One-pot co-crystallized hexanal-loaded ZIF-8/quaternized chitosan film for temperature-responsive ethylene inhibition and climacteric fruit preservation.

Controlling ethylene production and microbial infection are key factors to prolong the shelf life of climacteric fruit. Herein, a nanocomposite film, hexanal-loaded ZIF-8/CS (HZCF) with "nano-barrier" structure, was developed by a one-pot co-crystallized of ZIF-8 in situ growth on quaternized chitosan (CS) and encapsulation of hexanal into ZIF-8 via microporous adsorption. The resultant film realized the temperature responsive release of hexanal via the steric hindrance and hierarchical pore structure as "nano-barrier", which can inhibit ethylene production in climacteric fruit on demand. Based on this, the maximum ethylene inhibition rate of HZCF was up to 52.6 %. Meanwhile, the film exhibits excellent antibacterial, mechanical, UV resistance and water retention properties, by virtue of the functional synergy between ZIF-8 and CS. Contributed to the multifunctional features, HZCF prolonged the shelf life of banana and mango for at least 16 days, which is 8 days longer than that of control fruit. More strikingly, HZCF is washable and biodegradable, which is expected to replace non-degradable plastic film. Thus, this study provides a convenient novel approach to simplify the encapsulation of active molecule on metal-organic frameworks (MOFs), develops a packaging material for high-efficient freshness preservation, and helps to alleviate the survival crisis caused by food waste.

Self-triggered carboxymethyl chitosan hydrogel for the convenient sustained release of ClO2 gas with environmental stability and long-term antimicrobial effect.

Challenges associated with the storage and uncontrolled release of ClO2 gas present significant hurdles to its practical application. Herein, a clever strategy for self-triggering the sustained release of chlorine dioxide (ClO2) gas is proposed by crosslinking carboxymethyl chitosan (CMCS) with Zn2+ to construct a novel CMCS-Zn@NaClO2 gel with eco-friendly, environmental stability, and convenient, long term, and efficient antibacterial activity. The precursor (NaClO2) in the CMCS solution was alkaline and triggered by the acidic Zn(NO3)2·6H2O solution to achieve sustained self-triggering ClO2 release. The ClO2 gas self-release could be sustained on demand at different temperatures for at least 20 days due to the environmental structure stability of the gel. The hydrogels showed an increase in pore size after sustained release. Molecular dynamics simulations showed the spontaneous release of ClO2 gas at room temperature and the contraction of the CMCS agglomeration, which were consistent with the macroscopic behaviour. The gel displayed a long-acting and high antibacterial efficacy, resulting in a bacteria-killing rate of over 99.9% (inhibitory concentrations of 2.5 mg mL-1 against E. coli and 0.16 mg mL-1 against S. aureus). The hydrogels could effectively extend the shelf life of fruits and demonstrated an excellent wide range of antibacterial properties. This work provides a new approach to solving the storage difficulty of ClO2 gas and offers a fresh perspective on the design of materials with convenient self-triggering release by a precursor, as well as the relationship between the material microstructure and sustained-release behaviour.

Multifunctional Starch-Based Sensor with Non-Covalent Network to Achieve "3R" Circulation.

With the consumption of disposable electronic devices increasing, it is meaningful but also a big challenge to develop reusable and sustainable materials to replace traditional single-use sensors. Herein, a clever strategy for constructing a multifunctional sensor with 3R circulation (renewable, reusable, pollution-reducing biodegradable) is presented, in which silver nanoparticles (AgNPs) with multiple interactions are introduced into a reversible non-covalent cross-linking network composed of biocompatible and degradable carboxymethyl starch (CMS) and polyvinyl alcohol (PVA) to simultaneously obtain high mechanical conductivity and long-term antibacterial properties by a one-pot method. Surprisingly, the assembled sensor shows high sensitivity (gauge factor up to 4.02), high conductivity (0.1753 S m-1 ), low detection limit (0.5%), long-term antibacterial ability (more than 7 days), and stable sensing performance. Thus, the CMS/PVA/AgNPs sensor can not only accurately monitor a series of human behavior, but also identify handwriting recognition from different people. More importantly, the abandoned starch-based sensor can form a 3R circulation. Especially, the fully renewable film still shows excellent mechanical performance, achieving reusable without sacrificing its original function. Therefore, this work provides a new horizon for multifunctional starch-based materials as sustainable substrates for replacing traditional single-use sensors.

Enhanced antibacterial effect and biodegradation of coating via dual-in-situ growth based on carboxymethyl cellulose.

The lack of antimicrobial effect of commercial paper coating for food packaging makes it difficult to prevent food spoilage and harms the environment by non-biodegradation. Herein, carboxymethyl cellulose (CMC) provides negatively charged sites for anchoring Ag+ and Zn2+ to grow AgNPs and ZIF-8 in situ on its molecular chains. The ZIF-8/AgNPs@CMC paper coating has excellent synergistic antibacterial activity to prolong the shelf-life of food. It not only has good thermal stability but binds closely to the paper and its adhesion force reaches 628.9 nN. Besides, the ZIF-8/AgNPs@CMC coated paper has better mechanical properties, water vapor barrier, and resists water solubility. Interestingly, due to the confinement effect of ZIF-8, the cumulative release of AgNPs after 168 h is only 2.66 % to avoid possible food safety risks. Especially, the coating can be almost biodegraded in the soil after 30 days, which provides the possibility to replace the non-biodegradable coatings in food packaging.

Hybridization of carboxymethyl chitosan with bimetallic MOFs to construct renewable metal ion "warehouses" with rapid sterilization and long-term antibacterial effects.

Pathogens transmitted through the water environment pose a great threat to human health. Hence developing more reliable and efficient antibacterial materials to eliminate bacterium in water environments is urgent. Herein, we posed a novel strategy of interweaving carboxymethyl chitosan (CMCS) and Ag/Cu-MOFs to construct renewable Ag/Cu-BTC@CMCS composite beads with rapid sterilization, long-term antibacterial effects and high biosafety. Characterizations revealed that CMCS and bimetallic MOFs act as the "warehouses" of metal ions and played key roles in anchoring, storage, delivery, and controlled release of metal ions. The synergistic antibacterial effect achieved by the combination of Ag+ and Cu2+ provides the composite beads with high antibacterial efficiency, resulting in low minimum inhibitory concentrations (0.32 mg/mL against E. coli and 0.16 mg/mL against S. aureus) and over 99.9 % bacteria killing rate. Benefiting from the rapid release of metal ions from polymer chains and the long-term release from MOFs, the composite beads can effectively sterilize the simulated swimming pool water in 2 h and persistently inhibit bacterial reproduction over 48 h, and show a safe level of residual heavy metals because of the chelation of CMCS. This work provides new insights and promises a strategy for the design and commercial application of novel water fungicides.

Convenient, nondestructive monitoring and sustained-release of ethephon/chitosan film for on-demand of fruit ripening.

The microstructure changes (such as micro defects and free volume, etc.) is a deep factor that determines the sustained release behavior of polymer film. However, there are few reports exploring the micro defects of sustained-release materials. Herein, we develop a facile method to non-destructive monitoring and sustained-release ethylene within chitosan. The comprehensive means of positron annihilation lifetime spectroscopy, atomic force microscopy and Raman spectrums are performed together to study the microstructures change of ethylene sustained-release and its mechanism. When ethylene is in chitosan film, it shows good ripening performance and mechanical properties. The sustained-release ethylene improves its bioavailability and can control the fruit-ripening on-demand. More importantly, the microstructural changes of cavities have a significant impact on the sustained release of ethylene, due to the creation of cavities, the free volume of positrons undergoes a process of increasing from less to more and then gradually decreasing, reaching a maximum at 120 h. Furthermore, the ethephon/chitosan film could on-demand control the ripening time of mangoes and bananas. Therefore, this research presents a comprehensive means to study of microstructure change monitoring and controllable sustained release, and provides the possibility to solve the problem of on-demand ripening of fruit and reducing pesticide residue.

A self-matching, ultra-fast film forming and washable removal bio-crosslinked hydrogel films for perishable fruits.

Spoilage of food has aggravated the issue of food shortage worldwide. Here, we report a strategy for ultrafast hydrogel film forming within 10 s on fruit surfaces with good self-matching, washable removal and preservative property. This carboxymethyl chitosan (CMCS)/tannic acid (TA) hydrogel film (CTHF) is fabricated by bio-material of CMCS and TA via in-situ rapidly crosslinking with high-density hydrogen bonds. Simply blending TA and CMCS solution at room temperature can form CTHF with different roughness (Ra: ranges from 123 to 1.55 nm) on different fruit surfaces, so as to perfectly match the hydrogel protective layer of pericarp. The CTHF slows down fruit decay by its outstanding antioxidant and antibacterial activity. It is soluble and easily removed (within 3-5 min) by washing without environmental pollution and food safety issues. As natural polymer, CTHF shows high promise as sustainable substitutes for conventional plastics packing because of its non-toxic, edible, biodegradable, and environmentally friendly.

Synthesis of Surface-Oxygen-Vacancy-Rich (GaN)0.5(ZnO)0.5 Particles with Enhanced Visible-Light Photodegradation Performance.

In this study, zinc-gallium oxynitrides with a Zn:Ga mole ratio of 1:1 [(GaN)0.5(ZnO)0.5] were synthesized from a Zn/Ga/CO3 layered double hydroxide (LDH) precursor. The microstructure and photoactivity of the (GaN)0.5(ZnO)0.5 particles were tuned by adjusting the nitridation conditions of the LDH. It is revealed that the quantity of the LDH, or, equivalently, the partial pressure of the water during nitridation, plays a pivotal role in the defect structure of the obtained oxynitrides. A reduction in the quantity of the LDH precursor can effectively suppress the formation of defects including Ga(Zn)-O bonding, bulk anion vacancies, and surface-deposited Ga/ON···VGa complexes, leading to a better charge-separation efficiency for the photogenerated electron-hole pairs in the oxynitride. Furthermore, a suitable introduction of methane during nitridation would not only increase the crystallinity of the bulk materials but also enhance the density of the surface oxygen vacancy (VO), which would raise the charge-injection efficiency by working as an electron trap and a reaction site to form O2•-. O2•-, as well as photogenerated holes, have been proven to be the dominant active species for the photodegradation of phenol. 25CH4-ZnGaNO, with the lowest density of bulk defects and the highest density of surface VO, exhibited the best photoactivity under visible-light irradiation for the photodegradation of Rhodamine B and phenol. The obtained surface-VO-rich (GaN)0.5(ZnO)0.5 particles can be applied as a high-performance visible-light-driven photocatalyst in the photodegradation of organic pollutants.