MOF Hybrid for Long-Term Pest Management and Micronutrient Supply Triggered with Protease.

Advanced intelligent systems for delivery of pesticides or fertilizers require formulations that allow for long-term efficacy. In this work, a metal-organic framework (MOF) hybrid was developed for long-term pest management and micronutrient supply. Zeolitic imidazolate framework-8 was fabricated for crop micronutrients (Zn2+) supply and insecticide dinotefuran (DNF) encapsulation. Polymethylmethacrylate was polymerized in situ to impart the MOF hybrid with sustained cargo delivery. Then, zein was introduced to facilitate protease-triggered cargo release associated with the microenvironment of pests and targeted release. The resulting MOF hybrid exhibited stimulus-responsive, slow-release behaviors. Sustained DNF delivery was achieved over a period of at least 32 days in soil. Compared with that of free DNF, the UV resistance of DNF in the MOF hybrid increased by nearly 10 times, and the insecticidal efficiency increased 33.3% with leaching treatment and 40.1% after incubating in a greenhouse for 14 days. This MOF hybrid provides a controlled, targeted, and sustained delivery formulation for long-term pest management and crop micronutrient supply and has huge application prospects in sustainable agriculture.

Noncovalent Muscle-Inspired Hydrogel with Rapid Recovery and Antifatigue Property under Cyclic Stress.

Designing muscle-inspired hydrogels that possess structure and bioactivity similar to muscles is an eternal pursuit in material sciences and tissue engineering. However, the development of a muscle-inspired hydrogel via the formation of noncovalent interactions remains challenging, and its application in sustained loading situations such as cyclic stresses is limited. Herein, H-bonds and microcrystalline domains were introduced, and a noncovalent muscle-inspired hydrogel was developed to mimic both the physical structure and functionality of muscles at the macroscopic level. The hydrogel exhibited excellent mechanical properties (a fracture strength of 2.16 ± 0.08 MPa, fracture strain of 830 ± 23%, elastic modulus of 275 ± 9 KPa, and toughness of 7.04 ± 0.80 MJ/m3), a large energy dissipation (2.00 ± 0.27 MJ/m3 at 600% elongation), and a rapid self-recovery (92 ± 1% toughness recovery within 20 min). Antifatigue behavior of the muscle-inspired hydrogel was observed upon successive tensile and compressive cyclic loadings. Under 100 cycles of loadings, the robustness of the hydrogel has been maintained and even improved, which are achieved due to strain-induced orientation. Furthermore, the hydrogel was found to be self-healed. This hydrogel promises to be among the most relevant drivers for the development of new-generation muscle-inspired hydrogels in the next decade.

Polysaccharides based injectable hydrogel compositing bio-glass for cranial bone repair.

Bone disease is a public health problem around the word, and it is urgent to develop novel tissue engineering scaffolds for the complicated cranial bone regeneration. The present work developed a novel triple crosslinked polysaccharides based injectable hydrogel to composite bio-glass (BG) for cranial bone repair. Dynamic mechanical analysis showed the storage modulus (G') of the hydrogel reached to ∼4000Pa. While after compositing BG, G' exceeded 4500Pa. The degradation behavior of the hydrogel is influenced by hydrogel composition, crosslinking methods and degradation environment. Through compositing BG for rat cranial bone repair, excellent bone regeneration effect was achieved (chunks of "white" new tissue was detected in the defected site, HE histopathological analysis confirmed the new tissue was bone tissue). Thus, the hydrogel is suitable as the carrier of BG for bone repair, demonstrating the prepared triple crosslinked hydrogel is potential for bone tissue engineering applications.

Dual crosslinked chondroitin sulfate injectable hydrogel formed via continuous Diels-Alder (DA) click chemistry for bone repair.

In the present work, a thermosensetive copolymer with a low gelation concentration under 37°C, F127@ChS (F127 crosslinked chondroitin sulfate) was synthesized via DA click chemistry between F127-AMI (maleimido terminated F127) and ChS-furan (furfurylamine grafted chondroitin sulfate). Then, dual crosslinked hydrogels were prepared based on F127@ChS and PEG-AMI (maleimido terminated polyethylene glycol). The physical crosslinking of F127@ChS affords the hydrogel fast gelation behavior, while in situ DA click reaction occurred between F127@ChS and PEG-AMI affords the hydrogel system covalent crosslinking. The dual crosslinked injectable hydrogel was applied as scaffold to load BMP-4 for rat cranial defect repair. As indicated by X-ray imaging, cranial digital images and histological (HE and Masson) staining analysis, new bone tissues were formed in the defected area after 12 weeks repair. The results demonstrate that the novel dual crosslinked injectable hydrogel offer an interesting option for cranial bone tissue engineering.

An injectable and self-healing hydrogel with covalent cross-linking in vivo for cranial bone repair.

Current hydrogels based on chondroitin sulfate (ChS) generally lack the necessary strength and precise mechanical tunability. Addressing these limitations, covalent cross-linking has evolved to produce hydrogels with desirable properties. However, such a methodology always precludes injection and self-healing. In this study, we employ DA click chemistry and dynamic acylhydrazone bond cross-linking for hydrogel formation that overcomes the limitations of current ChS hydrogels. Dynamic acylhydrazone bonds afford the hydrogel injectability and self-healing ability, while DA click chemistry facilitates the employment of covalent crosslinking for stabilization in vivo and modulating hydrogel properties in vivo. The study reveals that the obtained hydrogel possesses highly tunable viscoelastic and rheological properties, swelling and degradation behavior, and injectability and self-healing ability compared with ChS hydrogels cross-linked by single DA click chemistry or acylhydrazone bonds. Meanwhile, this hydrogel shows increased viability and reduced apoptosis of rat mesenchymal stem cells, and excellent tissue adhesive ability in vivo. The hydrogel was loaded with BMP-4 and used as a scaffold for rat cranial bone tissue engineering. The results demonstrated that new bone tissue was detected in the defected area of the cranial bone. Thus, this cytocompatible, injectable and self-healing hydrogel with tunable properties can be used as a scaffold for cranial bone tissue engineering and promote bone formation.

Synthesis and characterization of carboxymethyl potato starch and its application in reactive dye printing.

Carboxymethyl potato starch (CMPS) was synthesized with a simple dry and multi-step method as a product of the reaction of native potato starch and monochloroacetic acid in the presence of sodium hydroxide. The influence of the molar ratio of sodium hydroxide to anhydroglucose unit, the volume of 95% (v/v) ethanol, the rotation rate of motor driven stirrer and the reaction time for degree of substitution (DS) were evaluated. The product was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffractometry (XRD). FTIR spectrometry showed new bonds at 1618 and 1424 cm⁻¹ when native starch underwent carboxymethylation. SEM pictures showed that the smooth surface of native starch particles was mostly ruptured. XRD revealed that starch crystallinity was reduced after carboxymethylation. The viscosity of the mixture paste of carboxymethyl starch and sodium alginate (SA) was measured using a rotational viscometer. In addition, the applied effect of mixed paste in reactive dye printing was examined by assessing the fabric stiffness, color yield and sharp edge to the printed image in comparison with SA. And the results indicated that the mixed paste could partially replace SA as thickener in reactive dye printing. The study also showed that the method was low cost and eco-friendly and the product would have an extensive application in reactive dye printing.

Utilization of wheat straw for the preparation of coated controlled-release fertilizer with the function of water retention.

With the aim of improving fertilizer use efficiency and minimizing the negative impact on the environment, a new coated controlled-release fertilizer with the function of water retention was prepared. A novel low water solubility macromolecular fertilizer, poly(dimethylourea phosphate) (PDUP), was "designed" and formulated from N,N'-dimethylolurea (DMU) and potassium dihydrogen phosphate. Simultaneously, an eco-friendly superabsorbent composite based on wheat straw (WS), acrylic acid (AA), 2-acryloylamino-2-methyl-1-propanesulfonic acid (AMPS), and N-hydroxymethyl acrylamide (NHMAAm) was synthesized and used as the coating to control the release of nutrient. The nitrogen release profile and water retention capacity of the product were also investigated. The degradation of the coating material in soil solution was studied. Meanwhile, the impact of the content of N-hydroxymethyl acrylamide on the degradation extent was examined. The experimental data showed that the product with good water retention and controlled-release capacities, being economical and eco-friendly, could be promising for applications in agriculture and horticulture.

Synthesis, characterization and functional properties of low substituted acetylated corn starch.

Acetylated corn starch (ACS) was synthesized by the reaction of native corn starch (NCS) with acetic anhydride (AA) in an aqueous medium in the presence of sodium hydroxide as a catalyst. The factors that could affect the degree of substitution (DS) and reaction efficiency (RE) of corn starch were investigated which included the reaction temperature and time, the mass ratio of AA to starch, the ratio of the water volume to starch mass and pH. The optimal DS of 0.071 and RE of 67.05% was obtained. FTIR spectrometry showed new bands at 1733, 1375 and 1252 cm(-1). The SEM of the ACS indicated some cavities on the granules which fused together, compared with NCS. Wide angle X-ray diffraction revealed that ACS had a similar profile as NCS (A type). However, the intensity of peaks were diminished. DSC thermograms exhibited that ACS had some lower gelatinization temperatures and enthalpies than NCS. The functional properties of ACS such as the swelling power, solubility, water absorption, clarity, freeze-thaw stability, retrogradation and viscosity were also studied. The results suggest that the ACS has much better functional properties than the NCS, and could be expected to have wide applications especially in food industry.

Synthesis and characterization of a novel potato starch derivative with cationic acetylcholine groups.

A novel substance, cationic acetylcholine potato starch (CAPS), was developed for the first time. The synthesis process had three steps: first, carboxymethyl potato starch (CMPS) was synthesized under sodium hydroxide alkaline condition and in isopropyl alcohol organic media; second, bromocholine chloride (BCC) was synthesized with sulphuric acid as a catalytic agent; finally, CAPS was synthesized by the reaction of CMPS with BCC in N,N'-dimethylformamide (DMF). The degree of substitution (DS) of CAPS was determined by ammonia gas-sensing electrode and elemental analysis. CAPS was characterized by Fourier transformed infrared (FTIR) and near infrared (FTNIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC).

Synthesis of oxidized guar gum by dry method and its application in reactive dye printing.

The aim of this study was to prepare oxidized guar gum with a simple dry method, basing on guar gum, hydrogen peroxide and a small amount of solvent. To obtain a product with suitable viscosity for reactive dye printing, the effects of various factors such as the amount of oxidant and solvent, reaction temperature and time were studied with respect to the viscosity of reaction products. The product was characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, scanning electron microscopy and differential scanning calorimetry. The hydrated rate of guar gum and oxidized guar gum was estimated through measuring the required time when their solutions (1%, w/v) reached the maximum viscosity. The effects of the salt concentration and pH on viscosity of the resultant product were studied. The mixed paste containing oxidized guar gum and carboxymethyl starch was prepared and its viscosity was determined by the viscometer. The rheological property of the mixed paste was appraised by the printing viscosity index. In addition, the applied effect of mixed paste in reactive dye printing was examined by assessing the fabric stiffness, color yield and sharp edge to the printed image in comparison with sodium alginate. And the results indicated that the mixed paste could partially replace sodium alginate as thickener in reactive dye printing. The study also showed that the method was low cost and eco-friendly and the product would have an extensive application in reactive dye printing.

Environmentally friendly slow-release nitrogen fertilizer.

To sustain the further world population, more fertilizers are required, which may become an environmental hazard, unless adequate technical and socioeconomic impacts are addressed. In the current study, slow-release formulations of nitrogen fertilizer were developed on the basis of natural attapulgite (APT) clay, ethylcellulose (EC) film, and sodium carboxymethylcellulose/hydroxyethylcellulose (CMC/HEC) hydrogel. The structural and chemical characteristics of the product were examined. The release profiles of urea, ammonium sulfate, and ammonium chloride as nitrogen fertilizer substrates were determined in soil. To further compare the release profiles of nitrogen from different fertilizer substrates, a mathematical model for nutrient release from the coated fertilizer was applied to calculate the diffusion coefficient D. The influence of the product on water-holding and water-retention capacities of soil was determined. The experimental data indicated that the product can effectively reduce nutrient loss, improve use efficiency of water, and prolong irrigation cycles in drought-prone environments.

Multifunctional slow-release organic-inorganic compound fertilizer.

Multifunctional slow-release organic-inorganic compound fertilizer (MSOF) has been investigated to improve fertilizer use efficiency and reduce environmental pollution derived from fertilizer overdosage. The special fertilizer is based on natural attapulgite (APT) clay used as a matrix, sodium alginate used as an inner coating and sodium alginate-g-poly(acrylic acid-co-acrylamide)/humic acid (SA-g-P(AA-co-AM)/HA) superabsorbent polymer used as an outer coating. The coated multielement compound fertilizer granules were produced in a pan granulator, and the diameter of the prills was in the range of 2.5-3.5 mm. The structural and chemical characteristics of the product, as well as its efficiency in slowing the nutrients release, were examined. In addition, a mathematical model for nutrient release from the fertilizer was applied to calculate the diffusion coefficient D of nutrients in MSOF. The degradation of the SA-g-P(AA-co-AM)/HA coating was assessed by examining the weight loss with incubation time in soil. It is demonstrated that the product prepared by a simple route with good slow-release property may be expected to have wide potential applications in modern agriculture and horticulture.