Fabrication and Characterization of Carrageenan/ZnO/Chitosan Composite Films.

In this study, a high-performance carrageenan/ZnO/chitosan composite film (FCA/ZnO/CS) was fabricated by the solution/dispersion casting method and layer-by-layer method. The first layer was nano-ZnO dispersed in carrageenan solution, and the second layer was chitosan dissolved in acetic acid. The morphology, chemical structure, surface wettability, barrier properties, mechanical properties, optical properties, and antibacterial activity of FCA/ZnO/CS were evaluated compared with a carrageenan film (FCA) and carrageenan/ZnO composite film (FCA/ZnO). This study revealed that the Zn element in FCA/ZnO/CS existed in the form of Zn2+ in FCA/ZnO/CS. There existed electrostatic interaction and hydrogen bonding between CA and CS. As a result, the mechanical strength and transparency of FCA/ZnO/CS were enhanced and the water vapor transmittance of FCA/ZnO/CS was decreased compared with that of FCA/ZnO. Furthermore, the addition of ZnO and CS greatly enhanced the antibacterial activity of Escherichia coli and also had a certain inhibitory effect on Staphylococcus aureus. FCA/ZnO/CS is expected to be a potential candidate material for food packaging, wound dressings, and various surface antimicrobial coatings.

NiFe Nanoparticle-Encapsulated Ultrahigh-Oxygen-Doped Carbon Layers as Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries.

There is an urgent demand for developing highly efficient bifunctional electrocatalysts with excellent stability toward the oxygen evolution and reduction reactions (OER and ORR, respectively) for rechargeable Zn-air batteries (ZABs). In this work, NiFe nanoparticles encapsulated within ultrahigh-oxygen-doped carbon quantum dots (C-NiFe) as bifunctional electrocatalysts are successfully obtained. The accumulation of carbon layers formed by carbon quantum dots results in abundant pore structures and a large specific surface area, which is favorable for improving catalytic active site exposure, ensuring high electronic conductivity and stability simultaneously. The synergistic effect of NiFe nanoparticles enriched the number of active centers and naturally increased the inherent electrocatalytic performance. Benefiting from the above optimization, C-NiFe shows excellent electrochemical activity for both OER and ORR processes (the OER overpotential is only 291 mV to achieve 10 mA cm-2). Furthermore, the C-FeNi catalyst as an air cathode displays an impressive peak power density of 110 mW cm-2, an open-circuit voltage of 1.47 V, and long-term durability over 58 h. The preparation of this bifunctional electrocatalyst provides a design idea for the construction of bimetallic NiFe composites for high-performance Zn-air batteries.

Zero-Carbon Emission Chemical Method to Remove Formaldehyde without Catalyst by Highly Porous Polymer Composites at Room Temperature.

Herein, the fabrication of reduced graphene oxide (RGO)-templated polymer composites for chemical removal of gaseous formaldehyde under ambient conditions is presented. The chemical removal of formaldehyde is achieved by a nucleophilic addition reaction between formaldehyde and aminooxy groups on the polymer chain ends to form the oxime bonds with the only byproduct of H2 O. RGO is essential since it not only has an ultralarge surface area but also can act as a perfect template for immobilizing pyrene-terminated and aminooxy-functionalized polymers via strong π-π stacking interactions, while melamine foam provides a three-dimensional skeleton for loading RGO/polymer composites to afford a porous 3D structure for efficient formaldehyde removal. Since the oxime bond can be cleaved into aminooxy group in acidic media, the RGO/polymer composite can be regenerated for repeatable usage, which shows an excellent performance of adsorbing 14 mg of formaldehyde by 100 mg of the polymer at ambient condition.

Precisely Defining Local Gradients of Stimuli-Responsive Hydrogels for Complex 2D-to-4D Shape Evolutions.

The intellectualization and complication of existing self-shaping materials are limited by the inseparable monotonic relationship between their deformation rate and deformation degree (i.e., a higher deformation rate is accompanied by a high deformation degree). This causes that they can only deform from 2D to 3D states. Here, a simple yet versatile strategy to decouple the monotonic correlation between the deformation rate and deformation degree of self-shaping hydrogels is presented for achieving complex deformations from 2D to temporary 3D to 3D (2D-to-4D). It is demonstrated that when the gradient hydrogels prepared by photopolymerization possess dense polymer networks, the local regions with a high deformation rate can exhibit a low deformation degree. The resulting hydrogels can thus deform in a novel 2D-to-4D mode under external stimuli. During the deformation, they first transform into the temporary shapes induced by the local deformation rate difference, and then transform into the final shapes determined by the local deformation degree difference. Through controlling the ultraviolet irradiation direction and time to precisely program the local gradients of self-shaping hydrogels, they can be designed to produce various unprecedented yet controllable 2D-to-4D shape evolutions on demand, such as transformable origami, sequential gesture actions in finger-guessing games, mobile octopuses, time switch, etc.

Oxygen Reduction Activity of B←N-Containing Organic Molecule Affected by Asymmetric Regulation.

Organic molecular catalysts have received great attention as they have the merits of well-controlled molecular structures for the development of catalytic chemistry. Herein, the electronic distribution of active sites is regulated by asymmetrically introducing S-heterocycle on one side of the molecular core. As a result, the asymmetric as-PYT and as-BNT show higher oxygen reduction performance than their symmetric counterparts without (s-PY, s-PY2T) or with two S-heterocycle units (s-BN, s-BN2T). Density functional theory calculations reveal that the carbon atoms (site-12) at symmetric s-BN and s-BN2T are the catalytic active sites, while for asymmetric as-BNT, it has changed to amino-N atom (site-14). Due to the non-uniform charge distribution and increased dipole moment of as-BNT caused by asymmetric molecular configuration, the kinetics of catalytic reaction has changed significantly. The catalytically active sites of specific N atoms are further verified experimentally and theoretically by using sterically hindered phenyl groups. This work provides a simple but efficient method to design metal-free oxygen reduction electrocatalysts.

Organometallic Magnesium Complex with Aggregation Induced Emission Properties: Synthesis, Characterization, and Fluorescent Fibers Applications.

In this work, a novel organomagnesium complex with outstanding aggregation induced emission (AIE) properties is synthesized using dibenzoylmethane (DBM) as the ligand. The structure of the complex is confirmed to be one magnesium ion coordinated to the dione groups of two DBM molecules, and the magnesium ion adopts a distorted octahedrally geometry. The obvious emission is found for Mg(DBM)2 powder and not in the solution, making this the first reported organomagnesium complex with AIE property. The properties of the complex were investigated by using UV-vis absorption and fluorescence emission spectroscopy, cyclic voltammetry, and density functional theory calculations. Moreover, the Mg(DBM)2 solution dispersed in filter paper was is colorless, which may be made into a convenient anti-counterfeiting and encryption tool. Mg(DBM)2 /alginate fibers were prepared by wet-spinning process and further processed into paper, which can be used in the fields of sensors, anti-counterfeiting, and encryption. Sweat contains a wealth of chemical information that could potentially indicate the body's deeper biomolecular state. The prepared fluorescent fibers were used to detect sweat due to its non-toxic, low-cost efficient and fast response to analytes.

Strong and tough self-wrinkling polyelectrolyte hydrogels constructed via a diffusion-complexation strategy.

Self-wrinkling hydrogels enable various engineering and biomedical applications. The major challenge is to couple the self-wrinkling technologies and enhancement strategies, so as to get rid of the poor mechanical properties of existing self-wrinkling gels. Herein we present a facile diffusion-complexation strategy for constructing strong and ultratough self-wrinkling polyelectrolyte hydrogels with programmable wrinkled structures and customizable 3D configurations. Driven by the diffusion of low-molecular-weight chitosan polycations into the polyanion hydrogels, the high-modulus polyelectrolyte complexation shells can form directly on the hydrogel surface. Meanwhile, the polyanion hydrogels deswell/shrink due to the low osmotic pressure, which applies an isotropous surface compressive stress for inducing the formation of polygonal wrinkled structures. When the diffusion-complexation reaction occurs on a pre-stretched hydrogel sheet, the long-range ordered wrinkled structures can form during the springback/recovery of the hydrogel matrix. Moreover, through controlling the regions of diffusion-complexation reaction on the pre-stretched hydrogels, they can be spontaneously transformed into various 3D configurations with ordered wrinkled structures. Notably, because of the introduction of plenty of electrostatic binding (i.e., sacrificial bonds), the as-prepared self-wrinkling gels possess outstanding mechanical properties, far superior to the reported ones. This diffusion-complexation strategy paves the way for the on-demand design of high-performance self-wrinkling hydrogels.

Controlled Asymmetric Charge Distribution of Active Centers in Conjugated Polymers for Oxygen Reduction.

Active center reconstruction is essential for high performance oxygen reduction reaction (ORR) electrocatalysts. Usually, the ORR activity stems from the electronic environment of active sites by charge redistribution. We introduce an asymmetry strategy to adjust the charge distribution of active centers by designing conjugated polymer (CP) catalysts with different degrees of asymmetry. We synthesized asymmetric backbone CP (asy-PB) by modifying B←N coordination bonds and asymmetric sidechain CP (asy-PB-A) with different alkyl chain lengths. Both CPs with backbone and sidechain asymmetry exhibit superior ORR performance to their symmetric counterparts (sy-P and sy-PB). The asy-PB with greater asymmetry shows higher catalytic activity than asy-PB-A with relatively smaller asymmetry. DFT calculations reveal that the increased dipole moment and non-uniform charge distribution caused by asymmetric structure endows the center carbon atom of bipyridine with efficient catalytic activity.

Anti-Swelling Gradient Polyelectrolyte Hydrogel Membranes as High-Performance Osmotic Energy Generators.

Emerging asymmetric ionic membranes consisting of two different porous membranes show great superiority in harvesting clean and renewable osmotic energy. The main barriers constraining their applications are incompatible interfaces and a low interfacial ionic transport efficiency, which are detrimental to the long-term stability and improvement of the power density. Here, continuous-gradient all-polysaccharide polyelectrolyte hydrogel membranes prepared by ultrafast reaction/diffusion have been demonstrated to enable high-performance osmotic energy conversion. Besides an inherent high ion conductivity and excellent ion selectivity, the anti-swelling polyelectrolyte gradient membranes preserve the ionic diode effect of the asymmetric membranes to facilitate one-way ion diffusion but circumvent adverse interfacial effects. In consequence, they can present ultrahigh power densities of 7.87 W m-2 by mixing seawater and river water, far superior to state-of-the-art membranes.

Preparation of Ion-Exchanged TEMPO-Oxidized Celluloses as Flame Retardant Products.

Cellulose, as one of the most abundant natural biopolymers, has been widely used in textile industry. However, owing to its drawbacks of flammability and ignitability, the large-scale commercial application of neat cellulose is limited. This study investigated some TEMPO-oxidized cellulose (TOC) which was prepared by selective TEMPO-mediated oxidation and ion exchange. The prepared TOC was characterized by Fourier transform infrared (FT-IR) spectroscopy and solid-state 13C-nuclear magnetic resonance (13C-NMR) spectroscopy. The thermal stability and combustion performance of TOC were investigated by thermogravimetry analysis (TG), microscale combustion calorimetry (MCC) and limiting oxygen index (LOI). The results demonstrated that the thermal stability of TOC was less than that of the pristine material cellulose, but the peak of heat release rate (pHHR) and the total heat release (THR) of all TOC were significantly reduced. Additionally, the LOI values of all TOC products were much higher 25%. In summary, the above results indicated that the modified cellulose with carboxyl groups and metal ions by selective oxidation and ion exchange endows efficient flame retardancy.

Heterocyclization Strategy for Construction of Linear Conjugated Polymers: Efficient Metal-Free Electrocatalysts for Oxygen Reduction.

Exploring cost-effective and efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR) is crucial for the development of energy conversion and storage technologies. Reported here is a novel heterocyclization strategy to construct efficient ORR catalysts based on linear conjugated polymers (LCPs), which are composed of N-, S-, or Se-heterocycles. Among these polymers, the covalently linked pyridine and thiophene molecule (P-T) with reduced graphene oxide (rGO) exhibits a remarkable half-wave potential of 0.79 V (vs. RHE) and excellent electrochemical stability, which are among the highest values for metal-free polymers as ORR catalysts. Density-functional theory (DFT) calculations reveal that the molecule with a phenyl unit (P-Ph) is catalytically inactive, and when a thiophene unit is introduced to replace the phenyl unit in the conjugated backbone it features highly efficient electrocatalytic active sites. More importantly, the well-defined molecular structures and controllable active sites in the pyrolysis and metal-free polymers highlight new opportunities for the catalytic metal-free ORR.

Scalable and Cost-Effective Synthesis of Highly Efficient Fe2N-Based Oxygen Reduction Catalyst Derived from Seaweed Biomass.

A simple and scalable synthesis of a 3D Fe2N-based nanoaerogel is reported with superior oxygen reduction reaction activity from waste seaweed biomass, addressed the growing energy scarcity. The merits are due to the synergistic effect of the 3D porous hybrid aerogel support with excellent electrical conductivity, convenient mass transport and O2 adsorption, and core/shell structured Fe2N/N-doped amorphous carbon nanoparticles.

Double-Helix Structure in Carrageenan-Metal Hydrogels: A General Approach to Porous Metal Sulfides/Carbon Aerogels with Excellent Sodium-Ion Storage.

The metal sulfide-carbon nanocomposite is a new class of anode material for sodium ion batteries, but its development is restricted by its relative poor rate ability and cyclic stability. Herein, we report the use of double-helix structure of carrageenan-metal hydrogels for the synthesis of 3D metal sulfide (Mx Sy ) nanostructure/carbon aerogels (CAs) for high-performance sodium-ion storage. The method is unique, and can be used to make multiple Mx Sy /CAs (such as FeS/CA, Co9 S8 /CA, Ni3 S4 /CA, CuS/CA, ZnS/CA, and CdS/CA) with ultra-small nanoparticles and hierarchical porous structure by pyrolyzing the carrageenan-metal hydrogels. The as-prepared FeS/CA exhibits a high reversible capacity and excellent cycling stability (280 mA h-1 at 0.5 A g-1 over 200 cycles) and rate performance (222 mA h-1 at 5 A g-1 ) when used as the anode material for sodium-ion batteries. The work shows the value of biomass-derived metal sulfide-carbon heterostuctures in sodium-ion storage.

Two-photon excited quantum dots with compact surface coatings of polymer ligands used as an upconversion luminescent probe for dopamine detection in biological fluids.

Water-soluble multidentate polymer coated CdTe quantum dots (QDs) were prepared via a stepwise addition of raw materials in a one-pot aqueous solution under ambient conditions. Just by adjusting the compositions of raw materials, different sized CdTe QDs were achieved within a short time. The as-prepared QDs showed compact surface coating (1.6-1.8 nm) of polymer ligands and photoluminescence (PL) emitted at 533-567 nm, as well as high colloidal/photo-stability and quantum yields (58-67%). Moreover, these QDs exhibited significant upconversion luminescence (UCL) upon excitation using an 800 nm femtosecond laser. Experimental results confirm that the UCL was ascribed to the two-photon assisted process via a virtual energy state. Then, the two-photon excited QDs were further developed as a novel UCL probe of dopamine (DA) due to self-assembled binding of DA molecules with QDs via non-covalent bonding. As a receptor, the DA attached onto the QD surface induced an electron transfer from QDs to DA, triggering UCL quenching of QDs. This UCL probe of DA presented a low limit of detection (ca. 5.4 nM), and high selectivity and sensitivity in the presence of potential interferences. In particular, it was favorably applied to the detection of DA in biological fluids, with quantitative recoveries (96.0-102.6%).

Biosorption Behavior of Ciprofloxacin onto Enteromorpha prolifera: Isotherm and Kinetic Studies.

The studies aimed at the feasibility of using Enteromorpha prolifera for the removal of ciprofloxacin from aqueous solutions. Batch experiments were carried out for the biosorption of ciprofloxacin onto Enteromorpha prolifera. The factors affecting the biosorption process such as the initial concentration, dosage, pH and the contact time were studied. Enteromorpha prolifera exhibited a maximum biosorption capacity of 21.7 mg/g. The pseudo-second-order kinetic model described the ciprofloxacin biosorption process with a good fitting. The optimum pH of ciprofloxacin adsorbed by Enteromorpha prolifera was 10. Biosorption equilibrium studies demonstrated that the biosorption followed Freundlich isotherm model, which implied a heterogeneous biosorption phenomenon.

Lightweight, flame retardant Janus carboxymethyl cellulose aerogel with fire-warning properties for smart sensor.

Lightweight, flame retardant biomass aerogels combining with multi-functionalities are promising for thermal insulation, noise absorption and smart sensors. However, high flammability hinders the application of these aerogels in extreme condition. Herein, lightweight, flame retardant aerogel with fire-warning properties fabricated from resource-abundant graphite and green carboxymethyl cellulose (CMC) is reported. During sonicating expandable graphite (EG) in CMC solution, CMC not only fabricates the downsizing process via hydrogen bonding effect but also forms stable dispersions. Then biomass aerogel is fabricated by freeze-drying strategy and enhanced by metal ionic cross-linking method. This aerogel demonstrates Janus properties for electrical conductivity and thermal conductivity. Due to the synergistic flame retardant effect of graphite nanocomposite and metal ions with a barrier effect and catalytic carbonization capacity, the flame retardancy of these aerogels are enhanced with fire-warning properties. Furthermore, these aerogels are used for monitoring physical deformations as smart sensors, which provides inspiration and a sustainable solution for developing low-cost biomass aerogel with multifunction.

Effect of the pre-crosslinking of Ba2+ ions on wet spinning of agar fibers.

Decreased coagulation bath concentration and difficult recovery are classical issues observed during the wet spinning of fibers. In this paper, a novel method was presented for preparing environment-friendly agar fibers using deionized water as the coagulation and stretch baths. The addition of Ba2+ into the spinning solution increased the crosslinking time and improved the performance of spinning solution. The results showed that the introduction of Ba2+ in the spinning solution increased the viscosity of the spinning solution. Particularly, when the concentration of BaCl2 in the spinning solution was 7 wt%, the viscosity increased to 39.29 Pa·s, which made the molecular chain arrangement of agar more compact and ordered and promoted the gelation transformation of the spinning solution, resulting in an increase in the gel temperature from 0.2 °C (Ba-0/agar) to 5.4 °C (Ba-7/agar). The spinning solution was more conducive to the formation of fibers in deionized water. In addition, the physical and chemical properties of agar fibers were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, tensile testing, and scanning electron microscopy. The results showed that the use of deionized water as the coagulation bath can improve the color of fiber and solve the problem of fiber adhesion, whereas the mechanical strength of agar fibers with pre-cross-linking metal ions was also improved. For example, the breaking strength of Ba-7/agar/DIW was 0.73 cN/dtex while the breaking strength of Ba-0/agar/DIW was only 0.62 cN/dtex.

Preparation of high-strength photochromic alginate fibers based on the study of flame-retardant properties.

Color-changing fibers have attracted much attention for their wide applications in camouflage, security warnings, and anti-counterfeiting. The inorganic color-changing material tungsten trioxide (WO3) has been widely investigated for its good stability, controllability, and ease of synthesis. In this study, photochromic alginate fibers (WO3@Ca-Alg) were prepared by incorporating UV-responsive hybrid tungsten trioxide nanoparticles in the fiber production process. The prepared photochromic alginate fibers changed from white to dark blue after 30 min of UV irradiation and returned to their original color after 64 h. It can be seen that WO3@Ca-Alg has the advantage of long color duration. The strength of this fiber reached 2.61 cN/dtex and the limiting oxygen index (LOI) was 40.9 %, which indicates that the fiber exhibited mechanical resistance and flame-retardant properties. After the cross-linking of WO3@Ca-Alg by sodium tetraborate, a new core-shell structure was generated, which was able to encapsulate tungsten trioxide in it, thus reducing the amount of tungsten trioxide loss, and its salt and washing resistance was greatly improved. This photochromic alginate fiber can be mass produced and spun into yarn.

Core-shell heterostructured Ni(OH)2@activation Zn-Co-Ni layered double hydroxides electrode for flexible all-solid-state coaxial fiber-shaped asymmetric supercapacitors.

The increasing requirements for wearable and portable electronics are driving the interests of high performance fiber supercapacitor. Layered double hydroxide (LDH) is broadly used in electrode materials, owing to the adjustability of components and the unique lamellar structure. However, limited active sites and poor electrical conductivity hinder its applications. Herein, the core-shell heterostructured Ni(OH)2@activation Zn-Co-Ni layered double hydroxides (Ni(OH)2@A-ZnCoNi-LDH) electrode was fabricated by loading pseudocapacitance material on the A-ZnCoNi-LDH to improve the electrochemical performance. Significantly, benefits from the synergistic effect of the multi-metal ions and the core-shell heterostructure, the electrodes demonstrated a capacitance of 2405 mF·cm-2 at 1 mA·cm-2. Furthermore, Ni(OH)2@A-ZnCoNi-LDH was used as the core electrode and carbon nanotube (CNT) film coated with Fe2O3@reduced graphene oxide (rGO) was wrapped around the core electrode to assemble coaxial fiber asymmetric supercapacitor, which illustrated an ultrahigh energy density of 177.7 µWh·cm-2 at 0.75 mW·cm-2. In particular, after consecutive charging and discharging 7000 cycles, the capacitance retention of the device was 95 %, indicating the excellent cycling stability. Furthermore, the device with high flexibility can be woven into textiles in different shapes. The fabricated device has an excellent development prospect as an energy source in wearable electronic devices.

Insurance Reimbursement for Special Foods and Phenylalanine Levels in Patients With PKU in China.

Importance: Recent changes in China's social medical insurance reimbursement policy have impacted the financial burden of patients with phenylketonuria (PKU) for special foods. However, whether this policy change is associated with their blood phenylalanine (PHE) concentration is unclear. Objective: To investigate the association between the reimbursement policy and blood PHE concentration in patients with PKU. Design, Setting, and Participants: This cohort study measured the blood PHE concentrations of 167 patients with PKU across 4 newborn screening centers in China from January 2018 to December 2021. The reimbursement policy for special foods for patients with PKU at 2 centers was canceled in 2019 and restored from 2020 onwards. In contrast, the other 2 centers consistently implemented the policy. Data were analyzed from September 10 to December 6, 2023. Exposures: The implementation and cancelation of the reimbursement policy for special foods of patients with PKU. Main Outcomes and Measures: The blood PHE concentration was regularly measured from 2018 to 2021. A 1-sided Z test was used to compare the mean of the blood PHE concentration between different years. Results: Among 167 patients with PKU (mean [SD] age, 84.4 [48.3] months; 87 males [52.1%]), a total of 4285 measurements of their blood PHE concentration were collected from 2018 to 2021. For patients at the center that canceled the reimbursement policy in 2019, the mean (SD) of the blood PHE concentrations in 2019 was 5.95 (5.73) mg/dL, significantly higher than 4.84 (4.11) mg/dL in 2018 (P < .001), 5.06 (5.21) mg/dL in 2020 (P = .006), and 4.77 (4.04) mg/dL in 2021 (P < .001). Similarly, for patients at the other center that canceled the policy in 2019, the mean (SD) of the blood PHE concentrations in 2019 was 5.95 (3.43) mg/dL, significantly higher than 5.34 (3.45) mg/dL in 2018 (P = .03), 5.13 (3.15) mg/dL in 2020 (P = .003), and 5.39 (3.46) mg/dL in 2021 (P = .03). On the contrary, no significant difference was observed between any of the years for patients at the 2 centers that consistently implemented the policy. Conclusions and Relevance: In this cohort study of patients with PKU from multiple centers, the implementation of the reimbursement policy for special foods was associated with controlling the blood PHE concentration. Special foods expenditure for patients with PKU should be included in the scope of long-term social medical insurance reimbursement.