Fabrication of zein-coated brush-like silica nanocarriers for high foliage deposition and responsive release of pesticide.

Responsive release systems have received extensive attention to enhance pesticide utilization efficiency and reduce environmental pollution. In this study, pH/GSH dual responsive release system based on brush-like silica (bSiO2) carriers was constructed to enhance the utilization of pesticides. The bSiO2 carriers present core-shell structure, length of 550 nm, diameter of 350 nm and shell thickness of 100 nm. The carrier had a high pesticide loading (20.0 %, w/w) for dinotefuran (Din). After loading Din, zein was covalently linked with cysteine-bridge to seal the loaded pesticides (namely Din@bSiO2@Zein). The Din@bSiO2@Zein exhibited superior foliar affinity, retention and photostability, and retention rate still remain above 95 % with 220 min UV irradiation. Din@bSiO2@Zein displayed pH/GSH responsive release and the cumulative release within 92 h was up to 81 % under pH=9/CGSH=6 mM, mimicking the microenvironment of lepidopteran. The Din@bSiO2@Zein possessed good control efficacy against Plutella xylostella. Appreciably, Din@bSiO2@Zein could be transported bi-directionally to various regions of tobacco plants within 24 h, which had potential to promote pesticide efficacy. This work offers a strategy to minimize the pesticide dosage and encourage sustainable agricultural development.

Multifunctional Mesoporous Silica Nanosheets for Smart Pesticide Delivery and Enhancing Pesticide Deposition.

A multifunctional nanopesticide delivery system is considered to be a novel and efficient tool for controlling pests in modern agriculture. In this study, a mesoporous silica nanosheet (H-MSN) carrier for intelligent delivery of pesticides was prepared by the sol-gel method. The prepared H-MSN carrier had obvious hexagonal flat structure, with a specific surface area of 759.9 m2/g, a transverse diameter of about 340 nm, a thickness of about 80 nm, and regular channels being perpendicular to the plane. Polyethylene glycol diacrylate (PEGDA) and sulfhydryl-modified polyethylenimide (PEI-SH) were used to block the insecticide after loading the insecticide imidacloprid (IMI). The introduction of hydrophilic PEI-SH/PEGDA greatly improved the leaf wettability and adhesion ability of H-MSN. The retention amount of IMI@H-MSN@PEI-SH/PEGDA on cucumber and cabbage leaves was up to 46.0 mg/cm2 and 19.0 mg/cm2, respectively. IMI@H-MSN@PEI-SH/PEGDA showed pH- and GSH-responsive release. Compared with pure IMI, IMI entrapped in MSN carriers has favorable biocompatibility and antiphotolytic properties.

Carboxymethyl ß-cyclodextrin grafted hollow copper sulfide@mesoporous silica carriers for stimuli-responsive pesticide delivery.

Stimuli-responsive controlled release systems have received extensive attention to improve the pesticide bioavailability and minimize environmental pollution. Herein, a multiple stimuli-responsive IMI@HCuS@mSiO2 @ -ss-CßCD delivery system was constructed using modified carboxymethyl ß-cyclodextrin (CßCD-ss-COOH) as sealing materials, hollow copper sulfide nanoparticles with amino-functionalized mesoporous silica shell (HCuS@mSiO2-NH2) as carriers and imidacloprid (IMI) as the model drug. The cavity structure of HCuS@mSiO2-NH2 would provide a large space for pesticide loading. The results revealed that HCuS@mSiO2-ss-CßCD was approximately 230 nm in size and the loading efficiency for IMI was 25.7%, and exhibited better biosafety on bacteria and seed. HCuS carriers were also served as photothermal agent and possessed high photothermal conversion effect (η = 38.4%). IMI@HCuS@mSiO2 @ -ss-CßCD displayed excellent foliage adhesion and multiple stimuli-responsive release properties to pH, α-amylase, GSH, and NIR. The photostability of IMI embedded in CuS@mSiO2 @ -ss-CßCD was approximately 10 times that of IMI solution. This work provides an efficient nanoplatform for realizing pesticide delivery.

Polydopamine-encapsulated cap-like mesoporous silica based delivery system for responsive pesticide release and high retention.

Nanopesticides formulation has been applied in modern agriculture, but the effective deposition of pesticides on plant surfaces is still a critical challenge. Here, we developed a cap-like mesoporous silica (C-mSiO2) carrier for pesticide delivery. The C-mSiO2 carriers with surface amino groups present uniform cap-like shape and have an mean diameter of 300 nm and width of 100 nm. This structure would reduce the rolling and bouncing of carriers on plant leaves, leading to improving the foliage deposition and retention. After loading dinotefuran (DIN), polydopamine (PDA) was used to encapsulate the pesticide (DIN@C-mSiO2@PDA). The C-mSiO2 carriers exhibit high drug loading efficiency (24.7%) and benign biocompatibility on bacteria and seed. Except for pH/NIR response release, the DIN@C-mSiO2@PDA exhibited excellent photostability under UV irradiation. Moreover, the insecticidal activity of DIN@C-mSiO2@PDA was comparable to that of pure DIN and DIN commercial suspension (CS-DIN). This carrier system has the potential for improving the foliage retention and utilization of pesticides.

pH and NIR responsive polydopamine-doped dendritic silica carriers for pesticide delivery.

The stimuli-responsive pesticide delivery system provides a powerful strategy for enhancing the effective utilization of pesticides and reducing environmental pollution. Here, we prepared a new polydopamine doped dendritic silica (SiO2/PDA) nanocarriers for pesticide delivery. The SiO2/PDA nanocarriers present uniform spheres with an average diameter of 250 nm and carry center-radial inner pores. After loading dinotefuran (DNF) insecticide, polyethyleneimine (PEI) was used to cap the loaded-pesticide pores. The resulting SiO2/PDA@PEI displays high photothermal conversion effect (η = 35.1 %) and pH and near infrared (NIR) light-responsive release behavior. Meanwhile, the SiO2/PDA and SiO2/PDA@PEI carriers displayed high adhesion and wettability to leaves, and the photostability of DNF encapsulated in SiO2/PDA@PEI was improved by nearly 10 times greater than for free DNF. Importantly, the SiO2/PDA carriers possessed a benign biocompatibility on Escherichia coli (E. coli), seed and cells. Therefore, this work provides a promising approach to improve the utilization of pesticide.

Synthesis of CuO and PAA-Regulated Silver-Carried CuO Nanosheet Composites and Their Antibacterial Properties.

With the aid of a facile and green aqueous solution approach, a variety of copper oxide (CuO) with different shapes and polyacrylic-acid (PAA)-regulated silver-carried CuO (CuO@Ag) nanosheet composites have been successfully produced. The point of this article was to propose a common synergy using Ag-carried CuO nanosheet composites for their potential antibacterial efficiency against three types of bacteria such as E. coli, P. aeruginosa, and S. aureus. By using various technical means such as XRD, SEM, and TEM, the morphology and composition of CuO and CuO@Ag were characterized. It was shown that both CuO and CuO@Ag have a laminar structure and exhibit good crystallization, and that the copper source and reaction duration have a sizable impact on the morphology and size distribution of the product. In the process of synthesizing CuO@Ag, the appropriate amount of polyacrylic acid (PAA) can inhibit the agglomeration of Ag NPs and regulate the size of Ag at about ten nanometers. In addition, broth dilution, optical density (OD 600), and electron microscopy analysis were used to assess the antimicrobial activity of CuO@Ag against the above three types of bacteria. CuO@Ag exhibits excellent synergistic and antibacterial action, particularly against S. aureus. The antimicrobial mechanism of the CuO@Ag nanosheet composites can be attributed to the destruction of the bacterial cell membrane and the consequent leakage of the cytoplasm by the release of Ag+ and Cu2+. The breakdown of the bacterial cell membrane and subsequent leakage of cytoplasm caused by Ag+ and Cu2+ released from antimicrobial agents may be the cause of the CuO@Ag nanosheet composites' antibacterial action. This study shows that CuO@Ag nanosheet composites have good antibacterial properties, which also provides the basis and ideas for the application research of other silver nanocomposites.

Facile One-Step Deposition of Ag Nanoparticles on SiO2 Electrospun Nanofiber Surfaces for Label-Free SERS Detection and Antibacterial Dressing.

The fabrication of highly active and free-standing surface-enhanced Raman scattering (SERS) substrates in a simple and low-cost manner has been a crucial and urgent challenge in recent years. Herein, SiO2 nanofiber substrates modified with size-tunable Ag nanoparticles were prepared by the combination of electrospinning and in situ chemical reduction. The results demonstrate the presence and uniform adsorption of Ag nanoparticles on the SiO2 matrix surface. The free-standing composite nanofibrous substrates show high-performance SERS response toward 4-mercaptophenol and 4-mercaptobenzoic acid, and the detection limit can be as low as 10-10 mol/L. Most importantly, the as-prepared substrate as a versatile SERS platform can realize label-free detection of bio-macromolecules of bacteria, i.e., Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Furthermore, the substrates also possess outstanding antibacterial activities against S. aureus and E. coli. Briefly, the significance of this study is that size-tunable Ag nanoparticles can be decorated on SiO2 nanofiber surfaces with triethanolamine as a bridging and reducing agent through a one-pot reaction, and the as-prepared nanofibrous membranes are expected to act as a candidate for label-free SERS detection as well as antibacterial dressing.

Loading of Au/Ag Bimetallic Nanoparticles within and Outside of the Flexible SiO2 Electrospun Nanofibers as Highly Sensitive, Stable, Repeatable Substrates for Versatile and Trace SERS Detection.

In this paper, we propose a facile and cost-effective electrospinning technique to fabricate surface-enhanced Raman scattering (SERS) substrates, which is appropriate for multiple analytes detection. First of all, HAuCl4∙3H2O was added into the TEOS/PVP precursor solution, and flexible SiO2 nanofibers incorporated with gold nanoparticles (SiO2@Au) were prepared by electrospinning and calcination. Subsequently, the nanofibrous membranes were immersed in the tannic acid and 3-aminopropyltriethoxysilane solution for surface modification through Michael addition reaction. Finally, the composite nanofibers (Ag@T-A@SiO2@Au) were obtained by the in-situ growth of Ag nanoparticles on the surfaces of nanofibers with tannic acid as a reducing agent. Due to the synergistic enhancement of Au and Ag nanoparticles, the flexible and self-supporting composite nanofibrous membranes have excellent SERS properties. Serving as SERS substrates, they are extremely sensitive to the detection of 4-mercaptophenol and 4-mercaptobenzoic acid, with an enhancement factor of 108. Moreover, they could be utilized to detect analytes such as pesticide thiram at a low concentration of 10-8 mol/L, and the substrates retain excellent Raman signals stability during the durability test of 60 days. Furthermore, the as-fabricated substrates, as a versatile SERS platform, could be used to detect bacteria of Staphylococcus aureus without a specific and complicated bacteria-aptamer conjugation procedure, and the detection limit is up to 103 colony forming units/mL. Meanwhile, the substrates also show an excellent repeatability of SERS response for S. aureus organelles. Briefly, the prime novelty of this work is the fabrication of Au/Ag bimetallic synergetic enhancement substrates as SERS platform for versatile detection with high sensitivity and stability.

A Facile Method for the Fabrication of Silver Nanoparticles Surface Decorated Polyvinyl Alcohol Electrospun Nanofibers and Controllable Antibacterial Activities.

Polyvinyl alcohol (PVA) electrospun nanofibers (NFs) are ideal carriers for loading silver nanoparticles (Ag NPs) serving as antibacterial materials. However, it is still a challenge to adjust the particles size, distribution, and loading density via a convenient and facile method in order to obtain tunable structure and antimicrobial activities. In this study, Ag NPs surface decorated PVA composite nanofibers (Ag/PVA CNFs) were fabricated by the solvothermal method in ethylene glycol, which plays the roles of both reductant and solvent. The morphology and structure of the as-fabricated Ag/PVA CNFs were characterized by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X-ray diffraction, UV-visible spectroscopy, and Fourier transform infrared spectroscopy. Ag NPs had an average diameter of 30 nm, the narrowest size distribution and the highest loading density were successfully decorated on the surfaces of PVA NFs, at the AgNO3 concentration of 0.066 mol/L. The antibacterial properties were evaluated by the methods of absorption, turbidity, and growth curves. The as-fabricated Ag/PVA hybrid CNFs exhibit excellent antimicrobial activities with antibacterial rates over 98%, especially for the sample prepared with AgNO3 concentration of 0.066 mol/L. Meanwhile, the antibacterial effects are more significant in the Gram-positive bacteria of Staphylococcus aureus (S. aureus) than the Gram-negative bacteria of Escherichia coli (E. coli), since PVA is more susceptive to S. aureus. In summary, the most important contribution of this paper is the discovery that the particles size, distribution, and loading density of Ag NPs on PVA NFs can be easily controlled by adjusting AgNO3 concentrations, which has a significant impact on the antibacterial activities of Ag/PVA CNFs.

Highly Sensitive Surface-Enhanced Raman Spectroscopy Substrates of Ag@PAN Electrospinning Nanofibrous Membranes for Direct Detection of Bacteria.

Surface-enhanced Raman spectroscopy (SERS) can be applied for biological detection because of its high sensitivity and noninvasiveness for analytes. Herein, we engineer plasmonic free-standing substrates composed of Ag nanoparticles (NPs) supported on polyacrylonitrile (PAN) electrospinning nanofibrous felts as sensors for bacterial detection. Ag NPs are evenly distributed on PAN nanofibers after preimpregnation and impregnation of PAN nanofibers in Tollens' reagent. The size and loading density of Ag NPs are tunable by adjusting the reaction time of glucose and Tollens' reagent, thereby allowing the tuning of the surface plasmon resonance. Using 4-mercaptophenol (4-MPh) and 4-mercaptobenzoic acid (4-MBA) as probe molecules, SERS effects of Ag@PAN composite nanofibers are investigated, and the substrates allow the detection of 4-MPh and 4-MBA at a low concentration of 10-9 mol/L. Importantly, the substrates exhibit a high sensitivity of SERS performance for bacterial identification without a specific bacteria-aptamer conjugation. The SERS substrates also show good uniformity of SERS response for bacterial organelles. Furthermore, the antimicrobial property was evaluated, and the results indicate that the sample of Ag@PAN nanofiber mats possesses excellent antibacterial properties against Escherichia coli and Staphylococcus aureus.