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Protein properties can be modified by thermal treatment at different pH values, resulting in the formation of protein aggregates with diverse morphologies and functionalities. This study investigated the morphology of aggregates of Antarctic krill protein (AKPS) formed by thermal treatment (90 °C, 15 min) at pH 2, 3, 4, and 6-12, characterized the different morphologies of AKPS, and determined the metal ion (Ca 2+ , Fe 2+ , and Zn 2+ )-binding capacities. Results showed that heat treatment with different pH values generated various AKPS with distinct morphology and metal ion-binding abilities. AKPS have formed fibrils at pH ≤ 3, particles at pH 4-7, and amorphous aggregates at pH ≥ 8. Fibrous AKPS (pH 2) exhibited a high solubility (80.36%) and strong reducing effect on iron. The binding capacities of Ca 2+ and Fe 2+ reached 36.08% and 66.75%. Particulate AKPS (pH 6 and 7) primarily only showed Zn 2+ -binding capacity similar to that of casein phosphopeptide (17.33%). Amorphous AKPS (pH 9-11) displayed the optimal capacity to bind Zn 2+ and Fe 2+ (26.90% and 74.94%). The alterations in morphology and functional characteristics of AKPS permit the design of various nanostructures for food-derived mineral supplements, thus developing their potential for application in functional foods.

The implantation of digestive tract stents at various lesion sites can effectively improve digestive tract patency, opening up an excellent treatment method for diseases that are currently incurable or resistant to conventional surgery. Digestive tract stents have been extensively studied and widely used worldwide due to their unique advantages of simple implantation, low trauma, satisfactory effect, and low complication rate. Among the various types of stents, metallic stents have been developed to improve surgical efficacy due to their excellent mechanical properties and are constantly being improved. This review provides an overview of the design and development of conventional nonbiodegradable metallic digestive tract stents such as nitinol (NiTi alloy), stainless steel, and cobalt-based alloy stents. Furthermore, biodegradable metallic stents for the digestive tract, such as magnesium-based, iron-based, and zinc-based stents, are described. This paper also evaluates the advantages and disadvantages of existing metallic digestive stents as well as future research directions and challenges in the development of metallic digestive tract stents.

Effective recovery of Li, Co, Ni and Mn from cathode materials of spent lithium-ion batteries (LIBs) has become a global concern. In this study, electrolysis of copper sulfate to produce sulfuric acid and electrons were utilized to recover Li, Co, Ni and Mn from spent LIBs. The obtained results showed that 93 % of Ni, 91 % of Co, 89 % of Mn and 94 % of Li were leached and 99 % of Cu was deposited during leaching process by adopting the 0.225 mol/L of copper sulfate with a solid/liquid ratio of 15 g/L at a current density of 50 mA/m 2 and 80 °C for 4.5 h. Then, a current efficiency of 72 % for the cathode and 30 % for the anode was achieved at a current density of 40 mA/m 2 , 70 °C and pH 2.5 during electrodeposition process. The Ni-Co deposition followed the principle of anomalous codeposition and the complete deposition time of Co, Ni and Mn were 3 h, 9 h and 10 h, respectively. Eventually, the Ni, Co, Mn, Li and Cu can be recovered as Ni-Co alloy, MnO 2 and Li 2 CO 3 and Cu metals with the corresponding recovery rates of 99.40 %, 91.00 %, 90.68 %, 85.59 % and 89.55 %, respectively. This study proposes a promising strategy for recycling cathode materials from spent LIBs without addition of chemical reductants and acids., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Sediment-derived dissolved organic matter (SDOM) is instrumental in the cycling of nutrients and heavy metals within lakes, influencing ecological balance and contaminant distribution. Given the influence of photodegradation on the alteration and breakdown of SDOM, further understanding of this process is essential. In this research, the properties of the SDOM photodegradation process and its metal-binding reactions in Nansi Lake were analyzed using the EEM-PARAFAC and 2D-SF/FTIR-COS techniques. Our study identified three sorts of humic-like components and one protein-like component in SDOM, with the humic-like material accounting for 71.3 ± 5.19% of the fluorescence intensity (F max ). Photodegradation altered the abundance and structure of SDOM, with a 41.6 ± 5.82% decrease in a 280 and a 29.1 ± 9.31% reduction in F max after 7 days, notably reducing the protein-like component C4 by 54.0 ± 5.17% and the humic-like component C2 by 48.5 ± 2.54%, which led to SDOM being formed with lower molecular weight and aromaticity. After photodegradation, the LogK Cu values for humic-like and protein-like substances decreased (humic-like C2: LogK Cu : 1.35 ± 0.10-1.11 ± 0.15, protein-like C4: 1.49 ± 0.14-1.29 ± 0.34), yet the preferential binding sequence of protein-like materials and specific functional groups with Cu 2+ such as aliphatic C-OH, amide (I) C=O and polysaccharide C-O groups remained unaltered. Our results enhance the knowledge of light-induced SDOM alterations and offer insights into SDOM-metal interactions in aquatic ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

During a radiotherapy (RT) course, geometrical variations of target volumes, organs at risk, weight changes (loss/gain), tumor regression and/or progression can significantly affect the treatment outcome. Adaptive RT has become the effective methods along with technical advancements in imaging modalities including cone-beam computed tomography (CBCT). Planning CT (pCT) can be modified via deformable image registration (DIR), which is applied to the pair of pCT and CBCT. However, the artifact existed in both pCT and CBCT is a vulnerable factor in DIR. The dose calculation on CBCT is also suggested. Missing information due to the artifacts hinders the accurate dose calculation on CBCT. In this study, we aim to develop a deep learning-based metal artifact reduction (MAR) model to reduce the metal artifacts in CBCT for head and neck cancer RT. To train the proposed MAR model, we synthesized the kV-CBCT images including metallic implants, with and without metal artifacts (simulated image data pairs) through sinogram image handling process. We propose the deep learning architecture which focuses on both artifact removal and reconstruction of anatomic structure using a dual-encoder architecture. We designed four single-encoder models and three dual-encoder models based on UNet (for an artifact removal) and FusionNet (for a tissue restoration). Each single-encoder model contains either UNet or FusionNet, while the dual-encoder models have both UNet and FusionNet architectures. In the dual-encoder models, we implemented different feature fusion methods, including simple addition, spatial attention, and spatial/channel wise attention. Among the models, a dual-encoder model with spatial/channel wise attention showed the highest scores in terms of peak signal-to-noise ratio, mean squared error, structural similarity index, and Pearson correlation coefficient. CBCT images from 34 head and neck cancer patients were used to test the developed models. The dual-encoder model with spatial/channel wise attention showed the best results in terms of artifact index. By using the proposed model to CBCT, one can achieve more accurate synthetic pCT for head and neck patients as well as better tissue recognition and structure delineation for CBCT image itself., Competing Interests: Declarations Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

The release of harmful compounds, particularly dangerous metal ions, into the environment has drawn deep concern from the scientific community. Therefore, it has become common in research to evaluate and quantify the harmful concentrations in the presence of these metal ions in several real samples (food, water, and biological samples). To increase sensitivity and lessen the impact of the matrix, sample pretreatment is a helpful strategy to implement before analysis. The limitations of conventional methods have been recently significantly reduced by developing new analytical approaches such as microextraction techniques. The miniaturization of conventional solid-phase extraction (SPE) led to solid-phase microextraction (SPME), drastically reducing both adsorbent use and extraction phase volume. SPME is defined in the present context as a modified extraction technique that employs a portable syringe system attached to micropipette tips. The SPME is considered one of the most appropriate sample preparation tools due to its compatibility with different detection techniques for different metal ions. The current review focuses on SPME based on a portable syringe (attaches to a micropipette tip) system because it has many advantages over conventional solid-phase extraction. It can be designed very simply in a syringe system, a very small quantity of the sorbent has to be kept in the tip, tube, or inside a syringe as a plug and combined with various analytical instruments. Many researchers have designed their own by using homemade tips packed with a sorbent to increase extraction capability and selectivity. According to the current review, there is a lot of potential for increasing the efficacy and efficiency of metal ion extraction from complicated matrices using portable syringe SPME. Studies have shown that when compared to conventional approaches, it performs better in terms of sensitivity, selectivity, and user-friendliness. Furthermore, its application to a wider range of sample types has been enhanced by the flexibility in constructing unique sorbent tips. Conclusively, the developments in portable syringe SPME have addressed several limitations of conventional techniques, positioning it as a robust and versatile tool for environmental monitoring and analysis of hazardous metal ions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This critical review comprehensively analyses nano-sized metal oxide fertilizers (NMOFs) and their transformative potential in sustainable agriculture. It examines the characteristics and benefits of different NMOFs, such as zinc, copper, iron, magnesium, manganese, nickel, calcium, titanium, cerium, and silicon oxide nanoparticles. NMOFs offer unique advantages such as increased reactivity, controlled-release mechanisms, and targeted nutrient delivery to address micronutrient deficiencies, enhance crop resilience, and improve nutrient efficiency. The review underscores the essential role of micronutrients in plant metabolism, crop growth, and ecosystem health, highlighting their importance alongside macronutrients. NMOFs present significant benefits over traditional fertilizers, including enhanced plant uptake, reduced nutrient losses, and decreased environmental impact. However, the review also critically examines potential risks associated with NMOFs, such as nanoparticle toxicity and environmental persistence. A comparative analysis of different metal types used in nanofertilizers is provided, detailing their primary advantages and potential drawbacks. The review emphasizes the need for cautious management of NMOFs to ensure their safe and effective use in agriculture. It calls for comprehensive research to understand the long-term effects of NMOFs on plant health, soil ecosystems, and human health. By integrating insights from material science, plant biology, and environmental science, this review offers a holistic perspective on the potential of NMOFs to address global food security challenges amid resource constraints and climate change. The study concludes by outlining future research directions and advocating for interdisciplinary collaboration to advance sustainable agricultural practices and optimize the benefits of NMOFs.

The burgeoning field of cancer theranostics has been significantly advanced by the development of Metal-Phenolic Networks (MPNs), a new class of supramolecular architectures that integrate the advantages of metals and polyphenols. This review focuses on MPNs and their promising applications in cancer theranostics. Through a systematic literature search spanning from 2010 to 2023 in databases including PubMed, Scopus, and Web of Science. The period of search was justified by the rapid evolution of nanomaterials in cancer therapy, with MPNs emerging as a significant player in biomedical applications within the specified timeframe. This review discusses the classification and structure of polyphenolic compounds, as well as their mechanisms of action in cancer treatment. The applications of MPNs in chemotherapy drug delivery, photothermal therapy, chemodynamic therapy, biomedical imaging, and synergistic therapy are especially detailed. The authors emphasize the significance of MPNs in cancer nanomedicine and look forward to their future development directions., Competing Interests: The authors report no conflicts of interest in this work., (© 2024 Li et al.)

Two-dimensional transition metal carbides and nitrides (MXenes) and MXene-based membranes hold promise for applications including water purification and seawater desalination; however, their environmental behavior and fate in these matrices remain unknown. In this study, we systematically assessed the reaction efficiencies of Ti 3 C 2 T x at varying important environmental conditions. Our experiments revealed that copper and iron ions accelerated the oxidation rate of Ti 3 C 2 T x 55.4 and 33.4 times, respectively. TiO 2 and amorphous carbon were identified as the primary solid products. Based on in situ water-phase atomic force microscopy, atomic high-angle annular dark-field scanning transmission electron microscopy, and theoretical results, we postulate that metal ions enhance Ti 3 C 2 T x oxidation by spontaneously migrating and anchoring at Ti vacancies, which then become active sites for this reaction. This process increases the adsorption of H 2 O and oxygen, making the Ti vacancy-rich surface convex area the most vulnerable site to attack. The findings in this study provide useful information for a comprehensive understanding of the interaction between MXene structural defects and metal ions as well as for the design and modification of MXene membranes resistant to metal ion impact.

Hydrogel-based sorbents show promise in the removal of toxic metals from water. However, optimizing their performance through conventional trial-and-error methods is both costly and challenging due to the inherent high-dimensional parameter space associated with complex condition combinations. In this study, machine learning (ML) was employed to uncover the relationship between the fabrication condition of hydrogel sorbent and their efficiency in removing toxic metals. The developed XGBoost models demonstrated exceptional accuracy in predicting hydrogel adsorption coefficients (K d ) based on synthesis materials and fabrication conditions. Key factors such as reaction temperature (50-70 °C), time (5-72 h), initiator ((NH 4 ) 2 S 2 O 8 : 2.3-10.3 mol%), and crosslinker (Methylene-Bis-Acrylamide: 1.5-4.3 mol%) significantly influenced K d . Subsequently, ten hydrogels were fabricated utilizing these optimized feature combinations based on Bayesian optimization, exhibiting superior toxic metal adsorption capabilities that surpassed existing limits (logK d (Cu): increased from 2.70 to 3.06; logK d (Pb): increased from 2.76 to 3.37). Within these determined combinations, the error range (0.025-0.172) between model predictions and experimental validations for logK d (Pb) indicated negligible disparity. Our research outcomes not only offer valuable insights but also provide practical guidance, highlighting the potential for custom-tailored hydrogel designs to combat specific contaminants, courtesy of ML-based Bayesian optimization., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Optimization of the efficiency of the photocatalytic degradation of organic and pharmaceutical pollutants represents a matter of fundamental and practical interest. The present experimental and DFT study deals with evaluation of OH radical binding energy as a simple computational descriptor of the catalytic activity of d- metal-decorated TiO 2 photocatalysts for the photodegradation of the widely used antibiotic ciprofloxacin. Five d- metals commonly used in catalytic materials (Zr, Pt, Pd, Fe, and Cu) were deposited on the TiO 2 surface, and the obtained photocatalysts were characterized experimentally (XRPD, ICP-OES, and SEM) and theoretically (DFT). Attention was also paid to the mechanistic insights and degradation byproducts (based on UV-Vis spectrometry and LC/MS analysis) in order to obtain systematic insight into their structure/performance relationships and confirm the proposed model of the degradation process based on OH radical reactivity.

We discussed and summarized the latest data from the global literature on the action of polyphenolic antioxidants and their metal complexes. The review also includes a summary of the outcomes of theoretical computations and our many years of experimental experience. We employed various methods, including spectroscopy (FT-IR, FT-Raman, NMR, UV/Vis), X-ray diffraction, thermal analysis, quantum calculations, and biological assays (DPPH, ABTS, FRAP, cytotoxicity, and genotoxicity tests). According to our research, the number and position of hydroxyl groups in aromatic rings, as well as the delocalization of electron charge and conjugated double bonds, have a major impact on the antioxidant effectiveness of the studied compounds. Another important factor is metal complexation, whereby high ionic potential metals (e.g., Fe(III), Cr(III), Cu(II)) enhance antioxidant properties by stabilizing electron charge, while the low ionic potential metals (e.g., Ag(I), Hg(II), Pb(II)) reduce efficacy by disrupting electron distribution. However, we observed no simple correlation between ionic potential and antioxidant capacity. This paper gives insights that will aid in identifying new, effective antioxidants, which are vital for nutrition and the prevention of neurodegenerative illnesses. Our results outline the connections between biological activity and molecular structure, offering a foundation for the methodical design of antioxidants. Our review also shows in detail how we use various complementary methods to assess the impact of metals on the electronic systems of ligands. This approach moves beyond the traditional "trial and error" method, allowing for the more efficient and rational development of future antioxidants.

Coal fired power plants are significant contributors to CO 2 emissions and produce solid waste in the form of coal fly ash, posing severe environmental challenges. This study explores the application of dry-impregnated coal fly ash for CO 2 capture from gas stream. The modification of coal fly ash was achieved using alkaline earth metal oxides, specifically CaO and MgO, to alter its physical and chemical properties. Characterization techniques like X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and BET (Brunauer-Emmett-Teller) analysis were employed for physio-chemical changes in the adsorbent. Breakthrough experiments were conducted using a laboratory-scale fixed packed-bed reactor to assess the influence of temperature and gas flow rate on CO 2 adsorption. Among the synthesized sorbents, calcium oxide-impregnated ash showed the highest CO 2 uptake capacity, achieving 9.41 mg/g at 30 °C and a flow rate of 20 L/hr under atmospheric pressure. Isotherm modeling indicated a heterogeneous adsorbent surface, with the data best fitting the Sips isotherm model. Furthermore, the adsorption data conformed well to the Yoon-Nelson and Thomas kinetic models, affirming their relevance in characterizing the adsorption process under varying conditions. This research emphasizes the potential of coal fly ash-an abundant, cost-free material-as an effective CO 2 adsorbent, contributing to both CO 2 mitigation and landfill waste reduction., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The determination of metal-containing additives in plastic materials via acid digestion protocols has attracted growing interest to address potential environmental implications. However, the lack of protocol harmonization hinders data comparability within the literature. Here, six acid digestion protocols were employed to determine the metal(loid) content in plastics: these included three different acid mixtures (HNO 3 combined with H 2 SO 4 , HCl or H 2 O 2 ) for microwave-assisted digestion, with or without an additional room-temperature digestion step with H 2 O 2 . Each protocol was first validated for seven metal(loid)s (As, Cd, Cr, Pb, Sb, Sn and Zn) using a low-density polyethylene (LDPE) certified reference material (ERM®-EC681m). Then, validated protocols were applied on end-use materials, including conventional (i.e., LDPE) and compostable (i.e., PBAT/TPS) plastics. The combination of H 2 SO 4 and HNO 3 with a further digestion step with H 2 O 2 was the most suitable protocol: it successfully passed validation thresholds for all metal(loid)s (recoveries in the range 98.6-101.0 %) and yielded the highest concentrations in end-use materials. All other protocols resulted in a less efficient digestion of the sample matrix, leading to lower recoveries and the formation of solid residues. Notably, end-use plastics showed a great variability in metal(loid) concentrations, likely due to their additive-rich composition, in contrast to the minimal content of acid-soluble additives of the reference material. This study represents an initial step towards the harmonization of acid digestion protocols and highlights new challenges in accurately analyzing end-use plastic materials, due to their complex additive composition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The quest for a good life, urbanization, and industrialization have led to the widespread distribution of endocrine-disrupting chemicals (EDCs) in water bodies through anthropogenic activities. This poses an imminent threat to both human and environmental health. In recent years, the utilization of advance materials for the removal of EDCs from wastewater has attracted a lot of attention. Metal-oxide nanocatalysts have emerged as promising candidates due to their high surface area, reactivity, and tunable properties, as well as enhanced surface properties such as mesoporous structures and hierarchical morphologies that allow for increased adsorption capacity, improved photocatalytic activity, and enhanced selectivity towards specific EDCs. As a result, they have shown extraordinary efficacy in removing a wide range of EDCs from aqueous solutions, including pharmaceuticals, agrochemicals, personal care items, and industrial chemicals. This study give insight into the unique physicochemical characteristics of metal-oxide nanocatalysts to effectively and efficiently remove harmful EDCs from wastewater. It also discussed the advances in the synthesis, and properties of metal-oxide nanocatalysts, and insight into understanding the fundamental mechanisms underlying the adsorption and degradation of EDCs on metal-oxide nanocatalysts using advanced characterization techniques such as spectroscopic analysis and electron microscopy. The findings of the study present metal-oxide nanocatalysts as a good candidate for the spontaneous sequestration of EDCs from wastewater is an intriguing approach to mitigating water pollution and safeguarding public health and the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Triboelectric nanogenerators (TENGs) have garnered significant attention as efficient energy-harvesting systems for sustainable energy sources in the field of self-powered wearable devices. Various conductive materials are used to build wearable devices, among which, gallium-based liquid metal (LM) is a preferred electrode owing to its fluidity and metallic conductivity even when strained. In this study, a stretchable, elastic, and wearable triboelectric nanogenerator is designed using a single electrode fabricated by embedding LM grid patterns into a stretchable silicone substrate through a two-step spray-coating process. Contrary to conventional double-electrode TENG that is challenging to integrate to human body, the LM grid-patterned single-electrode TENG (LMG-SETENG) has a simplified design and provides more flexibility. The LMG-SETENG can generate voltages of up to 100 V via triboelectrification upon contact with the human body, even under various degrees of strain, owing to the fluidity of the LM electrode. The generated energy can be utilized as a sustainable energy source to power various small appliances. Moreover, the proposed LMG-SETENG can be utilized in soft robotics, electronic skin, and healthcare devices., (© 2024 Wiley‐VCH GmbH.)

Cancer immunotherapy, as an emerging cancer treatment approach, harnesses the patient's own immune system to effectively prevent tumor recurrence or metastasis. However, its clinical application has been significantly hindered by relatively low immune response rates. In recent years, metal-based biomaterials have been extensively studied as effective immunomodulators and potential tools for enhancing anti-tumor immune responses, enabling the reversal of immune suppression without inducing toxic side effects. This review introduces the classification of bioactive metal elements and summarizes their immune regulatory mechanisms. In addition, we discuss the immunomodulatory roles of biomaterials constructed from various metals, including aluminum, manganese, gold, calcium, zinc, iron, magnesium, and copper. More importantly, a systematic overview of their applications in enhancing immunotherapy is provided. Finally, the prospects and challenges of metal-based biomaterials with immunomodulatory functions in cancer immunotherapy are outlined., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Meticulously engineered nanomaterials achieve significant advances in the diagnosis and therapy of solid tumors by improving tumor delivery efficiency; and thereby, enhancing imaging and therapeutic efficacy. Currently, polydopamine (PDA) attracts widespread attention because of its biocompatibility, simplicity of preparation, abundant surface groups, and high photothermal conversion efficiency, which can be applied in drug delivery, photothermal therapy, theranostics, and other nanomedicine fields. Inspired by PDA structures that are rich in catechol and amino functional groups that can coordinate with various metal ions, which have charming qualities and characteristics, metal-coordinated PDA structures are exploited for tumor theranostics, but are not thoroughly summarized. Herein, this review summarizes the recent progress in the fabrication of metal-coordinated PDA structures and their availabilities in tumor imaging and therapy, with further in-depth discussion of the challenges and future perspectives of metal-coordinated PDA structures, with the aim that this systematic review can promote interdisciplinary intersections and provide inspiration for the further growth and clinical translation of PDA materials., (© 2024 Wiley‐VCH GmbH.)

X-ray imaging frequently introduces varying degrees of metal artifacts to computed tomography (CT) images when metal implants are present. For the metal artifact reduction (MAR) task, existing end-to-end methods often exhibit limited generalization capabilities. While methods based on multiple iterations often suffer from accumulative error, resulting in lower-quality restoration outcomes. In this work, we innovatively present a generalized diffusion model for Metal Artifact Reduction (DiffMAR). The proposed method utilizes a linear degradation process to simulate the physical phenomenon of metal artifact formation in CT images and directly learn an iterative restoration process from paired CT images in the reverse process. During the reverse process of DiffMAR, a Time-Latent Adjustment (TLA) module is designed to adjust time embedding at the latent level, thereby minimizing the accumulative error during iterative restoration. We also designed a structure information extraction (SIE) module to utilize linear interpolation data in the image domain, guiding the generation of anatomical structures during the iterative restoring. This leads to more accurate and robust shadow-free image generation. Comprehensive analysis, including both synthesized data and clinical evidence, confirms that our proposed method surpasses the current state-of-the-art (SOTA) MAR methods in terms of both image generation quality and generalization.

An effective approach to producing sophisticated miniaturized and nanoscale materials involves arranging nanomaterials into layered hierarchical frameworks. Nanostructured layered materials are constructed to possess isolated propagation assets, massive surface areas, and envisioned amenities, making them suitable for a variety of established and novel applications. The utilization of various techniques to create nanostructures adorned with metal nanoparticles provides a secure alternative or reinforcement for the existing physicochemical methods. Supported metal nanoparticles are preferred due to their ease of recovery and usage. Researchers have extensively studied the catalytic properties of noble metal nanoparticles using various selective oxidation and hydrogenation procedures. Despite the numerous advantages of metal-based nanoparticles (NPs), their catalytic potential remains incompletely explored. This article examines metal-based nanomaterials that are supported by layers, and provides an analysis of their manufacturing, procedures, and synthesis. This study incorporates both 2D and 3D layered nanomaterials because of their distinctive layered architectures. This review focuses on the most common metal-supported nanocomposites and methodologies used for photocatalytic degradation of organic dyes employing layered nanomaterials. The comprehensive examination of biological and ecological cleaning and treatment techniques discussed in this article has paved the way for the exploration of cutting-edge technologies that can contribute to the establishment of a sustainable future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Biomass-encapsulated liquid metals (LMs) composite gels have aroused tremendous attention as epidermal smart materials due to their biocompatibility and sustainability. However, they can still not simultaneously possess toughness, adhesion, and recoverability. In this work, the tough, sticky, and recyclable protein-encapsulated LMs organogels (GLM x ) are fabricated through the micro-interfacial stabilization of LMs by lignin and the following preparation of food-making inspired gels. With the help of lignin modification, the LMs micro-drops demonstrated uniform dispersion in the protein matrix, as well as dense non-covalent interactions (e.g., H─bond and hydrophobic interaction) with amino acid residues in peptide chains, which endowed the GLM x with high conductivity (≈5.4 S m -1 ), toughness (≈738.2 kJ m -3 ), self-adhesiveness (a maximal lap-shear strength of ≈58.3 kPa), and recoverability. By tightly adhering onto human skin, the GLM x can act as epidermal sensors to detect drastic (e.g., joint bending) and subtle body movements (e.g., swallowing) and even recognize handwriting and speaking in real-time. Moreover, the organogels can also harvest solar energy and convert it into heat and electricity, which is promising in self-powered intelligent devices. Thus, this work paves a facile way to prepare protein/LMs composite organogels that are suitable for multiple applications like healthcare, human-robot interactions, and solar energy conversion., (© 2024 Wiley‐VCH GmbH.)

Nanomaterials with enzyme-like properties are known as 'nanozymes'. Nanozymes are preferred over natural enzymes due to their nanoscale characteristics and ease of tailoring of their physicochemical properties such as size, structure, composition, surface chemistry, crystal planes, oxygen vacancy, and surface valence state. Interestingly, nanozymes can be precisely controlled to improve their catalytic ability, stability, and specificity which is unattainable by natural enzymes. Therefore, tailor-made nanozymes are being favored over natural enzymes for a range of potential applications and better prospects. In this context, metal oxide nanoparticles with nanozyme-mimicking characteristics are exclusively being used in biomedical sectors and opening new avenues for future nanomedicine. Realising the importance of this emerging area, here, we discuss the mechanistic actions of metal oxide nanozymes along with their key characteristics which affect their enzymatic actions. Further, in this critical review, the recent progress towards the development of point-of-care (POC) diagnostic devices, cancer therapy, drug delivery, advanced antimicrobials/antibiofilm, dental caries, neurodegenerative diseases, and wound healing potential of metal oxide nanozymes is deliberated. The advantages of employing metal oxide nanozymes, their potential limitations in terms of nanotoxicity, and possible prospects for biomedical applications are also discussed with future recommendations., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Metals in living organisms and environments are essential for key biological functions such as enzymatic activity, and DNA and RNA synthesis. This means that disruption of metal ion homeostasis and exchange between cells can lead to diseases. EVs are believed to play an essential role in transporting metals between cells, but the mechanism of metal packaging and exchange remains to be elucidated. Here, we established the elemental composition of EVs at the nanoscale and single-vesicle level and showed that the metal content depends on the cell type and culture microenvironment. We also demonstrated that EVs participate in the exchange of metal elements between cells. Specifically, we used two classes of EVs derived from papaya fermented fluid (PaEVs), and decidual mesenchymal stem/stromal cells (DEVs). To show that EVs transfer metal elements to cells, we treated human osteoblast-like cells (MG63) and bone marrow mesenchymal stem cells (BMMSCs) with both classes of EVs. We found that both classes of EVs contained various metal elements, such as Ca, P, Mg, Fe, Na, Zn, and K, originating from their parent cells, but their relative concentrations did not mirror the ones found in the parent cells. Single-particle analysis of P, Ca, and Fe in DEVs and PaEVs revealed varying element masses. Assuming spherical geometry, the mean mass of P was converted to a mean size of 62 nm in DEVs and 24 nm in PaEVs, while the mean sizes of Ca and Fe in DEVs were smaller, converting to 20 nm and 30 nm respectively. When EVs interacted with BMMSCs and MG63, DEVs increased Ca, P, and Fe concentrations in BMMSCs and increased Fe concentration in MG63, while PaEVs increased Ca concentrations in BMMSCs and had no effect on MG63. The EV cargo, including proteins, nucleic acids, and lipids, differs from their origin in composition, and this variation extends to the element composition of EVs in our study. This fundamental understanding of EV-mediated metal exchange between cells could offer a new way of assessing EV functionality by measuring their elemental composition. Additionally, it will contribute novel insights into the mechanisms underlying EV production and their biological activity.

This study delves into the nature of individual hydrogen bonds and the relationship between metal cations and hydrogen bonding in the Watson-Crick guanine-cytosine (GC) base pair and its alkali and alkaline earth cation-containing complexes (M n+ -GC). The findings reveal how metal cations affect the nature and strength of individual hydrogen bonds. The study employs interacting quantum atoms (IQA) analysis to comprehensively understand three individual hydrogen bonds within the GC base pair and its cationic derivatives. These analyses unveil the nature and strength of hydrogen bonds and serve as a valuable reference for exploring the impact of cations (and other factors) on each hydrogen bond. All the H ⋯ D interactions (H is hydrogen and D is oxygen or nitrogen) in the GC base pair are primarily electrostatic in nature, with the charge transfer component playing a substantial role. Introducing a metal cation perturbs all H ⋯ D interatomic interactions in the system, weakening the nearest hydrogen bond to the cation (indicated by a) and reinforcing the other (b and c) interactions. Notably, the interaction a, the strongest H ⋯ D interaction in the GC base pair, becomes the weakest in the M n+ -GC complexes. A broader perspective on the stability of GC and M n+ -GC complexes is provided through interacting quantum fragments (IQF) analysis. This approach considers all pairwise interactions between fragments and intra-fragment components, offering a complete view of the factors that stabilize and destabilize GC and M n+ -GC complexes. The IQF analysis underscores the importance of electron sharing, with the dominant contribution arising from the inter-fragment exchange-correlation term, in shaping and sustaining GC and M n+ -GC complexes. From this point of view, alkaline and alkaline earth cations have distinct effects, with alkaline cations generally weakening inter-fragment interactions and alkaline earth cations strengthening them. In addition, IQA and IQF calculations demonstrate that the hydration of cations led to small changes in the hydrogen bonding network. Finally, the IQA interatomic energies associated with the hydrogen bonds and also inter-fragment interaction energies provide robust indicators for characterizing hydrogen bonds and complex stability, showing a strong correlation with total interaction energies., (© 2024 Wiley Periodicals LLC.)

The general trend of increasing life expectancy will consistently drive the demand for orthopedic prostheses. In addition to the elderly, the younger population is also in urgent need of orthopedic devices, as bone fractures are a relatively common injury type; it is important to treat the patient quickly, painlessly, and eliminate further health complications. In the field of traumatology and orthopedics, metals and their alloys are currently the most commonly used materials. In this context, numerous scientists are engaged in the search for new implant materials and coatings. Among the various coating techniques, plasma electrolytic oxidation (PEO) (or micro-arc oxidation-MAO) occupy a distinct position. This method offers a cost-effective and environmentally friendly approach to modification of metal surfaces. PEO can effectively form porous, corrosion-resistant, and bioactive coatings on light alloys. The porous oxide surface structure welcomes organic molecules that can significantly enhance the corrosion resistance of the implant and improve the biological response of the body. The review considers the most crucial aspects of new combined PEO-organic coatings on metal implants, in terms of their potential for implantation, corrosion resistance, and biological activity in vitro and in vivo.

Context: Phosphodiester bonds, which form the backbone of DNA, are highly stable in the absence of catalysts. This stability is crucial for maintaining the integrity of genetic information. However, when exposed to catalytic agents, these bonds become susceptible to cleavage. In this study, we investigated the role of different metal dications (Ca 2 ⁺, Mg 2 ⁺, Zn 2 ⁺, Mn 2 ⁺, and Cu 2 ⁺) in promoting the hydrolysis of phosphodiester bonds. A minimal DNA model was constructed using two pyrimidine nucleobases (cytosine and thymine), two deoxyribose units, one phosphate group, and one metallic dication coordinated by six water molecules. The results highlight that Cu 2 ⁺ is the most efficient in lowering the energy barrier for bond cleavage, with an energy barrier of 183 kJ/mol, compared to higher barriers for metals like Zn 2 ⁺ (202 kJ/mol), Mn 2 ⁺ (202 kJ/mol), Mg 2 ⁺ (210 kJ/mol), and Ca 2 ⁺ (223 kJ/mol). Understanding the interaction between these metal ions and phosphodiester bonds offers insight into DNA stability and organic data storage systems., Methods: DFT calculations were employed using Gaussian 16 software, applying the B3LYP hybrid functional with def2-SVP basis sets and GD3BJ dispersion corrections. Full geometry optimizations were performed for the initial and transition states, followed by identifying energy barriers associated with phosphodiester bond cleavage. The optimization criteria included maximum force, root-mean-square force, displacement, and energy convergence thresholds., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The disposal of electronic waste (EW) in open landfills has caused several toxic environmental effects. The harmful metallic components released in the environment due to deposition of EW act as hazards for living systems. EW management has been widely studied in recent days across the world. Though, several processes are implemented in extraction, recycling and recovery of heavy metals from the EW, most of them are not effective in recovering the precious metals. Various chemical processes are executed for efficient extraction of precious metals from e-wastes. Though the techniques are easy to process and rapid, however, the chemical leaching also has detrimental environmental consequences. Biological approaches, on the other hand, solves the purpose for efficient and environmentally friendly recovery of precious metals. Thus, both resource recovery as well as remediation can be targeted simultaneously. Biotechnological methods offer sustainable and efficient solutions for metal recovery from electronic wastes, presenting a viable alternative to traditional methods. Continued advancements in this field hold significant promise for addressing the growing e-waste challenge., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

The exploration of artificial metal-peptide assemblies (MPAs) is one of the most exciting fields because of their great potential for simulating the dynamics and functionality of natural proteins. However, unfavorable enthalpy changes make forming discrete complexes with large and adaptable cavities from flexible peptide ligands challenging. Here, we present a strategy integrating metal-cluster building blocks and peptides to create chiral metal-peptide assemblies and get a family of enantiopure [R-/S-Ni 3 L 2 ] n (n = 2, 3, 6) MPAs, including the R-/S-Ni 6 L 4 capsule, the S-Ni 9 L 6 trigonal prism, and the R-/S-Ni 18 L 12 octahedron cage. X-ray crystallography shows MPA formation reactions are highly solvent-condition-dependent, resulting in significant changes in ligand conformation and discrete cavity sizes. Moreover, we demonstrate that a structure transformation from Ni 18 L 12 to Ni 9 L 6 in the presence of benzopyrone molecules depends on the peptide conformational selection in crystallization. This work reveals that a metal-cluster building block approach enables facile bottom-up construction of artificial metal-peptide assemblies., (© 2024. The Author(s).)

Tire wear particles are an increasing issue in particle emissions to the environment. Germany-wide approximately 100,000 t tire wear particles are emitted every year into the environment which are estimated to be one third of the microplastic emissions. Up to 20% are estimated to reach inland surface waters. Their behavior in the aquatic environment is understudied. Tire wear particles have an overly hydrophobic surface that is capable of adsorbing substances like trace elements. In this study we investigated the adsorption and desorption of trace metals onto and from the particle surface of tire-related samples in water samples of the Freiberger Mulde, a river with naturally elevated concentration of trace elements. The priority trace metals Cr, Ni, Zn, Cd and Pb show a significant adsorption onto the particle surface of tire-related samples. Tire wear particles themselves revealed adsorption of mainly Ni, Cd and Pb. Regarding the German classification for suspended matter in freshwaters, an endangering of the chemical water quality is expected due to the adsorption process and not due to the particles themselves. Upcoming electromobility is expected to increase the Zn (increased tire abrasion) and decrease the Cu amount (reduced brake abrasion) released to freshwaters., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Angus Rocha Vogel reports financial support was provided by German Federal Environmental Foundation. Angus Rocha Vogel reports a relationship with German Federal Environmental Foundation that includes: funding grants and travel reimbursement. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Metallic biomaterials, including traditional bioinert materials (such as stainless steel, cobalt-chromium alloys, pure titanium, and titanium alloys), novel biodegradable metals (such as pure magnesium and magnesium alloys, pure zinc and zinc alloys, and pure iron and iron alloys), and biomedical metallic glasses, have been widely used and studied as various biomedical implants and devices. Many scientists and researchers have investigated their superior biomechanical properties, corrosion behavior, and biocompatibility. However, their surface characteristics are of extreme importance due to continuing interactions between the surface/interface of an implanted metallic biomaterial and the surrounding physiological environment. Surface morphologies on these metallic biomaterials can modulate their in vitro and in vivo biological responses. In this review, we have summarized and investigated the effect of various surface morphologies on the corrosion behavior, cellular response, antibacterial activity, and osteogenesis of biomedical metallic materials. In addition, future research directions and challenges of surface morphologies on biomedical metallic materials have been elaborated. This review can lay a theoretical and practical foundation for further research and development on biomedical metallic materials.

Innovative strategies for targeted anticancer therapies have gained significant momentum, with metal complexes emerging as tunable catalysts for more effective and safer treatments. Rational design and engineering of metal complexes enable the development of tailored molecular structures optimized for precision oncology. The strategic incorporation of metal complex catalysts within combinatorial therapies amplifies their anticancer properties. This perspective highlights the advancements in synthetic strategies and rational design since 2019, showing how tailored metal catalysts are optimized by designing structures to release or in situ synthesize active drugs, leveraging the target-specific characteristics to develop more precise cancer therapies. This review explores metal-based catalysts, including those conjugated with biomolecules, nanostructures, and metal-organic frameworks (MOFs), highlighting their catalytic activity in biological environments and their in vitro / in vivo performance. To sum up, the potential of metal complexes as catalysts to reshape the landscape of anticancer therapies and foster novel avenues for therapeutic advancement is emphasized.

By means of their specific interactions with different metal ions, naturally occurring proteins control structures and functions of many biological processes and functions in organisms. In view of natural metallopeptides, scientists have proposed artificial peptides which coordinate with metal ions through their functional groups either for introducing a special reactivity or for constructing various sensors. However, the design of new peptide ligands requires a deep understanding of the structures, assembly properties, and dynamic behaviors of such peptides. This review briefly describes detection strategies of metal ions via coordination to the binding sites in peptides. The principles and functions of sensing systems are described as well. We also highlight some examples of a metal-induced peptide self-assembly with relevance to biotechnology applications.

Field determination of the metal adsorption capacity of microplastics (MPs) by using a passive sampler had been done in typical subtropical mariculture area in China. The adsorption of eight metals (Fe, Mn, Cu, Zn, As, Pb, Cr and Cd) by five types of MPs (low-density polyethylene, polypropylene, polystyrene, poly(ethylene terephthalate) and poly(vinyl chloride) (PVC) was compared, including metal types, mariculture types (cage and longline culture), metal residue content in ambient environment, polymer types and particle sizes of MPs. The results showed that Cu, Zn, As, Cd, Pb and Cr in the mariculture environment were contaminated compared with the quality criteria. The concentrations of these six metals adsorbed on five MPs increased linearly with those in seawater. More enriched Cu and As in MPs in marine cage culture than in longline culture, due to the obvious endogenous pollution emissions for the artificial diets, fish medicine and disinfectants. Aged PVC with more cracks and pores showed higher metal adsorption capacity than any other polymers. MPs with a smaller size range of 50-74 μm tended to accumulate higher amounts of metals than those with a larger size range of 74-178 μm, consisting with the surface characteristics of MPs. The significant positive relationship between the concentrations of nutrients in seawater and the adsorption amounts of Cu, Zn and As on MPs implies that the eutrophication would promote their pollution. Based on the ecological risk assessment, the occurrence of MPs could aggravate the potential risk of metals to marine organisms in intensive mariculture areas. This is the first time to reveal the impacts of the adsorption of metals on aged MPs on the potential ecological risks of metals to organisms under the realistic environmental condition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Liquid metal, as a novel material, has become ideal for the fabrication of flexible conductive fibers and has shown great potential in the field of biomedical sensing. This paper presents a comprehensive review of the unique properties of liquid metals such as gallium-based alloys, including their excellent electrical conductivity, mobility, and biocompatibility. These properties make liquid metals ideal for the fabrication of flexible and malleable biosensors. The article explores common preparation methods for liquid metal conductive fibers, such as internal liquid metal filling, surface printing with liquid metal, and liquid metal coating techniques, and their applications in health monitoring, neural interfaces, and wearable devices. By summarizing and analyzing the current research, this paper aims to reveal the current status and challenges of liquid metal conductive fibers in the field of biosensors and to look forward to their development in the future, which will provide valuable references and insights for researchers in the field of biomedical engineering.

Metal ions have important roles in supporting the catalytic activity of DNA-regulating enzymes such as topoisomerases (topos). Bacterial type II topos, gyrases and topo IV, are primary drug targets for fluoroquinolones, a class of clinically relevant antibacterials requiring metal ions for efficient drug binding. While the presence of metal ions in topos has been elucidated in biochemical studies, accurate location and assignment of metal ions in structural studies have historically posed significant challenges. Recent advances in X-ray crystallography address these limitations by extending the experimental capabilities into the long-wavelength range, exploiting the anomalous contrast from light elements of biological relevance. This breakthrough enables us to confirm experimentally the locations of Mg 2+ in the fluoroquinolone-stabilized Streptococcus pneumoniae topo IV complex. Moreover, we can unambiguously identify the presence of K + and Cl - ions in the complex with one pair of K + ions functioning as an additional intersubunit bridge. Overall, our data extend current knowledge on the functional and structural roles of metal ions in type II topos., Competing Interests: Competing interests statement:The authors declare no competing interest.

Specific lipid isomers are functionally critical, but their structural rigidity and usually minute geometry differences make separating them harder than other biomolecules. Such separations by ion mobility spectrometry (IMS) were recently enabled by new high-definition methods using dynamic electric fields, but major resolution gains are needed. Another problem of identifying many isomers with no unique fragments in ergodic collision-induced dissociation (CID) was partly addressed by the direct ozone-induced dissociation (OzID) that localizes the double bonds, but a low reaction efficiency has limited the sensitivity, dynamic range, throughput, and compatibility with other tools. Typically lipids are analyzed by MS as singly charged protonated, deprotonated, or ammoniated ions. Here, we explore the differential IMS (FAIMS) separations with OzID for exemplary lipids cationized by polyvalent metals. These multiply charged adducts have much greater FAIMS compensation voltages ( U C ) than the 1+ ions, with up to 10-fold resolution gain enabling baseline isomer separations even at a moderate resolving power of the SelexION stage. Concomitantly OzID speeds up by many orders of magnitude, producing a high yield of diagnostic fragments already in 1 ms. These capabilities can be ported to the superior high-definition FAIMS and high-pressure OzID systems to take lipidomic analyses to the next level.

Redox-inactive metal-ion-driven modulation of the oxidation behavior of high-valent metal-oxo complex has garnered significant interest in biological and chemical synthesis; however, their role in permanganate (Mn(VII)) oxidation for the removal of organic pollutants has been largely neglected. Here, we uncover the impact of six metal ions (i.e., Ca 2+ , Mg 2+ , Ni 2+ , Zn 2+ , Al 3+ , and Sc 3+ ) presenting in water environments on Mn(VII) activity. These ions uniformly boost the electron and oxygen transfer capabilities of Mn(VII) while impeding proton transfer, as evidenced by electrochemical tests, thioanisole probe analysis, and the kinetic isotope effect. The observed effects are intricately linked to the Lewis acidity of the metal ions. Further mechanistic insights reveal that Mn(VII) can interact with metal ions without direct reduction. Such interactions modify the electronic configuration of Mn(VII) and create an acidic microenvironment, thus increasing its electrophilicity and the energy barrier for the abstraction of proton from organic substrates. More importantly, the efficacy of Mn(VII) in removing phenolic pollutants is regulated by these ions through changing the driving force for proton and electron transfer, i.e., facilitated at pH > 4.5 and inhibited at lower pH. The contribution of active Mn intermediates is also discussed to reveal the oxidative mechanism of the metal ion/Mn(VII) system. These findings not only facilitate the rational design of Mn(VII) oxidation conditions in the presence of metal ions for water decontamination but also offer an alternative paradigm for enhancing electrophilic oxidation.

Nanozymes are a class of nanomaterials with enzyme-like activity that can mimic the catalytic properties of natural enzymes. The small size, high catalytic activity, and strong stability of nanozymes compared to those of natural enzymes allow them to not only exist in a wide temperature and pH range but also maintain stability in complex environments. Recently developed single-atom nanozymes have metal active sites composed of a single metal atom fixed to a carrier. These metal atoms can act as independent catalytically active centers. Metal single-atom nanozymes have a homogeneous single-atom structure and a suitable coordination environment for stronger catalytic activity and specificity than traditional nanozymes. The antioxidant metal single-atom nanozymes with the ability of removing reactive oxygen species (ROS) can simulate superoxidase dismutase, catalase, and glutathione peroxidase to show different effects in vivo . Furthermore, due to the similar structure of antioxidant enzymes, a metal single-atom nanozyme often has multiple antioxidant activities, and this synergistic effect can more efficiently remove ROS related to oxidative stress. The versatility of single-atom nanozymes encompasses a broad spectrum of biomedical applications such as anti-oxidation, anti-infection, immunomodulatory, biosensing, bioimaging, and tumor therapy applications. Herein, the nervous, circulatory, digestive, motor, immune, and sensory systems are considered in order to demonstrate the role of metal single-atom nanozymes in biomedical antioxidants.

The ISWI family protein SMARCA5 contains the ATP-binding pocket that coordinates the catalytic Mg2+ ion and water molecules for ATP hydrolysis. In this study, we demonstrate that SMARCA5 can also possess an alternative metal-binding ability. First, we isolated SMARCA5 on the cobalt column (IMAC) to near homogeneity. Examination of the interactions of SMARCA5 with metal-chelating supports showed that, apart from Co2+, it binds to Cu2+, Zn2+ and Ni2+. The efficiency of the binding to the last-listed metal was influenced by the chelating ligand, resulting in a strong preference for Ni-NTA over the Ni-CM-Asp equivalent. To gain insight in the preferential affinity for the Ni-NTA ligand, QM calculations were performed on model systems and metal-ligand complexes with a limited protein fragment of SMARCA5 containing the double-histidine (dHis) motif. The calculations correlated the observed affinity with the relative stability of the d-block metals to tetradentate ligand coordination over tridentate, as well as their overall octahedral coordination capacity. Likewise, binding free energies derived from model imidazole complexes mirrored the observed Ni-NTA/Ni-CM-Asp preferential affinity. Finally, similar calculations on complexes with a SMARCA5 peptide fragment derived from the AlphaFold structural prediction, captured almost accurately the expected relative stability of the TM complexes, and produced a large energetic separation (~10 kcal∙mol-1) between Ni-NTA and Ni-CM-Asp in favour of the former., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Andrikopoulos, Čabart. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Double metal cyanide (DMC) complexes represent a unique family of materials with an open framework structure. The main current application of these complexes in chemical industry is their use as catalysts (DMCCs) of the ring-opening polymerization of propylene oxide (PO), yielding branched polyols, highly demanded in production of polyurethanes and surfactants. The actual problem of chemical fixing carbon dioxide from the atmosphere gave new impetus to the development of DMCCs, which turned out to be effective in oxirane/CO 2 copolymerization. In recent years, new types and formulations of DMCCs were created, so that greater understanding of the reaction mechanisms was achieved and new fields of catalytic applications were found. In the present review, we summarized background and actual information about the synthesis, structure, and mechanisms of the action of DMCCs, as well as their application in the development of new materials and fine chemicals.

The small Cys-rich protein metallothionein (MT) binds several metal ions in clusters within two domains. While the affinity of MT for both toxic and essential metals has been well studied, the thermodynamics of this binding has not. We have used isothermal titration calorimetry measurements to quantify the change in enthalpy (ΔH) and change in entropy (ΔS) when metal ions bind to the two ubiquitous isoforms of MT. The seven Zn2+ that bind sequentially at pH 7.4 do so in two populations with different coordination thermodynamics, an initial four that bind randomly with individual tetra-thiolate coordination and a subsequent three that bind with bridging thiolate coordination to assemble the metal clusters. The high affinity of MT for both populations is due to a very favourable binding entropy that far outweighs an unfavourable binding enthalpy. This originates from a net enthalpic penalty for Zn2+ displacement of protons from the Cys thiols and a favourable entropic contribution from the displaced protons. The thermodynamics of other metal ions binding to MT were determined by their displacement of Zn2+ from Zn7MT and subtraction of the Zn2+-binding thermodynamics. Toxic Cd2+, Pb2+, and Ag+, and essential Cu+, also bind to MT with a very favourable binding entropy but a net binding enthalpy that becomes increasingly favourable as the metal ion becomes a softer Lewis acid. These thermodynamics are the origin of the high affinity, selectivity, and domain specificity of MT for these metal ions and the molecular basis for their in vivo binding competition., (© The Author(s) 2024. Published by Oxford University Press.)

Human endonuclease V (EndoV) catalytically removes deaminated nucleobases by cleaving the phosphodiester bond as part of RNA metabolism. Despite being implicated in several diseases (cancers, cardiovascular diseases, and neurological disorders) and potentially being a useful tool in biotechnology, details of the human EndoV catalytic pathway remain unclear due to limited experimental information beyond a crystal structure of the apoenzyme and select mutational data. Since a mechanistic understanding is critical for further deciphering the central roles and expanding applications of human EndoV in medicine and biotechnology, molecular dynamics (MD) simulations and quantum mechanics/molecular mechanics (QM/MM) calculations were used to unveil the atomistic details of the catalytic pathway. Due to controversies surrounding the number of metals required for nuclease activity, enzyme-substrate models with different numbers of active site metals and various metal-substrate binding configurations were built based on structural data for other nucleases. Subsequent MD simulations revealed the structure and stability of the human EndoV-substrate complex for a range of active site metal binding architectures. Four unique pathways were then characterized using QM/MM that vary in metal number (one versus two) and modes of substrate coordination [direct versus indirect (water-mediated)], with several mechanisms being fully consistent with experimental structural, kinetic, and mutational data for related nucleases, including members of the EndoV family. Beyond uncovering key roles for several active site amino acids (D240 and K155), our calculations highlight that while one metal is essential for human EndoV activity, the enzyme can benefit from using two metals due to the presence of two suitable metal binding sites. By directly comparing one- versus two-metal-mediated P-O bond cleavage reactions within the confines of the same active site, our work brings a fresh perspective to the "number of metals" controversy.

Multi-target antimicrobial agents are considered a viable alternative to target-specific antibiotics, resistance to which emerged as a global threat. Used centuries before the discovery of conventional antibiotics, metal(loid)-based antimicrobials (MBAs), which target multiple biomolecules within the bacterial cell, are regaining research interest. However, there is a significant limiting factor-the balance between cost and efficiency. In this article, we utilize a checkerboard assay approach to explore antimicrobial combinations of MBAs with commonly used quaternary ammonium compound (QAC) antiseptics in order to discover novel combinations with more pronounced antimicrobial properties than would be expected from a simple sum of antimicrobial effects of initial components. This phenomenon, called synergy, was herein demonstrated for several mixtures of Al3+with cetyltrimethylammonium bromide (CTAB) and TeO32- with benzalkonium chloride (BAC) and didecyldimethylammonium bromide (DDAB) against planktonic and biofilm growth of Pseudomonas aeruginosa ATCC27853. Biofilm growth of Escherichia coli ATCC25922 was synergistically inhibited by the Cu2 +and benzalkonium chloride (BAC) mixture. Multiple additive mixtures were identified for both organisms. The current study observed unexpected species and growth state specificities for the synergistic combinations. The benefit of synergistic mixtures will be captured in economy/efficiency optimization for antimicrobial applications in which MBAs and QACs are presently used., Importance: We are entering the antimicrobial resistance era (AMR), where resistance to antibiotics is becoming more and more prevalent. In order to address this issue, various approaches are being explored. In this article, we explore for synergy between two very different antimicrobials, the antiseptic class of quaternary ammonium compounds and antimicrobial metals. These two antimicrobials have very different actions. Considering a OneHealth approach to the problem, finding synergistic mixtures allows for greater efficacy at lower concentrations, which would also address antimicrobial pollution issues., Competing Interests: The authors declare no conflict of interest.

The Zrt/Irt-like protein (ZIP) family consists of ubiquitously expressed divalent d -block metal transporters that play central roles in the uptake, secretion, excretion, and distribution of several essential and toxic metals in living organisms. The past few years has witnessed rapid progress in the molecular basis of these membrane transport proteins. In this critical review, we summarize the research progress at the molecular level of the ZIP family and discuss the future prospects. Furthermore, an evolutionary path for the unique ZIP fold and a new classification of the ZIP family are proposed based on the presented structural and sequence analyses.

Structural DNA nanotechnology is an emerging field and is expected to be used for various applications in materials science. In this study, we designed a DNA tensegrity triangle to accommodate the bipyridine complexes with metal ions (Ni 2+ and Fe 2+ ) at the center of the space within the triangle. A metal-bipyridine-incorporated DNA tensegrity triangle was crystalized, and the presence of metals within it was confirmed through X-ray crystal structure analysis. A signal of the anomalous dispersion effect derived from metal was observed in the center of the DNA triangle.

This research developed five ensemble-based machine learning (ML) models to predict the adsorption capacity of both pristine and metal-doped activated carbon (AC) and identified key influencing features. Results indicated that Extreme Gradient Boosting (XGB) model provided the most accurate predictions for both types of AC, with metal-doped AC exhibiting 1.7 times higher adsorption capacity than pristine AC showing 254.66 and 148.28 mg/g, respectively. Feature analysis using SHAP values revealed that adsorbent characteristics accounted for 53.5 % of the adsorption capacity in pristine AC, while experimental conditions were crucial for metal-doped AC (61.3%), with surface area and initial concentration being the most significant features, showing mean SHAP values of 0.317 and 0.117, respectively. Statistical comparisons of adsorbent characteristics between pristine and metal-doped AC showed that metal doping significantly altered surface area (p-value = 0.0014), pore volume (p-value = 0.0029), and elemental composition (C% (p-value = 3.9513∗10^ -7 ) and O% (p-value = 0.0007)) of AC. Despite the reduction in surface area and consistent pore volume after metal doping, the enhanced adsorption capacity of metal-doped AC was attributed to increased oxygen content from 10.89% to 17.28 % as mean values. This suggests that oxygen-containing functional groups play a critical role in the improved adsorption capacity of metal-doped AC. This research lays the groundwork for optimizing AC adsorbents by identifying key factors in metal-doped AC and suggest further studies on the interaction between specific metal dopants and resulting functional groups to improve adsorption capacity and reduce repeated labor work., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Stored rainwater, the primary source of drinking water in the villages and towns of the Loess Plateau in northwest China, has been found to contain per- and polyfluoroalkyl substances (PFASs) and lacks necessary treatment measures. Coagulation is a common water treatment process, and enhancing its efficacy in removing PFASs can significantly improve treatment efficiency, reduce costs, and minimize the environmental and health risks associated with perfluorinated compounds. This study investigated the removal efficiency of perfluorobutanoic acid (PFBA), perfluorobutanesulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS) using inorganic salt coagulants alone and in combination with polydimethyldiallylammonium chloride (PDMDAAC). The results indicated that the removal efficiencies of the four PFASs by polyferric chloride (PFCl) and polyaluminum chloride (PACl) increased with alkalinity. PDMDAAC significantly enhanced the coagulation removal efficiency of the four PFASs. The removal efficiency of the four PFASs was highest when the raw water pH was near 7. Within the molecular weight range of 0-500,000 for PDMDAAC, the removal efficiency of the four PFASs increased with increasing molecular weight. Charge neutralization is the primary coagulation mechanism for the removal of anionic PFASs. Therefore, this study provides guidance for selecting coagulants to remove PFASs from stored rainwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The study of metal ion's role in the biological processes of Alzheimer's disease has spurred investigations into the coordination chemistry of amyloid beta peptide and its fragments. Nano-electrospray ionization mass spectrometry (nESI-MS) has been utilized to examine the stabilization of bound anions on multiprotein complexes without bulk solvent. However, the effects of anions on metal ion binding interactions with amyloid beta peptide have not been explored. This study directly examined metal-peptide complexes using nESI-MS and investigated the effects of various anions on the binding ratio and stability of these complexes from ammonium salt solutions. The results indicate that different anions have distinct effects on the binding ratio and stability of various metal-peptide complexes. Of these, the bicarbonate ion exhibits the highest binding ratios for metal-peptide complexes, while binding ratios for these complexes in phosphate are comparatively low. Our results suggest that acetate, formate, bicarbonate, and phosphate have weak affinities and act as weak stabilizers of the metal-peptide complex structure in the gas phase. Intriguingly, chloride and sulfate act as stabilizers of the metal-peptide complex in the gas phase. The rank order determined from these data is substantially different from the Hofmeister salt series in solution. Although this outcome was anticipated due to the reduced influence of anions and water solvation, our findings correlate well with expected anion binding in solution and emphasize the importance of both hydration layer and anion-metal-peptide binding effects for Hofmeister-type stabilization in solution. This approach proved useful in examining the interactions between metal ions and amyloid beta peptide, which are relevant to Alzheimer's disease, using direct ESI-MS., (© 2024 The Author(s). Journal of Mass Spectrometry published by John Wiley & Sons Ltd.)

Sediments contaminated with hazardous metals pose risks to humans and wildlife, yet viable management options are scarce. In a series of laboratory experiments, we characterized Polonite® - an activated calcium-silicate - as a novel sorbent for thin-layer capping of metal-contaminated sediments. We tested a fine-grained by-product from the Polonite production as a cheap and sustainable sorbent. First, Polonite was reacted with solutions of Cu, Pb, and Zn, and the surface chemistry of the Polonite was examined using, e.g., scanning electron microscopy to investigate metal sorption mechanisms. Batch experiments were conducted by adding Polonite to industrially contaminated harbor sediment to determine sorption kinetics and isotherms. Importantly, we measured if the Polonite could reduce metal bioavailability to sediment fauna by performing digestive fluid extraction (DFE). Finally, a cap placement technique was studied by applying a Polonite slurry in sedimentation columns. The results showed rapid metal sorption to Polonite via several mechanisms, including hydroxide and carbonate precipitation, and complexation with metal oxides on the Polonite surface. Isotherm data revealed that the sediment uptake capacity (K f ) for Cu, Pb, and Zn increased by a factor of 25, 21, and 14, respectively, after addition of 5% Polonite. The bioavailability of Cu, Pb, and Zn was reduced by 70%, 65%, and 54%, respectively, after a 25% Polonite addition. In conclusion, we propose that sediment treatment with low doses of the Polonite by-product can be a cheap, sustainable, and effective remediation method compared to other more intrusive methods such as dredging or conventional isolation capping., Competing Interests: Declaration of competing interest We have no conflicts of interests to disclose. The funding sources did not have any participation in the research., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Many studies have studied biochar immobilizing chromium (Cr) in soil. However, few studies were conducted to reduce the environmental risks due to biochar aging in soil. In this study, we adopt FeCl 3 , MgCl 2 , and AlCl 3 to activate sewage sludge to form modified biochar and produce biochar tubules. Then, the column experiments were carried out to study the effect of fluctuating groundwater table on Cr leaching behavior, total Cr, and fractions distribution with the insertion of biochar tubule. Results showed that the Cr immobilization performance was improved by metal-modification biochar, the biochar tubules can significantly decrease the Cr leaching amounts, retard the Cr downward migration in the soil, and there was a better effect with slightly Cr-contaminated soil. In addition, the immobilization effect is also impacted by the biochar's application mode and the hydrodynamic conditions. Detailedly, the Cr leaching amounts maximally decreased by 33.39%, the residual amounts maximally increased by 10.05% in the soil column, and the exchangeable (EX) and carbonates-bound (CB) fractions were maximally increased by 85.18%, 151.78% at the equal depth of soil column, respectively. BET, SEM-EDS, XRD, and FTIR analyses revealed that biochars' immobilization mechanisms on Cr involved reduction(predominately), physisorption, precipitation, and complexation. Risk assessment demonstrated that the sewage sludge biochar has very low environmental risk. This study indicates that the biochar tubule applied to immobilize Cr in soil has potential and provides new insights into reducing environmental risks due to biochar aging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)