Mingcai Wang, Yanxue Liu, Shangkun Gao, Mingshan Chang, Liangming Cao, Yaojun Zhu
Mangrove ecosystems represent critical coastal blue carbon sinks, whose ecological stability is essential for sustaining carbon sequestration capacity and coastal ecological security. Hyblaea puera, a dominant defoliating pest in mangrove habitats, exhibits abrupt population outbreaks and extreme destructive potential, severely threatening the integrity of blue carbon ecosystems. While conventional broad-spectrum chemical insecticides deliver adequate control efficacy, they often exert detrimental effects on non-target organisms and adjacent coastal marine environments, conflicting with core mangrove conservation objectives. Azadirachtin, a botanical insecticide with high lepidopteran target highly selective, is a promising eco-friendly alternative; nevertheless, the dual stresses of periodic tidal flushing and intense ultraviolet radiation in intertidal mangrove habitats drive rapid photodegradation and leaching loss of azadirachtin, leading to poor field persistence and slow lethal action of the free formulation. These limitations render neat azadirachtin insufficient to meet the urgent demand for rapid emergency control of H. puera during population outbreaks. To address these technical bottlenecks, we developed an azadirachtin-loaded dendritic mesoporous silica nanoparticle delivery system to simultaneously improve the environmental stability and fast-acting insecticidal efficacy of azadirachtin against H. puera. Specifically, dendritic mesoporous silica nanoparticles (DMSNs) were synthesized via a one-pot method, then loaded with azadirachtin (ADT) and further surface-modified with polyether-modified heptamethyltrisiloxane (PM) to fabricate the ADT@DMSN/PM nano-delivery system. The physicochemical properties, intertidal habitat adaptability, insecticidal activity, and environmental safety of the fabricated system were systematically evaluated. Characterization results showed that the as-synthesized DMSNs had a uniform particle size of 200-300 nm, a specific surface area of 260.99 m2/g, and an ADT loading efficiency of 66.6%. ADT@DMSNs exhibited prominent alkaline-responsive sustained-release behavior, with a cumulative ADT release of 57.0% at pH 8.2 (mangrove seawater conditions) over 500 h. Laboratory bioassays revealed that the 24 h median lethal concentrations (LC50) of ADT@DMSNs against third-, fourth-, and fifth-instar H. puera larvae were 84.36, 188.08, and 458.65 μg/mL, respectively, representing 2.38-, 2.63-, and 2.86-fold enhancements in insecticidal activity compared with free ADT. After modification with the PM adjuvant, the nanoformulation exhibited a significantly reduced contact angle on Avicennia marina leaves, over 3-fold higher foliar penetration efficiency, and markedly improved tidal wash-off resistance. Field cage bioassays demonstrate that the ADT@DMSN/PM nanoformulation yields a corrected mortality of approximately 95% against H. puera larvae at 1200 mg/L at 24 h. This nano-delivery system is precisely tailored to the unique environmental constraints of mangrove intertidal habitats, offering a novel eco-friendly technical approach to achieve rapid emergency control of H. puera outbreaks.