In Situ Construction of Zinc-Mediated Fe, N-Codoped Hollow Carbon Nanocages with Boosted Oxygen Reduction for Zn-Air Batteries.

The rational design of bifunctional oxygen electrocatalysts with unique morphology and luxuriant porous structure is significant but challenging for accelerating the reaction kinetics of rechargeable Zn-air batteries (ZABs). Herein, zinc-mediated Fe, N-codoped carbon nanocages (Zn-FeNCNs) are synthesized by pyrolyzing the polymerized iron-doped polydopamine on the surface of the ZIF-8 crystal polyhedron. The formation of the chelate between polydopamine and Fe serves as the covering layer to prevent the porous carbon nanocages from collapsing and boosts enough exposure and utilization of metal-based active species during carbonization. Furthermore, both the theoretical calculation and experimental results show that the strong interaction between polyhedron and polydopamine facilitates the evolution of high-activity zinc-modulated FeNx sites and electron transportation and then stimulates the excellent bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). As expected, the Zn-air battery with Zn-FeNCNs as an air cathode displays a superior power density (256 mW cm-2) and a high specific capacity (813.3 mA h gZn-1), as well as long-term stability over 1000 h. Besides, when this catalyst is applied to the solid-state battery, the device exhibited outstanding mechanical stability and a high round-trip efficiency under different bending angles.

Controllable and Reversible Assembly of Nanofiber from Natural Macromolecules via Protonation and Deprotonation.

Nanofiber is the critical building block for many biological systems to perform various functions. Artificial assembly of molecules into nanofibers in a controllable and reversible manner will create "smart" functions to mimic those of their natural analogues and fabricate new functional materials, but remains an open challenge especially for nature macromolecules. Herein, the controllable and reversible assembly of nanofiber (CSNF) from natural macromolecules with oppositely charged groups are successfully realized by protonation and deprotonation of charged groups. By controlling the electrostatic interaction via protonation and deprotonation, the size and morphology of the assembled nanostructures can be precisely controlled. A strong electrostatic interaction contributes to large nanofiber with high strength, while poor electrostatic interaction produces finer nanofiber or nanoparticle. And especially, the assembly, disassembly, and reassembly of the nanofiber occurs reversibly through protonation and deprotonation, thereby paving a new way for precisely controlling the assembly process and structure of nanofiber. The reversible assembly allows the nanostructure to dynamically reorganize in response to subtle perturbation of environment. The as-prepared CSNF is mechanical strong and can be used as a nano building block to fabricate high-strength film, wire, and straw. This study offers many opportunities for the biomimetic synthesis of new functional materials.

Carbon Fiber Film with Multi-Hollow Channels to Expedite Oxygen Electrocatalytic Reaction Kinetics for Flexible Zn-Air Battery.

The high oxygen electrocatalytic overpotential of flexible cathodes due to sluggish reaction kinetics result in low energy conversion efficiency of wearable zinc-air batteries (ZABs). Herein, lignin, as a 3D flexible carbon-rich macromolecule, is employed for partial replacement of polyacrylonitrile and constructing flexible freestanding air electrodes (FFAEs) with large amount of mesopores and multi-hollow channels via electrospinning combined with annealing strategy. The presence of lignin with disordered structure decreases the graphitization of carbon fibers, increases the structural defects, and optimizes the pore structure, facilitating the enhancement of electron-transfer kinetics. This unique structure effectively improves the accessibility of graphitic-N/pyridinic-N with oxygen reduction reaction (ORR) activity and pyridinic-N with oxygen evolution reaction (OER) activity for FFAEs, accelerating the mass transfer process of oxygen-active species. The resulting N-doped hollow carbon fiber films (NHCFs) exhibit superior bifunctional ORR/OER performance with a low potential difference of only 0.60 V. The rechargeable ZABs with NHCFs as metal-free cathodes possess a long-term cycling stability. Furthermore, the NHCFs can be used as FFAEs for flexible ZABs which have a high specific capacity and good cycling stability under different bending states. This work paves the way to design and produce highly active metal-free bifunctional FFAEs for electrochemical energy devices.

Enhanced Efficiency and Stability of Sky Blue Perovskite Light-Emitting Diodes via Introducing Lead Acetate.

All-inorganic metal halide perovskite is promising for highly efficient and thermally stable perovskite light-emitting diodes (PeLEDs). However, there is still great room for improvement in the film quality, including low coverage and high trap density, which play a vital role in achieving high-efficiency PeLEDs. In this work, lead acetate (Pb(Ac)2) was introduced into the perovskite precursor solution as an additive. Experimental results show that perovskite films deposited from a one-step anti-solvent free solution process with increased surface coverage and reduced trap density were obtained, leading to enhanced photoluminescence (PL) intensity. More than that, the valence band maximum (VBM) of perovskite films was reduced, bringing about a better energy level matching the work function of the hole-injection layer (HIL) poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS), which is facilitated for the hole injection, leading to a decrease in the turn-on voltage (Vth) of PeLEDs from 3.4 V for the control device to 2.6 V. Finally, the external quantum efficiency (EQE) of the sky blue PeLEDs (at 484 nm) increased from 0.09% to 0.66%. The principles of Pb(Ac)2 were thoroughly investigated by using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). This work provides a simple and effective strategy for improving the morphology of perovskite and therefore the performance of PeLEDs.

Tight Binding and Dual Encapsulation Enabled Stable Thick Silicon/Carbon Anode with Ultrahigh Volumetric Capacity for Lithium Storage.

Silicon (Si) is regarded as one of the most promising anode materials for high-performance lithium-ion batteries (LIBs). However, how to mitigate its poor intrinsic conductivity and the lithiation/delithiation-induced large volume change and thus structural degradation of Si electrodes without compromising their energy density is critical for the practical application of Si in LIBs. Herein, an integration strategy is proposed for preparing a compact micron-sized Si@G/CNF@NC composite with a tight binding and dual-encapsulated architecture that can endow it with superior electrical conductivity and deformation resistance, contributing to excellent cycling stability and good rate performance in thick electrode. At an ultrahigh mass loading of 10.8 mg cm-2 , the Si@G/CNF@NC electrode also presents a large initial areal capacity of 16.7 mA h cm-2 (volumetric capacity of 2197.7 mA h cm-3 ). When paired with LiNi0.95 Co0.02 Mn0.03 O2 , the pouch-type full battery displays a highly competitive gravimetric (volumetric) energy density of ≈459.1 Wh kg-1 (≈1235.4 Wh L-1 ).

Recent progress in regulating starch digestibility using natural additives and sustainable processing operations.

The development of a healthier and more sustainable food supply is a main concern of consumers, industry, governments, and international institutions. Foods containing high levels of rapidly digestible starches have been linked to a rise in the number of people suffering from diet-related chronic diseases. Consequently, there is interest in reducing the digestibility of starch to improve their healthiness. The ability of natural additives including proteins, dietary fibers, and polyphenols, and sustainable processing technologies such as high-intensity ultrasonic, pulsed electric field, non-thermal plasma, γ-ray irradiation that regulate reduce starch digestibility in foods are reviewed. The potential mechanisms of action, advantages, and disadvantages of each approach at inhibiting starch digestibility is highlighted. The potential for commercializing these technologies is discussed, and areas where further research are required are emphasized. Natural additives and sustainable processing operations can effectively reduce the digestibility of starch and inhibit postprandial sugar "spikes" in the bloodstream by adjusting the structural changes, which can be used to create healthier and more sustainable foods and have broad application prospects.

Recent trends of 3D printing based on starch-hydrocolloid in food, biomedicine and environment.

People are exploring the potential application of 3D printing in food, biomedicine and environment, but it is urgent to find suitable bio-ink. Bio-ink compounded with starch and hydrocolloid can not only improve the rheology, structure and printability of starch-based edible bio-ink, but also endow it with other functional characteristics, so that it can be applied to food, biomedicine and even the environment, and meet the strategic needs of national health, green and sustainable development. In this paper, hydrocolloids are reviewed as potential means to regulate the physicochemical properties of starch, which endows it with good printability and presents excellent printing products. The specific applications of the bio-ink in the fields of food, biomedicine and environment in hypoglycemic, lipid-lowering, swallowable food, delivery, intelligent materials, and bio-sensor are also discussed. Then, the challenges and future development trends of realizing large-scale application are prospected. Proper physicochemical properties of starch-hydrocolloid are positively correlated with printability. The presentation of excellent printability has realized the application in different fields, not only satisfies most people, but also create benefits for some specific people. This review is expected to provide some theoretical guidance for the further development of 3D printing technology and its large-scale application.

Progress on molecular modification and functional applications of anthocyanins.

Anthocyanins have attracted a lot of attention in the fields of natural pigments, food packaging, and functional foods due to their color, antioxidant, and nutraceutical properties. However, the poor chemical stability and low bioavailability of anthocyanins currently limit their application in the food industry. Various methods can be used to modify the structure of anthocyanins and thus improve their stability and bioavailability characteristics under food processing, storage, and gastrointestinal conditions. This paper aims to review in vitro modification methods for altering the molecular structure of anthocyanins, as well as their resulting improved properties such as color, stability, solubility, and antioxidant properties, and functional applications as pigments, sensors and functional foods. In industrial production, by mixing co-pigments with anthocyanins in food systems, the color and stability of anthocyanins can be improved by using non-covalent co-pigmentation. By acylation of fatty acids and aromatic acids with anthocyanins before incorporation into food systems, the surface activity of anthocyanins can be activated and their antioxidant and bioactivity can be improved. Various other chemical modification methods, such as methylation, glycosylation, and the formation of pyranoanthocyanins, can also be utilized to tailor the molecular properties of anthocyanins expanding their range of applications in the food industry.

Encapsulation of polyphenols in protein-based nanoparticles: Preparation, properties, and applications.

Polyphenols have a variety of physiological activities, including antioxidant, antimicrobial, and anti-inflammatory properties. However, their applications are often limited because due to the instability of polyphenols. Encapsulation technologies can be employed to overcome these problems and increase the utilization of polyphenols. In this article, the utilization of protein-based nanoparticles for encapsulating polyphenols is reviewed due to their good biocompatibility, biodegradability, and functional attributes. Initially, the various kinds of animal and plant proteins available for forming protein nanoparticles are discussed, as well as the fabrication methods that can be used to assemble these nanoparticles. The molecular interaction mechanisms between proteins and polyphenols are then summarized. Applications of protein-based nanoparticles for encapsulating polyphenols are then discussed, including as nutrient delivery systems, in food packaging materials, and in the creation of functional foods. Finally, areas where further research is need on the development, characterization, and application of protein-based polyphenol-loaded nanoparticles are highlighted.

Optimization of food-grade colloidal delivery systems for thermal processing applications: a review.

Colloidal delivery systems are widely used in the food industry to enhance the dispersibility, stability, efficacy, or bioavailability. However, when exposed to the high temperature, delivery systems are often prone to degradation, which limits its application in thermal processing. In this paper, the effects of thermal processing on the performance of traditional protein-based or starch-based delivery systems are firstly described, including the molecular structure changes of proteins, starches or lipids, and the degradation of embedded substances. These effects are unfavorable to the application of the delivery system in thermal processing. Then, strategies of improving the heat resistance of food grade colloid delivery system and their use in frying, baking and cooking food are mainly introduced. The heat resistance of the delivery system can be improved by a variety of strategies, including the development of new heat-resistant materials, the addition of heat-resistant coatings to the surface of delivery systems, the cross-linking of proteins or starches using cross-linking agents, the design of particle structures, the use of physical means such as ultrasound, or the optimization of the ingredient formula. These strategies will help to expand the application of heat-resistant delivery systems so that they can be used in real thermal processing.

Starch as edible ink in 3D printing for food applications: a review.

Three-dimensional (3D) printing has attracted more attention in food industry because of its potential advantages, including the ability to create customized products according to individual's sensory or nutritional requirements. However, the production of high-quality 3D printed foods requires the availability of edible bio-inks with the required physicochemical and sensory attributes. Starch, as one of the important sources of dietary energy, is widely used in food processing and is considered as one kind of versatile polymers. It is not only because starch has low prices and abundant sources, but also because desirable modified starch can be obtained by altering its physicochemical properties through physical, chemical and enzymatic methods. This article focuses on the utilization of starch as materials to create food-grade bio-inks. Initially, several kinds of commonly used 3D printers are discussed. The factors affecting the printing quality of starch-based materials and improvement methods are then reviewed, as well as areas where future researches are required. The applications of 3D printed starch-based materials in food industry are also introduced. Overall, starch appears to be one kind of useful substances for creating edible bio-inks that can be utilized within 3D food printing applications to create a wide variety of food products.

Activating Lattice Oxygen in Layered Lithium Oxides through Cation Vacancies for Enhanced Urea Electrolysis.

Despite the fact that high-valent nickel-based oxides exhibit promising catalytic activity for the urea oxidation reaction (UOR), the fundamental questions concerning the origin of the high performance and the structure-activity correlations remain to be elucidated. Here, we unveil the underlying enhanced mechanism of UOR by employing a series of prepared cation-vacancy controllable LiNiO2 (LNO) model catalysts. Impressively, the optimized layered LNO-2 exhibits an extremely low overpotential at 10 mA cm-2 along with excellent stability after the 160 h test. Operando characterisations combined with the theoretical analysis reveal the activated lattice oxygen in layered LiNiO2 with moderate cation vacancies triggers charge disproportion of the Ni site to form Ni4+ species, facilitating deprotonation in a lattice oxygen involved catalytic process.

Nickel-4'-(3,5-dicarboxyphenyl)-2,2',6',2″-terpyridine Framework: Efficient Separation of Ethylene from Acetylene/Ethylene Mixtures with a High Productivity.

A novel compound, [Ni(DCPTP)] n (termed Ni-DCPTP), based on the 4'-(3,5-dicarboxyphenyl)-2,2',6',2″-terpyridine (DCPTP2-) ligand was presented here. Ni-DCPTP has a three-dimensional structure with a ths topology featuring one-dimensional (1D) helical channels. Ni-DCPTP shows an efficient removal of a trace amount of C2H2 from a C2H2/C2H4 (1/99) mixture with an excellent C2H4 productivity as demonstrated by both the transient breakthrough simulations and breakthrough experiments, generating the polymer-grade C2H4 gas (C2H2 < 40 ppm). The carboxylate oxygen atoms on the surface of 1D channels are the preferential binding sites for C2H2 molecules. This work demonstrates an elegant example with carboxylate oxygen-functionalized pore channels for effective C2H2/C2H4 separation.

Label-Aware Dual Graph Neural Networks for Multi-Label Fundus Image Classification.

Fundus disease is a complex and universal disease involving a variety of pathologies. Its early diagnosis using fundus images can effectively prevent further diseases and provide targeted treatment plans for patients. Recent deep learning models for classification of this disease are gradually emerging as a critical research field, which is attracting widespread attention. However, in practice, most of the existing methods only focus on local visual cues of a single image, and ignore the underlying explicit interaction similarity between subjects and correlation information among pathologies in fundus diseases. In this paper, we propose a novel label-aware dual graph neural networks for multi-label fundus image classification that consists of population-based graph representation learning and pathology-based graph representation learning modules. Specifically, we first construct a population-based graph by integrating image features and non-image information to learn patient's representations by incorporating associations between subjects. Then, we represent pathologies as a sparse graph where its nodes are associated with pathology-based feature vectors and the edges correspond to probability of the co-occurrence of labels to generate a set of classifier scores by the propagation of multi-layer graph information. Finally, our model can adaptively recalibrate multi-label outputs. Detailed experiments and analysis of our results show the effectiveness of our method compared with state-of-the-art multi-label fundus image classification methods.

Co-encapsulation of quercetin and resveratrol: Comparison in different layers of zein-carboxymethyl cellulose nanoparticles.

Three nanoparticles were fabricated for the co-delivery of quercetin and resveratrol. Nanoparticles consisted of a zein and carboxymethyl cellulose assembled using antisolvent precipitation/layer-by-layer deposition method. Nanoparticles contained quercetin in the core and resveratrol in the shell, resveratrol in the core and quercetin in the shell or both quercetin and resveratrol in the core. The particle sizes of nanoparticles were 280.4, 214.8, and 181.8 nm, respectively. Zeta-potential was about -50 mV and PDI was about 0.3. The different positions of polyphenol distribution nanoparticles could reduce the competition between the two polyphenols, the encapsulation rate, loading rate and storage stability reached up to 91.7 %, 5.37 % and 97.1 %, respectively. FT-IR showed that hydrophobic and electrostatic interactions were the main driving forces of nanoparticle assembly. XRD showed that two polyphenols were successfully encapsulated in nanoparticles. TGA showed that distributing the nanoparticles in different layers would enhance thermal stability. TEM and SEM showed that polysaccharides attached to the surface of nanoparticles formed a core-shell structure with uniform particle size. All three nanoparticles could release two polyphenols slowly in simulated gastrointestinal digestion, Korsmeyer-Peppas was the most suitable kinetic release model. Therefore, biopolymer-based nanocarriers can be created to enhance the loading, stability, and bioaccessibility of co-encapsulated nutraceuticals.

An effective preserving strategy for strawberries by constructing pectin/starch coatings reinforced with functionalized eggshell fillers.

Food waste occurs frequently worldwide, though hunger and malnutrition issues have received global attention. Short-term spoilage of perishable foods causes a significant proportion of food waste. Developing simple, green, and low-cost strategies to preserve the freshness of perishable foods is important to address this issue and improving food safety. By using strawberries as the model perishable fruit, this study reported a pectin/carboxy methyl starch sodium (PC) based coating using epigallocatechin gallate-loaded eggshell powder (ES@EGCG) as the functional fillers. In comparison to PC coating, the PC-ES@EGCG coating displayed much-enhanced performance, such as enhanced mechanical (2 folds) and barrier (water vapor & oxygen) properties. This composite coating reduced the weight loss of strawberries from over 60% to around 30% after 7-day storage. Coated strawberries exhibit better freshness retention, which achieves the purpose of preserving strawberries during storage. This study provided a cost-effective and eco-friendly coating strategy for reducing food waste.

Effects of crosslinking agents on properties of starch-based intelligent labels for food freshness detection.

The impact of citric acid, carboxymethyl cellulose, carboxymethyl starch, sodium trimetaphosphate, or soybean protein on the crosslinking of starch-based films was examined. These crosslinking starch films were then used to create pH-sensitive food labels using a casting method. Blueberry anthocyanins were incorporated into these smart labels as a pH-sensitive colorimetric sensor. The mechanical properties, moisture resistance, and pH responsiveness of these smart labels were then examined. Crosslinking improved the mechanical properties and pH sensitivity of the labels. These different crosslinking agents also affected the hydrophobicity of the labels to varying degrees. Soybean protein was the only additive that led to labels that could sustain their structural integrity after immersion in water for 12 h. Because it increased the hydrophobicity of the labels, which decreased their water vapor permeability, moisture content, swelling index, and water solubility by 47 %, 29 %, 52 % and 10 %, respectively. The potential of using these labels to monitor the freshness of chicken breast was then examined. Only the films containing soybean protein exhibited good pH sensitivity, high structural stability, and low pigment leakage. This combination of beneficial attributes suggests that the composite films containing starch and soybean protein may be most suitable for monitoring meat freshness.

High water resistance starch based intelligent label for the freshness monitoring of beverages.

The traditional starch-based intelligent freshness labels struggle to maintain long-term structural stability when exposed to moisture. To solve this problem, we prepared composite crosslinked labels using phytic acid for double crosslinking of corn starch and soybean isolate proteins, with anthocyanin serving as the chromogenic dye. The mechanical properties, hydrophobic characteristics, and pH responsivity of these crosslinked labels were assessed in this study. The prepared double-crosslinked labels showed reduced moisture content (15.96%), diminished swelling (147.21%), decreased solubility (28.55%), and minimized water permeability, which suggested that they have enhanced hydrophobicity and densification. The crosslinked labels demonstrated the ability to maintain morphological stability when immersed in water for 12 h. Additionally, the mechanical properties of the crosslinked labels were enhanced without compromising their pH-sensing capabilities, demonstrated a color response visible to the naked eye for milk and coconut water freshness monitoring, suggesting great potential for application in beverages freshness monitoring.

Eggshell waste act as multifunctional fillers overcoming the restrictions of starch-based films.

Starch has great potential to replace petroleum-based plastics in food packaging applications. However, starch films often exhibit poor mechanical and barrier properties, and are vulnerable to moisture and bacterial contamination. This study proved that the incorporation of eggshell powder (ES) enhanced the hydrogen bonding in starch-based films significantly, which contributed to improved tensile strength, Young's modulus, and water resistance of the films. The performance of ES-incorporated films could be optimized by adjusting the size, concentration, and surface property of ES in the film matrix. Notably, adsorbing epigallocatechin gallate (EGCG) on the surface of porous ES contributed to enhanced dispersibility of the fillers in the film matrix, which increased the tortuous path of light, water vapor, and oxygen have to take through the films, resulting in increased UV screening performance, water vapor and oxygen barrier property of the films by 60 %, 7.2 %, and 27.9 %, respectively. Meanwhile, loading EGCG in ES also enable superior antibacterial activity of the final films. This study suggests that eggshell fillers offer a sustainable means of improving the functional performance of starch-based films, which may increase their application as packaging materials in the food industry.

Mass Production of Sulfur-Tuned Single-Atom Catalysts for Zn-Air Batteries.

Single-atom catalysts (SACs) show great potential for rechargeable Zn-air batteries (ZABs); however, scalable production of SACs from sustainable resources is difficult owing to poor control of the local coordination environment. Herein, lignosulfonate, a by-product of the papermaking industry, is utilized as a multifunctional bioligand for the mass production of SACs with highly active MN4 S sites (M represents Fe, Cu, and Co) via strong metalnitrogen/sulfur coordination. This effectively adjusts the charge distribution and promotes the catalytic performance, leading to highly durable and excellent performance in oxygen reduction and evolution reactions for ZABs. This study paves the way for the industrial production of cost-effective SACs in a sustainable manner.