TA-Cu) as the capping agent was established for controlling pyraclostrobin (PYR) release. The results showed the loading capacity of PYR@MSNs-TA-Cu nanoparticles for pyraclostrobin was 15.7 ± 0.5% and the TA-Cu complexes deposited on the MSNs surface could protect pyraclostrobin against photodegradation effectively. The nanoparticles had excellent pH responsive release performance due to the decomposition of TA-Cu complexes under the acid condition, which showed 8.53 ± 0.37%, 82.38 ± 1.67% of the encapsulated pyraclostrobin were released at pH 7.4, pH 4.5 after 7 d respectively. The contact angle and adhesion work of PYR@MSNs-TA-Cu nanoparticles on rice foliage were 86.3° ± 2.7° and 75.8 ± 3.1 mJ/m2 after 360 s respectively, indicating that TA on the surface of the nanoparticles could improve deposition efficiency and adhesion ability on crop foliage. The control effect of PYR@MSNs-TA-Cu nanoparticles against Rhizoctonia solani with 400 mg/L of pyraclostrobin was 85.82% after 7 d, while that of the same concentration of pyraclostrobin EC was 53.05%. The PYR@MSNs-TA-Cu nanoparticles did not show any phytotoxicity to the growth of rice plants. Meanwhile, the acute toxicity of PYR@MSNs-TA-Cu nanoparticles to zebrafish was decreased more than 9-fold compared with that of pyraclostrobin EC. Thus, pH-responsive PYR@MSNs-TA-Cu nanoparticles have great potential for enhancing targeting and environmental safety of the active ingredient.

Preparation of a Porphyrin Metal-Organic Framework with Desirable Photodynamic Antimicrobial Activity for Sustainable Plant Disease Management.

Considering the severity of plant pathogen resistance toward commonly used agricultural microbicides, as well as the potential threats of agrichemicals to the eco-environment, there is a pressing need for antimicrobial approaches that are capable of inactivating pathogens efficiently without the risk of inducing resistances and harm. In this work, a porphyrin metal-organic framework (MOF) nanocomposite was constructed by incorporating 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) as a photosensitizer (PS) in the cage of a variant MOF (HKUST-1) to efficiently produce singlet oxygen (1O2) to inactivate plant pathogens under light irradiation. The results showed that the prepared PS@MOF had a loading rate of PS about 12% (w/w) and excellent and broad-spectrum photodynamic antimicrobial activity in vitro against three plant pathogenic fungi and two pathogenic bacteria. Moreover, PS@MOF showed outstanding control efficacy against Sclerotinia sclerotiorum on cucumber in the pot experiment. Allium cepa chromosome aberration assays and safety evaluation on cucumber and Chinese cabbage indicated that PS@MOF had no genotoxicity and was safe to plants. Thus, porphyrin MOF demonstrated a great potential as an alternative and efficient new microbicide for sustainable plant disease management.

Allyl Isothiocyanate (AITC) Triggered Toxicity and FsYvc1 (a STRPC Family Member) Responded Sense in Fusarium solani.

Allyl isothiocyanate (AITC) is a natural product used as a food additive. Due to its strong volatility and broad biological activity, AITC is considered as a bio-fumigant to control soil-borne fungal diseases in agriculture, creating an urgent need for evaluation of the antifungal activity of AITC. Here we study the effect of AITC on Fusarium solani growth and explore the molecular mechanisms. The results indicated that AITC causes rapid inhibition of F. solani after 5 min, hyphal deformity, and electrolyte leakage. A yeast-like vacuolar transient receptor potential channel regulator (FsYvc1, a STRPC family member) was identified in F. solani that seems to play a role in this fungi AITC sensitivity. Genetic evidence suggests the gene FsYvc1 is involved in F. solani growth, development, and pathogenicity. Loss of FsYvc1 resulted in hypersensitivity of F. solani to AITC and induced reactive oxygen species (ROS) accumulation ∼ 1.3 to 1.45- folds that of the wild type (WT), and no difference responses to CaCl2, NaCl, KCl, SDS, and Congo red when compared with WT. In addition, ΔFsYvc1-17 showed significantly reduced (∼ 1-fold) glutathione-S-transferase (GST) expression compared with the WT without AITC induction. Upon exposure to 4.8 µg/mL AITC for 3 h, the relative expression levels were ∼ 12-30 fold higher in both the WT and ΔFsYvc1-17. Nevertheless, no difference in GST expression level was observed between the WT and ΔFsYvc1-17. The current study provides novel insights into the toxicity mechanisms of AITC. Considering our results that show the key role of FsYvc1, we propose that it could act as a new molecular target for future fungicide development.

Preparation of Acifluorfen-Based Ionic Liquids with Fluorescent Properties for Enhancing Biological Activities and Reducing the Risk to the Aquatic Environment.

In this work, 12 novel herbicidal ionic liquids (HILs) based on acifluorfen were prepared by pairing with the fluorescent hydrazides or different alkyl chains for increasing activities and reducing negative impacts on the aquatic environment. The results showed that the fluorescence of coumarin hydrazide in the HILs was applied as the internal and supplementary light source to meet the requirement of light wavelength range of acifluorfen, which improved the phytotoxicity of acifluorfen to weeds by enhancing singlet oxygen generation with increased sunlight utilization. The herbicidal activities of HILs were related positively with the length of chain of cation under high light intensity and depended mainly on the fluorescence characteristic of the cation under low light intensity, and the double salt IL forms of acifluorfen containing coumarin hydrazide and n-hexadecyltrimethylammonium had enhanced efficacies against broadleaf weeds in the field. Compared with acifluorfen sodium, HILs had lower water solubility, better surface activity, weaker mobility in soils, and higher decomposition temperature. These results demonstrated that HILs containing different cations provided a wider scope for fine-tuning of the physicochemical and biological properties of herbicides and established a promising way for the development of environmentally friendly herbicidal formulations.

Fabrication of smart stimuli-responsive mesoporous organosilica nano-vehicles for targeted pesticide delivery.

It is highly desirable to construct stimuli-responsive nanocarriers for improving pesticides targeting and preventing the pesticides premature release. In this work, a novel redox and α-amylase dual stimuli-responsive pesticide delivery system was established by bonding functionalized starch with biodegradable disulfide-bond-bridged mesoporous silica nanoparticles which loaded with avermectin (avermectin@MSNs-ss-starch nanoparticles). The results demonstrated that the loading capacity of avermectin@MSNs-ss-starch nanoparticles for avermectin was approximately 9.3 %. The starch attached covalently on the mesoporous silica nanoparticles could protect avermectin from photodegradation and prevent premature release of active ingredient. Meanwhile, the coated starch and disulfide-bridged structure of nanoparticles could be decomposed and consequently release of the avermectin on demand when nanoparticles were metabolized by glutathione and α-amylase in insects. The bioactivity survey confirmed that avermectin@MSNs-ss-starch nanoparticles had a longer duration in controlling Plutella xylostella larvae compared to avermectin emulsifiable concentrate. In consideration of the superior insecticidal activity and free of toxic organic solvent, this target-specific pesticide release system has promising potential in pest management.