Zinc Research Articles

Contamination Assessment of Sediments and Bivalves in Estuaries of the Southern Iberian Peninsula

Human activities directly impact estuaries, where the biota is exposed to sediment contamination. A contamination assessment was carried out in several estuaries in the Southern Iberian Peninsula. Sediment samples were analyzed for the presence of metals/metalloids, and bioaccumulation tests were conducted with clams (Ruditapes philippinarum). Huelva Estuary had the highest contamination levels, while the inner bay of Cádiz and the outer stations of the estuaries from Guadiana, Guadalquivir, Palmones, and Guadarranque were the lesser contaminated. All sampling points (except Huelva) had low contamination levels of As and Cd, but they had high concentrations of Cu. The elements Pb, Cd, Zn, Cu, As, and Hg displayed correlations between the concentrations in sediments and the biota. High bioaccumulation of Zn, Cu, and As was observed in Huelva and Barbate. Important insights into the sediment contamination in Southern Iberian Peninsula estuaries suggest greater management and conservation efforts in these critical ecosystems.

High-entropy strategy to suppress volumetric strain and enhance diffusion rate of Na3V2(PO4)2F3 cathode for durable and high-areal-capacity zinc-ion battery pouch cells

Aqueous zinc-ion batteries are pivotal contributors to the global energy transformation. Cathode materials with NASICON-type structures are promising candidates for zinc-ion batteries but are hindered by their low electrical conductivity, sluggish ionic diffusion, and structural instability. This work introduces a high-entropy, carbon-coated NASICON-type Na3V2(PO4)2F3 (HE-NVPF@C) cathode by incorporating five metal elements (Al, Zn, Mn, Cr, and Nb) mainly into the V sites of the VO4F2 octahedral structure. Systematic experimental and simulation studies of the Zn2+ storage mechanism in high-entropy NASICON-type cathode are presented for the first time. The high-entropy doping strategy contributes to significantly enhanced cycling stability by suppressing Jahn-Teller distortion, reducing lattice change during Zn2+ extraction and insertion, and decreasing the Zn2+ migration energy barrier. As a result, the HE-NVPF@C cathode demonstrates exceptional cycling stability over 6000 cycles at 20 C with a capacity loss of a mere 0.0031 % per cycle and a high areal capacity retention of 2.17 mAh cm−2. In addition, the pouch cell provides a long cycling lifespan with 90.8 % capacity retention at 5 C after 200 cycles. This feasible high-entropy approach broadens the perspective for developing practical zinc-ion batteries with a long cycle lifespan and high areal capacity.

Eco-friendly multi-function electrolyte additive enabling dendrite-free Zn anodes for rechargeable aqueous zinc batteries

Aqueous zinc ion batteries (AZIBs) are increasingly developing on account of their safety, high energy density, affordability and scalability. Nevertheless, the zinc anode encounters notable obstacles, including disruptive side reactions, unregulated dendrite growth and persistent hydrogen evolution. These challenges present barriers to the widespread adoption of AZIBs technology in practical applications. This study incorporates aspartame (ASPT) into the aqueous electrolyte to establish a novel interface between the anode and electrolyte, improve steric effects, and adjust the solvation structure of Zn2+. Theoretical computations elucidate how the ASPT additive interacts with both the electrolyte and Zinc anode. Experimental findings additionally validate the significant role of ASPT in concurrently managing the chemistry between the electrolyte environment and Zinc interface. Accordingly, Zn//Zn symmetric cells exhibit an enduring operational lifespan exceeding 3600 hours under a current of 1 mA cm−2 and 1 mA cm−2. Moreover, Zn//Ti asymmetric cells demonstrate prolonged durability with highly efficient Zn deposition and dissolution processes sustained over more than 300 cycles. Finally, the Zn//MnO2 full cells, upon assembly, demonstrate consistent cycling stability and retain high capacity throughout their operational cycle.

Zincophilic Tellurium Interface Layer Enables Fast Kinetics for Ultralow Overpotential and Highly Reversible Zinc Anode

AbstractCorrosion, hydrogen evolution, and dendrite formation seriously affect the Zn anode, significantly limiting the practical application of aqueous zinc ion batteries. Herein, the Zn anode surface is innovatively reconstructed by decorating a zincophilic tellurium layer (Te@Zn) to enhance the Zn deposition kinetics. Theoretical calculations and experimental characterizations demonstrate that the zincophilic Te provides an abundance of anchoring sites for Zn nucleation and homogenizes the interface electric field to suppress dendrite growth. The Te@Zn anode exhibits an ultralow overpotential of 14.8 mV at 1.0 mA cm−2 and 1.0 mAh cm−2 with high Coulombic efficiency, and maintains ultra‐stable operation for over 3600 h at 0.2 mA cm−2 and 0.2 mAh cm−2. The Te@Zn||KVOH full cells and soft–pack batteries also deliver a brilliant rate capability and long cycling stability. The interfacial manipulation strategy using the Te layer on Zn anode surface paves the way for large‐scale energy storage applications.

Changes in reactive oxygen species and autofluorescence under hypoxia at the hippocampal CA3 area: Role of calcium and zinc influxes

Reactive oxygen species (ROS) have an important role in cellular biology, being involved, in a way that depends on their levels, in cell signaling processes or in oxidative stress, probably associated with neurodegenerative and other diseases. Most of the studies about ROS formation were performed in ischemic conditions, and thus, there is limited knowledge about ROS formation in less severe hypoxic conditions. This study investigates neuronal ROS generation and autofluorescence changes in hypoxic conditions, focusing on the involvement of calcium and zinc. Using hippocampal slices from Wistar rats, ROS production was monitored by the permeant fluorescent indicator H2DCFDA under different oxygenation levels. Moderate hypoxia (40% O2) led to a small ROS increase, while severe hypoxia (0% O2) showed a more pronounced rise. KCl-induced depolarization significantly enhanced ROS formation, particularly under severe hypoxia. Inhibition of NMDA receptors reduced ROS generation without affecting autofluorescence, while chelation of zinc ions decreased ROS production and increased flavin adenine dinucleotide (FAD) autofluorescence. These findings suggest that, in hypoxic conditions, ROS formation is mediated by calcium entry through NMDA receptors and also by zinc influxes. Thus, these ions play a crucial role in oxidative stress, which may be related with neurodegenerative diseases associated with ROS dysregulation.

Correction: Environmental Friendly Fabrication of Graphene Oxide Immobilized in Chitosan Coupled with Carboxymethyl Cellulose for Removal of Zinc(II) Ions and Oxytetracycline from Aqueous Solution

Correction: Environmental Friendly Fabrication of Graphene Oxide Immobilized in Chitosan Coupled with Carboxymethyl Cellulose for Removal of Zinc(II) Ions and Oxytetracycline from Aqueous Solution

Synthesis, thermal and spectroscopic analysis, antimicrobial activities and molecular modeling of zinc(II) metal complex of benzoyl glycine

To analyze ligand characteristics and use, a benzamide-derived ligand(benzoyl glycine) was synthesized and characterized before complexing it with zinc(II) ions. The ligand was formed from benzamide and glycine, obtained upon purification and precipitation. FTIR and 1H NMR were used to characterize the ligand. Furthermore, thermogravimetric analysis (TGA) was used to study the thermal behavior of the ligand and its Zn(II) complex, revealing important thermodynamic characteristics. The zinc complex was subjected to X-ray powder diffraction experiments, which yielded structural insights. Density Functional Theory (DFT) calculations were used in molecular modeling to clarify structure and characteristics of the molecules. Moreover, anti-microbial tests were used to assess biological activity against E. Coli and A. Niger. This thorough investigation lays the foundation for future research in this area by offering insightful information about the synthesis, characterization, and possible uses of the ligand and its Zn(II) metal complexes.

Heavy Metal Analysis Using Inductively Couple Plasma – Optical Emission Spectrometry (ICP-OES) on Hair of Breast Cancer Patients

Heavy metals can be found in everyday environments and can enter the human body through food, water, and air. Heavy metals are categorized into three groups by the World Health Organization (WHO): essential elements such as Copper (Cu), Chromium (Cr), Cobalt (Co), Iron (Fe), and Zinc (Zn); potentially essential elements like Manganese (Mn) and Nickel (Ni); and potentially toxic elements such as Cadmium (Cd) and Lead. (Pb). The heavy metal is a systemic poison that causes organ dysfunction in humans. The aim of this research is to analyze the levels of heavy metal elements Copper (Cu), Iron (Fe), and Zinc (Zn) in the hair of breast cancer patients. The method used to measure heavy metal content is Inductively Coupled Plasma – Optical Emission Spectrometry. (ICP-OES). The levels of heavy metal elements Cu, Fe, and Zn in five hair samples from breast cancer patients differ from the standards GBW07601 and IAEA-086. The levels of Cu and Fe in breast cancer patients are lower than the standard, while the level of Zn is higher than the standard.

A Low-cost and Green Zinc-Iron Battery Achieved by Ethaline Deep Eutectic Solvent.

Deep eutectic solvents (DESs) were considered as a potential electrolyte because of their low price, harmless to environment and wider electrochemical window potential compared to water. In this work, Fe(Ⅲ)/Fe(Ⅱ) and Zn(Ⅱ)/Zn redox couples were used as the positive and negative active materials, respectively, in a DES system using choline chloride and ethylene glycol in a molar ratio of 1:2 (ethaline). The possible working mechanism of the battery was studied by cyclic voltammetry, spectroscopic and simulation methods. The effects of different temperatures, concentrations of zinc ions in the anolyte and current densities on battery performance were evaluated. The results showed that the designed zinc-iron battery should preferably be operated at a current density of 0.5 mA cm-2 and the temperature of 313~323 K, which will improve the energy efficiency and maintain a high coulombic efficiency. The variation of cycle performance test presents a different pattern from the usual batteries, which is due to the effect of RO- group. At 313 K and 0.5 mA cm-2, the coulombic efficiency increases from 14.1% to 100.2% after 46 cycles, and then remains at about 100% during the rest 54 cycles, which demonstrates a good cycle stability of DES-based zinc-iron battery.

Formulating Self-Repairing Solid Electrolyte Interface via Dynamic Electric Double Layer for Practical Zinc Ion Batteries.

Zinc ion batteries (ZIBs) encounter interface issues stemming from the water-rich electrical double layer (EDL) and unstable solid-electrolyte interphase (SEI). Herein, we propose the dynamic EDL and self-repairing hybrid SEI for practical ZIBs via incorporating the horizontally-oriented dual-site additive. The rearrangement of distribution and molecular configuration of additive constructs the robust dynamic EDL under different interface charges. And, a self-repairing organic-inorganic hybrid SEI is constructed via the electrochemical decomposition of additive. The dynamic EDL and self-repairing SEI accelerate interfacial kinetics, regulate deposition and suppress side reactions in the both stripping and plating during long-term cycles, which affords high reversibility for 500 h at 42.7 % depth of discharge or 50 mA ⋅ cm-1. Remarkably, Zn//NVO full cells deliver the impressive cycling stability for 10000 cycles with 100 % capacity retention at 3 A ⋅ g-1 and for over 3000 cycles even at lean electrolyte (7.5 μL ⋅ mAh-1) and high loading (15.26 mg ⋅ cm-2). Moreover, effectiveness of this strategy is further demonstrated in the low-temperature full cell (-30 °C).

Interlayer expanded magnesium vanadium bronze for high capacity stable aqueous zinc batteries and method for proton contribution calculation

Magnesium vanadium bronze, MgV6O16·6H2O, is demonstrated as a cathode material for aqueous zinc batteries. Its remarkable electrochemical performance is attributed to the hydrated magnesium pillar layer, which enhances zinc ion diffusion into the structure, yielding a high initial discharge capacity of 298 mAh g−1 and capacity retention above 97 % after 300 cycles. Zinc ions and protons are co-intercalated into the MgV6O16·6H2O structure, while zinc hydroxide sulfate forms on the surface during the discharge process. Ex-situ X-ray diffraction results and elemental analyses confirm the zinc and proton co-intercalation reaction within the MgV6O16·6H2O structure during cycling, providing detailed insights into the electrochemical mechanisms. These findings demonstrate the potential of MgV6O16·6H2O as a high-energy cathode material for aqueous zinc batteries and offer a comprehensive understanding of the zinc ion and proton co-intercalation mechanism in the MgV6O16·6H2O structure.

Light-Controlled Interconvertible Self-Assembly of Non-Photoresponsive Suprastructures

Achieving light-induced manipulation of controlled self-assembly in nanosized structures is essential for developing artificially dynamic smart materials. Herein, we demonstrate an approach using a non-photoresponsive hydrogen-bonded (H-bonded) macrocycle to control the self-assembly and disassembly of nanostructures in response to light. The present system comprises a photoacid (merocyanine, 1-MEH), a pseudorotaxane formed by two H-bonded macrocycles, dipyridinyl acetylene, and zinc ions. The operation of such a system is examined according to the alternation of self-assembly through proton transfer, which is mediated by the photoacid upon exposure to visible light. The host–guest complexation between the macrocycle and bipyridium guests was investigated by NMR spectroscopy, and one of the guests with the highest affinity for the ring was selected for use as one of the components of the system, which forms the host–guest complex with the ring in a 2:1 stoichiometry. In solution, a dipyridine and the ring, having no interaction with each other, rapidly form a complex in the presence of 1-MEH when exposed to light and thermally relax back to the free ring without entrapped guests after 4 h. Furthermore, the addition of zinc ions to the solution above leads to the formation of a polypseudorotaxane with its morphology responsive to photoirradiation. This work exemplifies the light-controlled alteration of self-assembly in non-photoresponsive systems based on interactions between the guest and the H-bonded macrocycle in the presence of a photoacid.

Exploring the interplay between zinc‐induced protein dyshomeostasis and mitochondrial dysfunction using viscosity‐sensitive sensor

AbstractMitochondria are crucial sites for protein quality control within cells. When mitochondrial stress is triggered by protein misfolding, it can accelerate abnormal protein aggregation, potentially inducing various diseases. This study developed a cascade‐responsive sensor, named AggHX, to monitor the microenvironment of protein aggregation induced by zinc (II) ions and the accompanying mitochondrial dysfunction. The AggHX consists of two key components: (1) A Zn2+ recognition group for triggering a fluorescent enhance response, and (2) a near‐infrared BODIPY scaffold that detects viscosity changes in cell aggregation via HaloTag. This sensor's mechanism of action is elucidated through photochemical and biochemical characterizations. To further investigate the relationship between protein aggregation and mitochondrial homeostasis, we employ fluorescence lifetime imaging microscopy to assess viscosity changes in protein aggregates under intracellular Zn2+ stress. This research provides insights into the dynamic behavior and spatial distribution of protein aggregates and mitochondria, contributing to a deeper understanding of their physiological roles in cellular processes and potential implications in disease pathology.

Nitrogen Doping Engineering of V2CTx based Zinc Ion Hybrid Microcapacitors with Quadruple High Energy Density

To accommodate the long-term and stable energy supply requirements for wearable electronics, the reported flexible zinc ion hybrid microcapacitor (ZIHMC) needs to further increase the energy density. So, a nitrogen doped V2CTx (N-V2CTx) based ZIHMC was proposed to achieve high electrochemical performance. The introduction of N heteroatoms by NH3 annealing can dramatically increase the electrical conductivity of V2CTx and simultaneously widen the voltage window to 1.9 V. In detail, the doped nitrogen atoms in V2CTx based device has a maximum capacity of 293.0 mF cm–2, four times higher than that of pure V2CTx based ZIHMC. The mechanism of the enhanced electrochemical performance by nitrogen doped V2CTx was revealed by the experimental analysis and theoretical simulation. And the N-V2CTx based ZIHMC demonstrated high energy density with 150.0 μWh cm–2 at a power density of 380.0 μW cm–2 and excellent stability with 94.80% capacitance retention after 3000 charge-discharge cycles. The N-V2CTx based ZIHMC also presents excellent flexibility without virtually capacity loss after 3000 bending cycles. The good electrochemical performance and flexibility of N-V2CTx ZIHMC make it has potential applications in flexible wearable electronics.

A Trianalyte µPAD for Simultaneous Determination of Iron, Zinc, and Manganese Ions.

In this work, a microfluidic paper-based analytical device (µPAD) for simultaneous detection of Fe, Zn, and Mn ions using immobilized chromogenic reagents Ferene S, xylenol orange, and 1-(2-pyridylazo)-2-naphthol, respectively, is presented. As the effective recognition of analytes via respective chromogens takes place under extremely different pH conditions, experiments reported in this publication are focused on optimization of the µPAD architecture allowing for the elimination of potential cross effects. The paper-based microfluidic device was fabricated using low-cost and well-reproducible wax-printing technology. For optical detection of color changes, an ordinary office scanner and self-made RGB-data processing program were applied. Optimized and stable over time, µPADs allow fast, selective, and reproducible multianalyte determinations at submillimolar levels of respective heavy metal ions, which was confirmed by results of the analysis of solutions mimicking real samples of wastewater. The presented concept of simultaneous determination of different analytes that required extremely different conditions for detection can be useful for the development of other multianalyte microfluidic paper-based devices in the µPAD format.

Primitive asteroids as a major source of terrestrial volatiles.

The origins of Earth's volatiles are debated. Recent studies showed that meteorites display unique mass-independent isotopic signatures of the volatile element Zn, suggesting that Earth's Zn originated from materials derived from different regions of the Solar System. However, these studies largely omitted meteorites from the differentiated planetesimals thought to represent the Earth's building blocks, which underwent melting and substantial volatile loss. Here, we characterize the mass-independent Zn isotope compositions of meteorites from such planetesimals. We incorporate these results in mixing models that aim to reproduce Earth's abundance and isotope compositions of Zn and other elements. Our results suggest that, while differentiated planetesimals supplied ~70% of Earth's mass, they provided only ~10% of its Zn. The remaining Zn was supplied by primitive materials that did not experience melting and associated volatile loss. Combined with other findings, our results imply that an unmelted primitive material is likely required to establish the volatile budgets of the terrestrial planets.

Synthesis of {AlMo14O44}-Based Supramolecular Structures with High Proton Conductivity.

Polyoxometalates (POMs) are esteemed for their remarkable stability and exceptionally high proton conductivity, rendering them ripe for extensive exploration owing to their research significance. Herein, we synthesized two bimolybdenum-capped {AlMoVI8MoV6O44} cluster-based coordination polymers through a solvothermal method. Single-crystal X-ray diffraction analysis elucidates that H[(H2bimb)3(AlMoVI8MoV6O44)] [bimb = 1,4-bis(imidazole-1-ylmethyl)benzene, compound 1] is the POMs-organic supramolecular structure. The introduction of zinc ions into the reaction environment facilitated the connection of initially dispersed ligands, which yielded the well-ordered structure H3[Zn2(bimb)4(AlMoVI8MoV6O44)]·4H2O (compound 2) with a layer distance of 11.8 Å. The proton conductivities (σ) of two compounds were measured under conditions of 85 °C and 98% relative humidity (RH), resulting in values of 3.89 × 10-2 and 4.76 × 10-2 S·cm-1, respectively. This study presents a novel approach to fabricating POMs as proton conductors through structural design and manufacturing adjustments.

A Metal Chelation Therapy to Effectively Eliminate Breast Cancer and Intratumor Bacteria While Suppressing Tumor Metastasis by Copper Depletion and Zinc Ions Surge.

The intratumor microbiota results in the immunosuppressive microenvironment and facilitates tumor growth and metastasis. However, developing a synergistic therapy with antitumor, antibacterial, and antimetastatic effects faces enormous challenges. Here, we propose anmetal chelation therapy to effectively eliminate tumor and intratumor bacteria and suppress tumor metastasis. Different from traditional chelation therapy that only consumes metal elements, this therapy not only eliminates the crucial metal elements for tumor metabolism but also releases new metal ions with antitumor and antibacterial properties. Based on the high demand for copper in breast cancer, we prepare a fibrous therapeutic nanoagent (Zn-PEN) by chelatingD-Penicillamine (D-PEN) with Zn2+. Firstly, Zn-PEN achieves dual inhibition of oxidative phosphorylationand glycolysis metabolism through copper depletion and Zn2+ activated cGAS-STING pathway, thus inducing tumor cell death. Secondly, Zn-PEN has the capability to eradicate Fusobacterium nucleatumin breast cancer, thereby mitigating its immunosuppressive impact on the tumor microenvironment. Finally, Zn-PEN effectively inhibits tumor metastasis through multiple routes, including the inhibition of epithelial-mesenchymal transition process, activation of cGAS-STING pathway, and elimination with F. nucleatum. Therefore, we verify the feasibility of Zn-PEN mediated metal chelation therapy in a 4T1 model infected with F. nucleatum, providing a new therapeutic strategy for inhibiting tumor metastasis.

A Metal Chelation Therapy to Effectively Eliminate Breast Cancer and Intratumor Bacteria While Suppressing Tumor Metastasis by Copper Depletion and Zinc Ions Surge

The intratumor microbiota results in the immunosuppressive microenvironment and facilitates tumor growth and metastasis. However, developing a synergistic therapy with antitumor, antibacterial, and antimetastatic effects faces enormous challenges. Here, we propose an metal chelation therapy to effectively eliminate tumor and intratumor bacteria and suppress tumor metastasis. Different from traditional chelation therapy that only consumes metal elements, this therapy not only eliminates the crucial metal elements for tumor metabolism but also releases new metal ions with antitumor and antibacterial properties. Based on the high demand for copper in breast cancer, we prepare a fibrous therapeutic nanoagent (Zn‐PEN) by chelating D‐Penicillamine (D‐PEN) with Zn2+. Firstly, Zn‐PEN achieves dual inhibition of oxidative phosphorylation and glycolysis metabolism through copper depletion and Zn2+ activated cGAS‐STING pathway, thus inducing tumor cell death. Secondly, Zn‐PEN has the capability to eradicate Fusobacterium nucleatum in breast cancer, thereby mitigating its immunosuppressive impact on the tumor microenvironment. Finally, Zn‐PEN effectively inhibits tumor metastasis through multiple routes, including the inhibition of epithelial‐mesenchymal transition process, activation of cGAS‐STING pathway, and elimination with F. nucleatum. Therefore, we verify the feasibility of Zn‐PEN mediated metal chelation therapy in a 4T1 model infected with F. nucleatum, providing a new therapeutic strategy for inhibiting tumor metastasis.

High-yield rice with rich nutrition and low toxicity can be obtained under potato-rice cropping system.

Rice is often rotated with dryland crops to produce sufficient foodstuff, as rice is the main food crop of humans. In order to verify whether under the intensive rice-based cropping system, high yield and good quality of rice can be achieved simultaneously to ensure food security. Five long-term paddy-upland rotations - wheat-rice (WR), rapeseed-rice (RR), garlic-rice (GR), broad beans-rice (BR) and potato-rice (PR) - were conducted from 2014 to investigate rice yield, along with the profiling of 24 elements in rice grain. Mg, Zn, Cu, As, Mo and Sb concentrations were highest in the aleurone layer, and Ag and Cd concentrations showed little variation among different parts of the rice grain. Al, Ti, V, Si, Fe and Tl concentrations in the endosperm under GR were higher, while the Se concentration under PR was the highest. Furthermore, the yield of GR and PR were higher than the other three rotations with N supplementation, and the sustainable yield index of PR and WR were larger than 0.8. When we consider the concentration of toxic (As, Cd and Pb) and nutrient elements (Ca, Fe, Zn, Se, Cu and Mg) in the endosperm and grain yields, PR can simultaneously achieve high yield, high nutrition and low toxicity with different nitrogen treatments. Here we provide novel insights regarding the selection of rice-based cropping systems, focused on producing nutritious and safe rice with high grain yield. © 2024 Society of Chemical Industry.