Preparation and optimization of agarose or polyacrylamide/amino acid-based double network hydrogels for photocontrolled drug release.

The high water content and biocompatibility of amino-acid-based supramolecular hydrogels have generated growing interest in drug delivery research. Nevertheless, the existing dominant approach of constructing such hydrogels, the exploitation of a single amino acid type, typically comes with several drawbacks such as weak mechanical properties and long gelation times, hindering their applications. Here, we design a near-infrared (NIR) light-responsive double network (DN) structure, containing amino acids and different synthetic or natural polymers, i.e., polyacrylamide, poly(N-isopropylacrylamide), agarose, or low-gelling agarose. The hydrogels displayed high mechanical strength and high drug-loading capacity. Adjusting the ratio of Fmoc-Tyr-OH/Fmoc-Tyr(Bzl)-OH or Fmoc-Phe-OH/Fmoc-Tyr(Bzl)-OH, we could drastically shorten the gelation time of the DN hydrogels at room and body temperatures. Moreover, introducing photothermal agents (graphene oxide, carbon nanotubes, molybdenum disulfide nanosheets, or indocyanine green), we equipped the hydrogels with NIR responsivity. We demonstrated the light-triggered release of the drug baclofen, which is used in severe spasticity treatment. Rheology and stability tests confirmed the positive impact of the polymers on the mechanical strength of the hydrogels, while maintaining good stability under physiological conditions. Overall, our study contributed a novel hydrogel formulation with high mechanical resistance, rapid gel formation, and efficient NIR-controlled drug release, offering new opportunities for biomedical applications.

Comparing the antibacterial activity of chitin nanocrystals with chitin: exploring the feasibility of chitin nanocrystals as novel pesticide nanocarriers in agriculture.

BACKGROUND: In recent years, nanomaterials-based pesticide carriers have garnered significant attention and sparked extensive research. However, most studies have primarily focused on investigating the impact of physical properties of nanomaterials, such as size and modifiable sites, on drug delivery efficiency of nano-pesticides. The limited exploration of biologically active nanomaterials poses a significant obstacle to the advancement and widespread adoption of nano-pesticides. In this study, we prepared chitin nanocrystals (ChNC) based on acid hydrolysis and systematically investigated the differences between nano- and normal chitin against plant bacteria (Pseudomonas syringae pv. tabaci). The primary objective was to seek out nanocarriers with heightened biological activity for the synthesis of nano-pesticides. RESULTS: Zeta potential analysis, Fourier Transform infrared spectrometry (FTIR), X-Ray diffraction (XRD), Atomic force microscopy (AFM) and Transmission electron microscopy (TEM) identified the successful synthesis of ChNC. ChNC showcased remarkable bactericidal activity at comparable concentrations, surpassing that of chitin, particularly in its ability to inhibit bacterial biofilm formation. Furthermore, ChNC displayed heightened effectiveness in disrupting bacterial cell membranes, resulting in the leakage of bacterial cell contents, structural DNA damage, and impairment of DNA replication. Lastly, potting experiments revealed that ChNC is notably more effective in inhibiting the spread and propagation of bacteria on plant leaves. CONCLUSION: ChNC exhibited higher antibacterial activity compared to chitin, enabling efficient control of plant bacterial diseases through enhanced interaction with bacteria. These findings offer compelling evidence of ChNC's superior bacterial inhibition capabilities, underscoring its potential as a promising nanocarrier for nano-pesticide research. © 2023 Society of Chemical Industry.

Washout-Resistant, pH-Responsive Anti-TMV Nanoimmune Inducer Based on Cellulose Nanocrystals.

The application of antiplant virus agents on leaf surfaces faces challenges due to their vulnerability to wear, instability, and limited duration, which in turn jeopardizes plant health and yield. In recent years, high-aspect-ratio nanomaterials have gained prominence as powerful carriers for disease treatment, thanks to their exceptional penetrability and precise drug delivery capabilities. Here, we synthesized a pH-responsive nanoimmune inducer (CNC-AMO) with strong leaf adhesion through a Schiff base reaction, achieved by grafting amino-oligosaccharides (AMOs) on the surface of aldehyde-based CNC (CNC-CHO). Fourier transform infrared spectrometry, zeta potential, X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, and elemental analysis were used to characterize the CNC-AMO. The CNC-AMO displayed the capability for pH-responsive AMO release, showcasing its potential for targeted and controlled delivery. When applied to plants, the CNC-AMO exhibited impressive anti-TMV efficacy during a weeklong observation period. Meanwhile, the CNC-AMO exhibited remarkable adhesion and scouring resistance on the surfaces of the plant leaves. We strongly believe that the synergy of environmentally friendly synthetic materials, efficient plant virus control, and streamlined scalability positions CNC-AMOs as a promising pesticide for plant virus therapy.

A chitosan-coated lentinan-loaded calcium alginate hydrogel induces broad-spectrum resistance to plant viruses by activating Nicotiana benthamiana calmodulin-like (CML) protein 3.

Control of plant virus diseases largely depends on the induced plant defence achieved by the external application of synthetic chemical inducers with the ability to modify defence-signalling pathways. However, most of the molecular mechanisms underlying these chemical inducers remain unknown. Here, we developed a chitosan-coated lentinan-loaded hydrogel and discovered how it protects plants from different virus infections. The hydrogel was synthesized by coating chitosan on the surface of the calcium alginate-lentinan (LNT) hydrogel (SL-gel) to form a CSL-gel. CSL-gels exhibit the capacity to prolong the stable release of lentinan and promote Ca2+ release. Application of CSL-gels on the root of plants induces broad-spectrum resistance against plant viruses (TMV, TRV, PVX and TuMV). RNA-seq analysis identified that Nicotiana benthamiana calmodulin-like protein gene 3 (NbCML3) is upregulated by the sustained release of Ca2+ from the CSL-gel, and silencing and overexpression of NbCML alter the susceptibility and resistance of tobacco to TMV. Our findings provide evidence that this novel and synthetic CSL-gel strongly inhibits the infection of plant viruses by the sustainable release of LNT and Ca2+ . This study uncovers a novel mode of action by which CSL-gels trigger NbCML3 expression through the stable and sustained release of Ca2+ .

Chitin nanocrystals supported copper: a new nanomaterial with high activity with P. syringae pv. Tabaci.

BACKGROUND: The application of chemical pesticides in control of plant bacterial disease may cause potential environmental pollution. Herein, based on the resistance-inducing ability and the special rod-like structure with high aspect ratio of bio-derived chitin nanocrystals (ChNC), a new Cu composite rod-like nanoparticle was fabricated (ChNC@Cu). The antibacterial activity of the composite nanoparticle was systematically studied, and its safety was evaluated. RESULTS: TEM, FTIR, ICP and other characterization methods proved that ChNC@Cu is a nano rod-like structure, with a Cu2+ loading capacity of 2.63%. In vitro experiments showed that the inhibition rate of ChNC@Cu to P. syringae pv. tabaci was more than 95% when the copper content was 41.6 µg mL-1 . In vivo experiments showed that ChNC@Cu had a good protective effect on P. syringae pv. tabaci of tobacco. In addition, ChNC@Cu exhibited stronger antibacterial activity than Thiodiazole copper (TC) at the same copper content. The study on the antibacterial mechanism of ChNC@Cu proved that ChNC@Cu caused bacterial death by destroying the bacterial cell membrane structure and damaging the DNA bacteria. And ChNC@Cu is highly safe for plants and can promote seed germination and plant growth. CONCLUSION: The special rod-like structure of ChNC can enrich Cu2+ to form ChNC@Cu. ChNC@Cu has a good protective effect on bacterial infection of tobacco, and achieves a great antibacterial activity at low Cu2+ concentration, which indicated that ChNC@Cu has induced resistance and antibacterial effect. As a novel green nanofungicide, ChNC@Cu has high potential application value in control of agricultural bacterial diseases. © 2023 Society of Chemical Industry.

Transcriptome analysis reveals the mechanism of zinc ion-mediated plant resistance to TMV in Nicotiana benthamiana.

Zinc ions (Zn2+) are used to promote plant growth and treat multiple diseases. However, it is still unclear which pathways in plants respond to Zn2+. In this study, we found that supplying (CH3COO)2Zn can effectively delay tobacco mosaic virus (TMV) replication and movement in Nicotiana benthamiana. To further understand the regulatory mechanism of antiviral activity mediated by Zn2+, we examined the transcriptomic changes of leaves treated with Zn2+. Three days after treatment, 7575 differential expression genes (DEGs) were enriched in the Zn2+ treatment group compared with the control group. Through GO and KEGG analysis, the pathway of phosphatidylinositol signaling system and inositol phosphate metabolism were significantly enriched after treated with Zn2+, and a large number of ethylene-responsive transcription factors (ERFs) involved in inositol phosphate metabolism were found to be enriched. We identified ERF5 performed a positive effect on plant immunity. Our findings demonstrated that Zn2+-mediated resistance in N. benthamiana activated signal transduction and regulated the expression of resistance-related genes. The results of the study uncover a global view of mRNA changes in Zn2+-mediated cellular processes involved in the competition between plants and viruses.

Synthetic chloroinconazide compound exhibits highly efficient antiviral activity against tobacco mosaic virus.

BACKGROUND: Development of anti-plant-virus compounds and improvement of biosafety remain hot research topics in controlling plant viral disease. Tobacco mosaic virus (TMV) infects all tobacco species as well as many other plants worldwide and causes severe losses in tobacco production. To date, no efficient chemical treatments are known to protect plants from virus infection. Therefore, the search for a highly active antiviral compound with high efficacy in field application is required. RESULTS: We reported the synthesis of a novel antiviral halogenated acyl compound Chloroinconazide (CHI) using tryptophan as a substrate and examined its anti-TMV activity. We found that CHI displayed the ability to strongly inhibit the infection of TMV on Nicotiana benthamiana via multiple mechanisms. We observed that CHI was able to impair the virulence of TMV by directly altering the morphological structure of virions and increasing the activity of anti-oxidative enzymes, resulting in reduced TMV-induced ROS production during infection of the plant. In addition, the expression of salicylic acid-responsive genes was significantly increased after CHI application. However, after application of CHI on SA-deficient NahG plants no obvious anti-TMV activity was observed, suggesting that the SA signaling pathway was required for CHI-induced anti-TMV activity associated with reduced infection of TMV. CHI exhibited no effects on plant growth and development. CONCLUSION: The easily synthesized CHI can actively induce plant resistance against TMV as well as act on virus particles and exhibits high biosafety, which provides a potential for commercial application of CHI in controlling plant virus disease in the future. © 2020 Society of Chemical Industry.

Fabrication of pH-Sensitive Tetramycin Releasing Gel and Its Antibacterial Bioactivity against Ralstonia solanacearum.

Ralstonia solanacearum (R. solanacearum)-induced bacterial wilt of the nightshade family causes a great loss in agricultural production annually. Although there has been some efficient pesticides against R. solanacearum, inaccurate pesticide releasing according to the onset time of bacterial wilt during the use of pesticides still hinders the disease management efficiency. Herein, on the basis of the soil pH change during R. solanacearum growth, and pH sensitivity of the Schiff base structure, a pH-sensitive oxidized alginate-based double-crosslinked gel was fabricated as a pesticide carrier. The gel was prepared by crosslinking oxidized sodium alginate (OSA) via adipic dihydrazide (ADH) and Ca2+. After loading tetramycin into the gel, it showed a pH-dependent pesticide releasing behavior and anti-bacterial activity against R. solanacearum. Further study also showed that the inhibition rate of the tetramycin-loaded gel was higher than that of industrial pesticide difenoconazole. This work aimed to reduce the difficulty of pesticide administration in the high incidence period of bacterial wilt and we believe it has a great application potential in nightshade production.

Reversible Mechanical Regulation and Splicing Ability of Alginate-Based Gel Based on Photo-Responsiveness of Molecular-Level Conformation.

In this study, benefiting from the sensitive molecular conformation transversion in azobenzene, a new strategy for fabricating alginate gels with the abilities of splicing and photo-responsive mechanical adjustment is reported. Firstly, a 4,4'-azobis(benzoylhydrazide) (Azo-hydrazide) linker was used to crosslink alginate physically via the electrostatic interaction between hydrazide groups and carboxyl groups. It was then shaped and transferred in situ to a chemically crosslinked gel via 450 nm light irradiation. Under the irradiation, the molecular conformation change of azobenzene in the linker was able to form covalent bonds at the crosslinking points of the gels. Furthermore, the reversible conformation transformation of azobenzene was able to induce the increase and decrease of the storage modulus under irradiation with 365 nm light and 450 nm light, respectively, while also providing gel-like mechanical properties, depending upon the irradiation time and given wavelength. Meanwhile, the results also indicated that active groups could contribute to the splicing ability of the gel and construct a hollow cavity structure. It is believed that this work could provide a versatile strategy for preparing photo-responsive gels with reversibly tunable mechanical properties.

Dual-Action Pesticide Carrier That Continuously Induces Plant Resistance, Enhances Plant Anti-Tobacco Mosaic Virus Activity, and Promotes Plant Growth.

Improving plant resistance against systemic diseases remains a challenging research topic. In this study, we developed a dual-action pesticide-loaded hydrogel with the capacity to significantly induce plant resistance against tobacco mosaic virus (TMV) infection and promote plant growth. We produced an alginate-lentinan-amino-oligosaccharide hydrogel (ALA-hydrogel) by coating the surface of an alginate-lentinan drug-loaded hydrogel (AL-hydrogel) with amino-oligosaccharide using electrostatic action. We determined the formation of the amino-oligosaccharide film using various approaches, including Fourier transform infrared spectrometry, the ζ potential test, scanning electron microscopy, and elemental analysis. It was found that the ALA-hydrogel exhibited stable sustained-release activity, and the release time was significantly longer than that of the AL-hydrogel. In addition, we demonstrated that the ALA-hydrogel was able to continuously and strongly induce plant resistance against TMV and increase the release of calcium ions to promote Nicotiana benthamiana growth. Meanwhile, the ALA-hydrogel maintained an extremely high safety to organisms. Our findings provide an alternative to the traditional approach of applying pesticide for controlling plant viral diseases. In the future, this hydrogel with the simple synthesis method, green synthetic materials, and its efficiency in the induction of plant resistance will attract increasing attention and have good potential to be employed in plant protection and agricultural production.

Cellulose Nanocrystal Surface Cationization: A New Fungicide with High Activity against Phycomycetes capsici.

At present, the management of Phytophthora capsici (P. capsici) mainly relies on chemical pesticides. However, along with the resistance generated by P. capsici to these chemical pesticides, the toxicity and non-degradability of this chemical molecule may also cause serious environmental problems. Herein, a new bio-based nano-antifungal material (CNC@CTAB) was made with coating hexadecyl trimethyl ammonium bromide (CTAB) on the surface of a cellulose nanocrystal (CNC). This material was then applied to the prevention of P. capcisi. This particle was facilely fabricated by mixing CTAB and sulfuric group modified CNC in an aqueous solvent. Compared to pure CTAB, the enrichment of CTAB on the CNC surface showed a better anti-oomycete activity both in vitro and in vivo. When CNC@CTAB was applied on P. capsici in vitro, the inhibition rate reached as high as 100%, while on the pepper leaf, the particle could also efficiently prevent the infection of P. capsici, and achieve a disease index as low as zero Thus, considering the high safety of CNC@CTAB in agricultural applications, and its high anti-oomycete activity against P. capsici, we believe that this CNC@CTAB has great application potential as a new green nano-fungicide in P. capsici management during the production of peppers or other vegetables.

Green Synthesis of an Alginate-Coated Silver Nanoparticle Shows High Antifungal Activity by Enhancing Its Cell Membrane Penetrating Ability.

As a kind of promising nanopesticide, in contrast to traditional synthesis strategies, the application of a polysaccharide in silver nanoparticle preparation can improve its stability and avoid the usage of harmful substances. In this work, a two-step strategy for synthesizing silver nanoparticles (A-AgNPs) from aldehyde-modified sodium alginate (ASA) was introduced. The size of the A-AgNPs synthesized can be controlled from 6 to 40 nm with a high dispersibility in water. Furthermore, compared to naked AgNPs (n-AgNPs), the A-AgNPs showed improved broad-spectrum antimicroorganism activity. We found that the A-AgNPs mainly exerted their antifungal activity through the changing of cell membrane permeability and affecting the soluble protein synthesis, destruction of DNA structure, and inhibition of DNA replication. Meanwhile, the A-AgNPs showed no inhibition of rice and N. benthamiana seed germination. Considering its high biocompatibility and the highly efficient antimicroorganism activity, A-AgNPs can be potentially applied in plant protection science research.

MgONPs Can Boost Plant Growth: Evidence from Increased Seedling Growth, Morpho-Physiological Activities, and Mg Uptake in Tobacco (Nicotiana tabacum L.).

In this study, we documented the impact of magnesium oxide nanoparticles (MgONPs) on the various morpho-physiological changes by root irrigation in tobacco plants in the matrix media, as well as the uptake and accumulation of the NPs over a range of concentrations (50⁻250 µg/mL). Our results showed that the seed germination rate was not affected following exposure to MgONPs for 5 days. Enhanced plant growth together with increased peroxidase activity (39.63 U mg-1 protein in the 250 µg/mL MgONPs treatment, 36.63 U mg-1 protein in the control), superoxide dismutase activity (30.15 U mg-1 protein compared to 26.95 U mg-1 protein in the control), and chlorophyll content (the chlorophyll a and b contents in 0 and 250 µg/mL of MgONPs were 0.21, 0.12 µg/g to 1.21, 0.67 µg/g, respectively) were observed after 30 days of MgONP treatment. However, the malondialdehyde, protein, and relative water contents did not differ significantly, indicating that the NPs in the test concentrations had no phytotoxicity and even promoted plant growth. Scanning electron microscopy and paraffin section observations indicated that the MgONPs did not affect the plant tissue structures and cells. In addition, an elevated Mg content was detected in the plant tissues exposed to MgONPs, suggesting that the Mg was taken up by the tobacco roots and translocated to the shoots and leaves, which were probably the most important tools to cause an increase in the chlorophyll content and stimulate growth. In particular, compared with the controls, a substantially higher Mg content was observed in the leaves (12.93 mg/g in the MgONPs treatment, 9.30 mg/g in the control) exposed to 250 µg/mL MgONPs, especially in the lower and middle leaves. This result confirmed that the contents of plant Mg-element in the old leaves were increased by MgONPs. In summary, this study investigated increased Mg uptake and growth stimulation, as well as the induction of various positive morpho-physiological changes to tobacco plants when exposed to MgONPs. Results elucidate the promotional impact of the NPs on plant health and their implications for agricultural safety and security.