Seaweeds as a major source of dietary microplastics exposure in East Asia.

Microplastics (MPs) occurrence in marine ecosystems is well known, but their accumulation in seaweeds and subsequent human exposure remain understudied. This research quantifies MPs presence in two commonly consumed seaweeds, kelp (Saccharina japonica) and nori (Pyropia yezoensis), in East Asia, revealing widespread contamination dominated by microfibers (<500 µm). Based on dietary patterns, human uptake through seaweed consumption was estimated and quantified. Notably, Chinese people consume an estimated 17,034 MPs/person/year through seaweed consumption, representing 13.1% of their total annual MPs intake. This seaweeds-derived exposure surpasses all other dietary sources, contributing up to 45.5% of overall MPs intake. The highest intake was in South Korea, followed by North Korea, China, and Japan. This research identifies seaweeds as a major, previously overlooked route of dietary MPs exposure. These findings are crucial for comprehensive risk assessments of seaweed consumption and the development of mitigation strategies, particularly for populations in East Asian countries.

Electronic Structure Regulated Nickel-Cobalt Bimetal Phosphide Nanoneedles for Efficient Overall Water Splitting.

Transition metal phosphides (TMPs) have been widely studied for water decomposition for their monocatalytic property for anodic or cathodic reactions. However, their bifunctional catalytic activity still remains a major challenge. Herein, hexagonal nickel-cobalt bimetallic phosphide nanoneedles with 1-3 µm length and 15-30 nm diameter supported on NF (NixCo2-xP NDs/NF) with adjusted electron structure have been successfully prepared. The overall alkaline water electrolyzer composed of the optimal anode (Ni0.67Co1.33P NDs/NF) and cathode (Ni1.01Co0.99P NDs/NF) provide 100 mA cm-2 at 1.62 V. Gibbs Free Energy for reaction paths proves that the active site in the hydrogen evolution reaction (HER) is Ni and the oxygen evolution reaction (OER) is Co in NixCo2-xP, respectively. In the HER process, Co-doping can result in an apparent accumulation of charge around Ni active sites in favor of promoting HER activity of Ni sites, and ΔGH* of 0.19 eV is achieved. In the OER process, the abundant electron transfer around Co-active sites results in the excellent ability to adsorb and desorb *O and *OOH intermediates and an effectively reduced ∆GRDS of 0.37 eV. This research explains the regulation of electronic structure change on the active sites of bimetallic materials and provides an effective way to design a stable and effective electrocatalytic decomposition of alkaline water.

Co-exposure of microplastics and polychlorinated biphenyls strongly influenced the cycling processes of typical biogenic elements in anoxic soil.

The co-exposure of microplastics (MPs) and polychlorinated biphenyls (PCBs) in soil is inevitable, but their combined effect on cycles of typical biogenic elements (e.g. C, N, Fe, S) is still unclear. And the co-exposure of MPs and PCBs caused more severe effects than single exposure to pollution. Therefore, in this study, a 255-day anaerobic incubation experiment was conducted by adding polyethylene microplastics (PE MPs, including 30 ± 10 µm and 500 µm) and PCB138. The presence of PE MPs inhibited the PCB138 degradation. Also, PE MPs addition (1%, w/w) enhanced the methanogenesis, Fe(Ⅲ) reduction, and sulfate reduction while inhibited nitrate reduction and the biodegradation of PCB138. And PCB138 addition (10 mg·kg-1) promoted the methanogenesis and Fe(Ⅲ) reduction, but inhibited sulfate reduction and nitrate reduction. Strikingly, the presence of PE MPs significantly reduced the impact of PCB138 on the soil redox processes. The abundance changes of special microbial communities, including Anaeromyxobate, Geobacter, Bacillus, Desulfitobacterium, Thermodesulfovibrio, Metanobacterium, etc., were consistent with the changes in soil redox processes, revealing that the effect of PE MPs and/or PCB138 on the cycle of typical biogenic elements was mainly achieved by altering the functional microorganisms. This study improves the knowledge of studies on the impact of MPs and combined organic pollutants to soil redox processes, which is greatly important to the stabilization and balance of biogeochemical cycling in ecology.

Electrostatic Interaction in Amino Protonated Chitosan-Metal Complex Anion Hydrogels: A Simple Approach to Porous Metal Carbides/N-Doped Carbon Aerogels for Energy Conversion.

In the face of the increasingly serious rapid depletion of fossil fuels, exploring alternative energy conversion technologies may be a promising choice to alleviate this crisis. Transition metal carbides (TMCs)/carbon composites are considered as prospective electrocatalysts due to their high catalytic activities and structural stability. In this work, we report the simple synthesis of TMCs/N-doping carbon aerogels (TMCs/NCAs, including Fe3C/NCA, Mo3C2/NCA, and Fe3C-Mo2C/NCA) for the oxygen reduction reaction (ORR) using protonated chitosan/metal complex anion-chelated aerogels. Among them, the Fe3C/NCA composite possesses efficient ORR activity (similar to Pt/C), and the Fe3C/NCA-assembled Zn-air battery exhibits high power densities of about 250 mW cm-2. The density functional theory calculation reveals that the presence of graphite-N, pyridine-N, and carbon defects in the carbon framework effectively reduces the free energy of ORR occurring in Fe3C. This work provides a simple and extensible strategy for the preparation of TMCs from chitosan, which is expected to be extended to other metal carbides.

Cu2Se nanowires shelled with NiFe layered double hydroxide nanosheets for overall water-splitting.

It is imperative but challenging to develop non-noble metal-based bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Our work reports a core-shell nanostructure that is constructed by the electrodeposition of ultrathin NiFe-LDH nanosheets (NiFe-LDHNS) on Cu2Se nanowires, which are obtained by selenizing Cu(OH)2 nanowires in situ grown on Cu foam. The obtained Cu2Se@NiFe-LDHNS electrocatalyst provides more exposed edges and catalytic active sites, thus exhibiting excellent OER and HER electrocatalytic performance in alkaline electrolytes. This catalyst needs only an overpotential of 197 mV for OER at 50 mA cm-2 and 195 mV for HER at 10 mA cm-2. Besides, when employed as a bifunctional catalyst for overall water-splitting, it requires a cell voltage of 1.67 V to reach 10 mA cm-2 in alkaline media. Furthermore, the corresponding water electrolyzer demonstrates robust durability for at least 40 h. The excellent performance of Cu2Se@NiFe-LDHNS might be ascribed to the synergistic effect from the ultrathin NiFe-LDHNS, the Cu2Se nanowires anchored on the Cu foam, and the formed core-shell nanostructure, which offers large surface area, ample active sites, and sufficient channels for gas and electrolyte diffusion. This work provides an efficient strategy for the fabrication of self-supported electrocatalysts for efficient overall water-splitting.

Electrochemical sensing for naphthol isomers based on the in situ growth of zeolitic imidazole framework-67 on ultrathin CoAl layered double hydroxide nanosheets by a reaction-diffusion technique.

It is established that ultrathin layered double hydroxide nanosheets (LDHNS) and zeolitic imidazole frameworks (ZIF) are desirable electrochemical sensing modifiers owing to their large surface area and abundant catalytic sites. Integration of them is thus an effective solution to maximize their electrocatalytic activity. Herein, a novel reaction-diffusion framework (RDF) technique is applied for the in situ growth of ZIF-67 on ultrathin CoAl-LDHNS (CoAl-LDHNS@ZIF-67). In a confined space of the agar gel matrix of RDF, the coordination reaction between organic ligands and CoAl-LDHNS without an additional Co2+ source achieves the controllable growth of ZIF-67 crystals through a long vertical diffusion. The prepared composite comprises both CoAl-LDHNS and ZIF-67 components with a certain ratio and provides a large surface area and amply catalytic sites, thus realizing a rapid transfer of electron and mass. The CoAl-LDHNS@ZIF-67 modified electrode is employed for the simultaneous detection of naphthol isomers by differential pulse voltammetry. Naphthol isomers display anodic reactions with a wide peak potential difference, allowing their simultaneous detection feasible. Voltammetric responses of α-naphthol and ß-naphthol follow good linearity against the concentration in a wide range from 0.3 to 150 µM with limits of detection of 54 and 82 nM, respectively. The proposed sensor also demonstrates excellent selectivity, stability, reproducibility, and practicability for the simultaneous detection of naphthol isomers.

Electrochemical sensing platform for naphthol isomers based on in situ growth of ZIF-8 on reduced graphene oxide by a reaction-diffusion technique.

Enhancing the dispersibility and conductivity is an effective solution to develop the application zeolitic imidazole frameworks (ZIF) in the electrochemical field. This work thus employs a novel reaction-diffusion framework (RDF) technique for the in situ growth of ZIF-8 crystals on graphene oxide (GO@ZIF-8) matrixes. In detail, the outer electrolyte of 2-methyl imidazole naturally diffuses into the inner agar gel matrix containing Zn2+ cations and GO nanosheets. The long reaction-diffusion makes the growth of ZIF-8 crystals controllable in a vertical gradient. After thermal treatment, the title product of ZIF-8 in situ grown on reduced graphene oxide (rGO@ZIF-8) is obtained and thus exhibits good dispersibility, high conductivity, large surface area, and more catalytic sites. The glassy carbon electrode (GCE) was modified by casting the rGO@ZIF-8 suspension. The obtained rGO@ZIF-8/GCE displays excellent catalytic activity toward naphthol (NAP) isomers. Under the optimal conditions, the amperometric currents of 1-NAP and 2-NAP demonstrate the good linear relationship in wide ranges of 0.05-12 µM and 0.02-15 µM, respectively. Their limits of detection are as low as 15 and 17 nM, respectively. The fabricated modified electrode exhibits excellent selectivity, stability, and reproducibility. The sensor is also utilized to detect NAP molecules in real water samples and indicates good accuracy and reliability.

Quantitative Structure-activity Relationships; Studying the Toxicity of Metal Nanoparticles.

BACKGROUND: Metal nanomaterials are widely used in various fields, including targeted therapy and diagnosis. They are extensively used in targeted drug delivery and local treatments. However, the toxicity associated with these materials could lead to severe adverse health effects. METHODS: In this study, we investigated the relationships between the toxicity and structures of metal nanoparticles by using theoretical calculations and quantitative structure-activity relationships. Twenty four physicochemical descriptors and toxicity data of 23 types of metal nanoparticles were selected as samples, and a multiple linear regression model was established to obtain a toxicity prediction equation with 5 descriptors with an R2 of 0.910. Structures of copper nanoparticles were designed based on the model, and the structure with low toxicity was searched. The multiple nonlinear regression model was used to further improve the prediction accuracy. RESULTS: The R2 values were 0.995 in the training set and 0.988 in the test set, which indicated that the prediction accuracy improved. Based on the result of multiple linear regression, we designed copper nanoparticles with low toxicity. CONCLUSION: The study confirmed that the quantitative structure-activity relationship was a reasonable method for predicting the toxicity and designing the structures with low toxicity of metal nanoparticles.

Multiple Vacancies on (111) Facets of Single-Crystal NiFe2 O4 Spinel Boost Electrocatalytic Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) as the rate-determining reaction of water splitting has been attracting enormous attention. At present, only some noble-metal oxide materials (IrO2 and RuO2 ) have been reported as efficient OER electrocatalysts for OER. However, the high cost and scarcity of these noble-metal oxide materials greatly hamper their large-scale practical application. Herein, we synthesize 100% (111) faceted NiFe2 O4 single crystals with multiple vacancies (cation vacancies and O vacancies). The (111) facets can supply enough platform to break chemical bonds and enhance electrocatalytic activity, due to its high density of atomic steps and kink atoms. Compared to NiFe2 O4 (without vacancies), the as-synthesized NiFe2 O4 -Ar (with vacancies) exhibits a dramatically improved OER activity. The NiFe2 O4 -Ar-30 shows the lowest onset potential (1.45 V vs RHE) and the best electrocatalytic OER activity with the lowest overpotential of 234 mV at 50 mA cm-2 . Furthermore, based on the theoretical calculations that the introduction of multiple vacancies can effectively modulate the electronic structure of active centers to accelerate charge transfer and reaction intermediates adsorption, which can reduce the reaction energy barrier and enhance the activity of electrochemical OER.

In situ growth of ZIF-67 on ultrathin CoAl layered double hydroxide nanosheets for electrochemical sensing toward naphthol isomers.

Zeolitic imidazole frameworks (ZIF) and ultrathin layered double hydroxide nanosheets (LDHNS) have drawn growing attention in the electrocatalysis field. Combining the merits and maximizing the electrocatalytic activity of each building block in the corresponding composite is imperative but challenging. This work thus proposes a simple strategy for the in situ growth of ZIF-67 on ultrathin CoAl-LDHNS (LDHNS@ZIF-67) without an additional Co2+ source. Thanks to the ultrathin nature, CoAl-LDHNS provide more Co reactive sites for the ordered growth of ZIF-67 nanocrystals on this 2D matrix via coordination interactions between Co2+ and 2-methylimidazole. The obtained LDHNS@ZIF-67 provides more convenient pathways to rapid electron transportation between the basal electrode and analytes. Hence, the modified electrode can be applied for the truly simultaneous detection of naphthol isomers by differential pulse voltammetry. α-naphthol and ß-naphthol exhibit irreversible oxidation peaks at 0.327 and 0.487 V vs. saturated calomel electrode, respectively, making their simultaneous detection feasible. The voltammetric responses of both isomers are linear in concentrations ranging from 0.3 to 150 µM with limits of detection of 62 and 94 nM, respectively. The sensor exhibits advantages including good reproducibility, stability, selectivity, and practicability for the simultaneous detection of naphthol isomers in real water samples.

Amperometric sensing of catechol by using a nanocomposite prepared from Ag/Ag2O nanoparticles and N,S-doped carbon quantum dots.

This work describes the synthesis of a nanocomposite consisting of Ag2O, silver nanoparticles and N,S-doped carbon quantum dots (Ag2O/Ag@NS-CQD). The NS-CQD were prepared by hydrothermal treatment of p-aminobenzenesulfonic acid. They act as both the reducing and stabilizing agent for synthesis of Ag2O/Ag@NS-CQD. The composite was characterized by UV-vis spectroscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The glassy carbon electrode (GCE) was modified by coating it with Ag2O/Ag@NS-CQD. It exhibits excellent amperometric response to catechol, typically at a low working potential of around 0.25 V. Under the best experimental conditions, the sensor has a wide linear response (0.2 to 180 µM) and a low detection limit (13 nM; at S/N = 3). The method was applied to analysis of spiked water samples and gave satisfactory results. Graphical abstract Schematic representation of the preparation of the Ag/Ag2O@N,S-doped carbon quantum dots composite using p-aminobenzenesulfonic acid and silver nitrate as the starting materials. The corresponding modified glassy carbon electrode exhibits the excellent amperometric sensing performance toward catechol at pH 7.0 with low detection limit and good selectivity.

Capture and separation of circulating tumor cells using functionalized magnetic nanocomposites with simultaneous in situ chemotherapy.

Circulating tumor cells (CTCs) are a type of rare cell that are firstly shed from solid tumors and then exist in the bloodstream. The effective capture and separation of CTCs has significant meaning in cancer diagnosis and prognosis. In this study, novel Fe3O4-FePt magnetic nanocomposites (Fe3O4-FePt MNCs) were constructed by integrating face centered cubic (fcc) FePt nanoparticles (NPs) onto the surface of the Fe3O4@SiO2 core. After further modification with NH2-PEG-COOH and the tumor-targeting molecule tLyP-1, the acquired Fe3O4-FePt MNCs possesses excellent biocompatibility and stability and could efficiently target and capture tLyP-1 receptor-positive CTCs. Based on the acidic microenvironment within cancer cells, the FePt layer could rapidly release active Fe2+ ions, which could catalyze H2O2 into reactive oxygen species (ROS) and further induce in situ apoptosis in cancer cells while having no distinct cytotoxicity to normal cells. Moreover, the Fe3O4@SiO2 core with its intrinsic magnetism has huge potential for the bioseparation of CTCs. The in vitro ROS fluorescence imaging experiments and cell capture and separation experiments indicated that the Fe3O4-FePt MNCs could specifically capture and separate cancer cells in the CTCs model and further induce in situ apoptosis. Therefore, the Fe3O4-FePt MNCs could serve as a promising multifunctional nanoseparator for efficiently capturing CTCs and simultaneously inducing in situ chemotherapy.

Sub-1.5 nm Ultrathin CoP Nanosheet Aerogel: Efficient Electrocatalyst for Hydrogen Evolution Reaction at All pH Values.

Transition metal phosphides (TMPs) are certified high performance electrocatalysts for the hydrogen evolution reaction (HER). The ultrathin 2D structure of TMPs can offer abundant adsorption sites to boost HER performance. Herein, an ice-templating strategy is developed to prepare CoP aerogels composed of 2D ultrathin CoP nanosheets (<1.5 nm) using sustainable alginate biomass (seaweed extract) as the precursor. The highly porous aerogel structure can not only deliver facile mass transfer, but also prevent aggregation of the nanosheets into layered structures. As expected, the obtained CoP nanosheet aerogels exhibit remarkable stability and excellent electrocatalytic HER performance at all pH values. For instance, the sample CoP-400 presents a low overpotential of 113, 154, and 161 mV versus RHE at a current density of 10 mA cm-2 in 0.5 m H2SO4, 1 m KOH, and 1 m phosphate buffer solution, respectively. In addition, CoP-400 displays low Tafel slopes at all pH values due to the interconnected highly porous structure of the aerogel, indicating that the sample can provide low-resistance channels for mass transport. Density functional theory calculations reveal that P-top and Co bridge on (011) facet of CoP are more favorable sites during the process of HER in acid and alkaline solutions, respectively.

Toward Aerogel Electrodes of Superior Rate Performance in Supercapacitors through Engineered Hollow Nanoparticles of NiCo2O4.

A biomass-templated pathway is developed for scalable synthesis of NiCo2O4@carbon aerogel electrodes for supercapacitors, where NiCo2O4 hollow nanoparticles with an average outer diameter of 30-40 nm are conjoined by graphitic carbon forming a 3D aerogel structure. This kind of NiCo2O4 aerogel structure shows large specific surface area (167.8 m2 g-1), high specific capacitance (903.2 F g-1 at a current density of 1 A g-1), outstanding rate performance (96.2% capacity retention from 1 to 10 A g-1), and excellent cycling stability (nearly without capacitance loss after 3000 cycles at 10 A g-1). The unique structure of the 3D hollow aerogel synergistically contributes to the high performance. For instance, the 3D interconnected porous structure of the aerogel is beneficial for electrolyte ion diffusion and for shortening the electron transport pathways, and thus can improve the rate performance. The conductive carbon joint greatly enhances the specific capacity, and the hollow structure prohibits the volume changes during the charge-discharge process to significantly improve the cycling stability. This work represents a giant step toward the preparation of high-performance commercial supercapacitors.

Creation of Ge-Nx-Cy Configures in Carbon Nanotubes: Origin of Enhanced Electrocatalytic Performance for Oxygen Reduction Reaction.

High-performance nitrogen and germanium codoped carbon nanotubes (N-Ge-CNTs) were synthesized as oxygen reduction reaction (ORR) catalysts by one-step sintering of carboxyethyl germanium sesquioxide and multiwalled CNTs in NH3 atmosphere. The ORR electrocatalytic activity evaluation was performed by using limited current density, selective reaction pathway, onset potential, H2O2 yields, and kinetic current density. In comparison with Ge or N solely doped CNTs, the codoped samples display more excellent ORR catalytic performance. It was observed that the codoped GeN3C, GeN4, and GeN4 + NC3 microstructures in N-Ge-CNTs are crucial to improving ORR catalytic performance, such as ideal 4 electron pathway (3.95) and positive onset potential (-0.08 V). The high ORR performance is attributed to the synergistic effect of N and Ge doping, which is capable of activating the π electrons of sp(2) hybridized orbital around carbon nantotubes. The ORR catalytic synergistic effect has also been verified by calculating the work function on the basis of density functional theory (DFT).

Egg-Box Structure in Cobalt Alginate: A New Approach to Multifunctional Hierarchical Mesoporous N-Doped Carbon Nanofibers for Efficient Catalysis and Energy Storage.

Carbon nanomaterials with both doped heteroatom and porous structure represent a new class of carbon nanostructures for boosting electrochemical application, particularly sustainable electrochemical energy conversion and storage applications. We herein demonstrate a unique large-scale sustainable biomass conversion strategy for the synthesis of earth-abundant multifunctional carbon nanomaterials with well-defined doped heteroatom level and multimodal pores through pyrolyzing electrospinning renewable natural alginate. The key part for our chemical synthesis is that we found that the egg-box structure in cobalt alginate nanofiber can offer new opportunity to create large mesopores (∼10-40 nm) on the surface of nitrogen-doped carbon nanofibers. The as-prepared hierarchical carbon nanofibers with three-dimensional pathway for electron and ion transport are conceptually new as high-performance multifunctional electrochemical materials for boosting the performance of oxygen reduction reaction (ORR), lithium ion batteries (LIBs), and supercapacitors (SCs). In particular, they show amazingly the same ORR activity as commercial Pt/C catalyst and much better long-term stability and methanol tolerance for ORR than Pt/C via a four-electron pathway in alkaline electrolyte. They also exhibit a large reversible capacity of 625 mAh g(-1) at 1 A g(-1), good rate capability, and excellent cycling performance for LIBs, making them among the best in all the reported carbon nanomaterials. They also represent highly efficient carbon nanomaterials for SCs with excellent capacitive behavior of 197 F g(-1) at 1 A g(-1) and superior stability. The present work highlights the importance of biomass-derived multifunctional mesoporous carbon nanomaterials in enhancing electrochemical catalysis and energy storage.

Nitrogen-doped one-dimensional (1D) macroporous carbonaceous nanotube arrays and their application in electrocatalytic oxygen reduction reactions.

A nitrogen(N)-doped one-dimensional (1D) macroporous carbonaceous nanotube array was fabricated by using an anodic alumina oxide (AAO) template. The large diameter of the nanotubes (∼200 nm) could overcome the sluggish mass transfer phenomena in the common micro/mesoporous carbon-based electrodes. Combining the activation of the π electrons of the sp(2) carbon array by N-doping, the novel 1D macroporous carbonaceous nanotube array exhibited high performance for the oxygen reduction reaction (ORR).

Thread-like supercapacitors based on one-step spun nanocomposite yarns.

Thread-like electronic devices have attracted great interest because of their potential applications in wearable electronics. To produce high-performance, thread-like supercapacitors, a mixture of stable dispersions of single-walled carbon nanotubes and conducting polyaniline nanowires are prepared. Then, the mixture is spun into flexible yarns with a polyvinyl alcohol outer sheath by a one-step spinning process. The composite yarns show excellent mechanical properties and high electrical conductivities after sufficient washing to remove surfactants. After applying a further coating layer of gel electrolyte, two flexible yarns are twisted together to form a thread-like supercapacitor. The supercapacitor based on these two yarns (SWCNTs and PAniNWs) possesses a much higher specific capacitance than that based only on pure SWCNTs yarns, making it an ideal energy-storage device for wearable electronics.

Fabrication and characterisation of α-chitin nanofibers and highly transparent chitin films by pulsed ultrasonication.

α-Chitin nanofibers were fabricated with dried shrimp shells via a simple high-intensity ultrasonic treatment under neutral conditions (60 KHz, 300 W, pH=7). The diameter of the obtained chitin nanofibers could be controlled within 20-200 nm by simply adjusting the ultrasonication time. The pulsed ultrasound disassembled natural chitin into high-aspect-ratio nanofibers with a uniform width (19.4 nm after 30 min sonication). The EDS, FTIR, and XRD characterisation results verified that α-chitin crystalline structure and molecular structure were maintained after the chemical purification and ultrasonic treatments. Interestingly, ultrasonication can slightly increase the degree of crystallinity of chitin (from 60.1 to 65.8). Furthermore, highly transparent chitin films (the transmittance was 90.2% at a 600 nm) and flexible ultralight chitin foams were prepared from chitin nanofiber hydrogels.