Hydrothermal Growth and Electrochemical Performance of Carbon-Coated Porous SnO2 Nanospheres.

The porous SnO2 nanospheres were fabricated by hydrothermal method and then the carbon layer was coated as a buffer cushion through a facile hydrothermal process in aqueous D-glucose followed by a subsequent calcination at 500 °C in a nitrogen (N2) atmosphere. The materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis and Raman spectra. Based on the experimental results, the thickness of carbon layer could be well-controlled by hydrothermal time and D-glucose concentration. The typical as-prepared carbon-coated porous SnO2 nanospheres show an initial discharge capacity of 711.26 mAhg-1 and a stabilized capacity at 414 mAhg-1 after 50 cycles. It was shown that the carbon-coated porous SnO2 nanospheres exhibited better electrochemical properties in terms of high Columbic efficiency and rate performance, which are attributed to the porous structure and the outer carbon layer.

Relationship Learning From Multisource Images via Spatial-Spectral Perception Network.

Advances in multisource remote sensing have allowed for the development of more comprehensive observation. The adoption of deep convolutional neural networks (CNN) naturally includes spatial-spectral information, which has achieved promising performance in multisource data classification. However, challenges are still found with the extraction of spatial distribution and spectrum relationships, which eventually limit the classification performance. To solve the issue, a spatial-spectral perception network (S2PNet) is proposed to extract the advantages of different data sources and the cross information between data sources in a targeted manner. Specifically, the spatial perception network is developed to build the spatial distribution relationship from high-resolution images, while the spectral perception network extracts the spectrum relationship from spectral images. For perceiving cross information, a memory unit is utilized to store the features from different data sources in succession. In addition, the distance loss and reconstruction loss are introduced to keep the feature integrity, and the cross-entropy loss ensures that features can distinguish different classes. The comprehensive experiments are conducted on several datasets to validate the superiority of the proposed algorithm. The proposed S2PNet outperforms the considered classifiers with an average improvement of +0.77%, +5.62%, +1.58%, and +1.79% for overall accuracy values.

pH/chitinase dual stimuli-responsive essential oil-delivery system based on mesoporous silica nanoparticles for control of rice blast.

BACKGROUND: Owing to their surface modifiability, smart mesoporous silica nanoparticles (MSNs) can be designed to respond to plant disease-microenvironmental stimuli, thereby achieving on-demand release of active ingredients to control disease by effectively improving citral (CT) stability. RESULTS: A pH/chitinase dual stimuli-responsive essential oil-delivery system (CT@HMS@CH/TA) was successfully fabricated by encapsulating CT in hollow mesoporous silica (HMS), and coating with tannic acid (TA) and chitosan (CH) within HMS by using the layer-by-layer assembly technique (LbL). CT@HMS@CH/TA with an average particle size of 125.12 ± 0.12 nm and a hollow mesoporous nanostructure showed high CT-loading efficiency (16.58% ± 0.17%). The photodegradation rate of CT@HMS@CH/TA under UV irradiation (48 h) was only 15.31%, indicating a 3.34-fold UV stability improvement. CT@HMS@CH/TA exhibited a higher CT release rate in response to acidic pH and the presence of chitinase, simulating the prevailing conditions as Magnaporthe oryzae infection. Furthermore, CT@HMS@CH/TA exhibited better adhesion without affecting normal rice growth, significantly upregulating chitinase gene expression and enhancing chitinase activity on M. oryzae, thus enhancing CT antifungal activity. CONCLUSION: CT@HMS@CH/TA improved CT stability and showed intelligent, controlled release-performance and higher antifungal efficacy, thus providing a new strategy for efficient application of essential oils for green control of rice blast disease. © 2024 Society of Chemical Industry.

Hyperspectral and SAR Image Classification via Multiscale Interactive Fusion Network.

Due to the limitations of single-source data, joint classification using multisource remote sensing data has received increasing attention. However, existing methods still have certain shortcomings when faced with feature extraction from single-source data and feature fusion between multisource data. In this article, a method based on multiscale interactive information extraction (MIFNet) for hyperspectral and synthetic aperture radar (SAR) image classification is proposed. First, a multiscale interactive information extraction (MIIE) block is designed to extract meaningful multiscale information. Compared with traditional multiscale models, it can not only obtain richer scale information but also reduce the model parameters and lower the network complexity. Furthermore, a global dependence fusion module (GDFM) is developed to fuse features from multisource data, which implements cross attention between multisource data from a global perspective and captures long-range dependence. Extensive experiments on the three datasets demonstrate the superiority of the proposed method and the necessity of each module for accuracy improvement.

Asymmetric Feature Fusion Network for Hyperspectral and SAR Image Classification.

Joint classification using multisource remote sensing data for Earth observation is promising but challenging. Due to the gap of imaging mechanism and imbalanced information between multisource data, integrating the complementary merits for interpretation is still full of difficulties. In this article, a classification method based on asymmetric feature fusion, named asymmetric feature fusion network (AsyFFNet), is proposed. First, the weight-share residual blocks are utilized for feature extraction while keeping separate batch normalization (BN) layers. In the training phase, redundancy of the current channel is self-determined by the scaling factors in BN, which is replaced by another channel when the scaling factor is less than a threshold. To eliminate unnecessary channels and improve the generalization, a sparse constraint is imposed on partial scaling factors. Besides, a feature calibration module is designed to exploit the spatial dependence of multisource features, so that the discrimination capability is enhanced. Experimental results on the three datasets demonstrate that the proposed AsyFFNet significantly outperforms other competitive approaches.

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.

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.

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.

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.

Dual stimuli-responsive fungicide carrier based on hollow mesoporous silica/hydroxypropyl cellulose hybrid nanoparticles.

The controlled release of pesticides based on nanoparticle platforms has emerged as a new technology for increasing the efficiency of pesticides and for reducing environmental pollution because of their size-dependent and target-modifying properties. In the present study, pH/cellulase dual stimuli-responsive controlled-release formulations (PYR-HMS-HPC) were designed by grafting hydroxypropyl cellulose onto pyraclostrobin-loaded hollow mesoporous silica nanoparticles via an ester linkage. The PYR-HMS-HPC formulations were characterized by Fourier transform infrared spectroscopy, thermogravimetric analyzer, transmission electron microscope and scanning electron microscope. The results demonstrated that PYR-HMS-HPC with a loading capacity of 12.1 wt% showed excellent pyraclostrobin release behaviors in response to acidic environments and the introduction of cellulase, could effectively prevented pyraclostrobin from photolysis. Compared with commercial pyraclostrobin formulations, the PYR-HMS-HPC formulations showed much stronger and statistically significant fungicidal activity against Magnaporthe oryzae from 7 to 21 days. Furthermore, the Allium cepa chromosome aberration assay demonstrated that the PYR-HMS-HPC formulations reduced the genotoxicity of pyraclostrobin. These pH/cellulase dual stimuli-responsive controlled-release formulations are of great interest for sustainable on-demand crop disease protection.

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.

Development of glycine-copper(ii) hydroxide nanoparticles with improved biosafety for sustainable plant disease management.

Cabbage black rot caused by Xanthomonas campestris pv. campestris (Xcc) leads to decrease of the production of up to 70%. Copper biocides are widely used to control this disease because of their low-cost application and broad-spectrum antimicrobial activities. Extensive spraying of traditional copper biocides would cause undesirable effects on plants and the environment. In this work, a novel copper-based microbicide was prepared by binding copper with glycine in sodium hydroxide solution (Gly-Cu(OH)2 NPs) and characterized by inductively coupled plasma atomic emission spectroscopy, high-resolution transmission electron microscopy, Fourier transformation infrared spectroscopy, and dynamic light scattering. The results showed that the prepared Gly-Cu(OH)2 NPs had a mean diameter of 240 nm with copper content more than 25.0% and their antimicrobial efficacies against Xcc were significantly better than Kocide 3000 at 400-800 mg L-1 of copper after spraying for 14 days. The phytotoxicity tests under greenhouse conditions showed that Gly-Cu(OH)2 NPs were safer to plants than Kocide 3000 and obviously promoted the growth of plants, which led to the increase of fresh weights of Chinese cabbage and tomato seedlings by 6.34% and 3.88% respectively at a concentration of 800 mg L-1 of copper. As a novel copper-based microbicide, the Gly-Cu(OH)2 NPs can improve effective utilization of copper-based bactericides and reduce phytotoxicity to plants and would be a potential alternative for sustainable plant disease management.

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.

α-Amylase triggered carriers based on cyclodextrin anchored hollow mesoporous silica for enhancing insecticidal activity of avermectin against Plutella xylostella.

α-Amylase-responsive carrier for controlled release of avermectin (AVM) was prepared based on α-cyclodextrin (α-CD) anchored hollow mesoporous silica (HMS) using α-CD as a capping molecule. The release of AVM was studied at different temperatures, pH values and in the presence or absence of α-amylase. The results revealed that the AVM-encapsulated controlled release formulation (AVM-CRF) has a drastic enzymatic dependence, an excellent encapsulation efficacy reaching 38%, and outstanding UV and thermal shielding ability. The AVM-CRF biological activity survey shows excellent toxicological properties against Plutella xylostella larvae, which confirms that α-CD caps could be uncapped enzymatically in vivo and release AVM, inducing P. xylostella larval death. AVM-CRF has a notable capability to keep 0.6 mg L-1 AVM biologically active until 14th day with 83.33% mortality of the target insect, which was 40% higher than that of treated with AVM commercial formulation. The study provides a theoretical basis for the application of pesticide reduction.

Synthesis and Insecticidal Activity of Enzyme-Triggered Functionalized Hollow Mesoporous Silica for Controlled Release.

In the present study, enzymatic responsive controlled release formulations (CRFs) were fabricated. The CRFs were achieved by anchoring mechanically interlocked molecules using α-cyclodextrin onto the surface pore rims of hollow mesoporous silica (HMS). The CRFs were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis. The results showed that the CRFs had extraordinary loading ability for chlorantraniliprole (42% w/w) and could effectively preserve chlorantraniliprole against degradation under thermal conditions and UV radiation. The CRFs have been proven to be enzyme-sensitive. The release ratio of chlorantraniliprole from CRFs can be accelerated observably when external α-amylase was introduced. The persistence of CRFs was evaluated by regular sampling feeding experiment using Plutella xylostella as the target insect. The results showed that the larval mortality of P. xylostella was much higher than that of Coragen under all concentrations after 14 days, which proved that CRFs had remarkable persistence.