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The presence of metalloids and heavy metals in the environment is of critical concern due to their toxicological impacts. However, not all metallic species have the same risk level. Specifically, the physical, chemical, and isotopic speciation of the metal(loids) dictate their metabolism, toxicity, and environmental fate. As such, speciation analysis is critical for environmental monitoring and risk assessment. In the past two decades, surface-enhanced Raman spectroscopy (SERS) has seen significant developments regarding trace metal(loid) sensing due to its ultrahigh sensitivity, readiness for in situ real-time applications, and cost-effectiveness. However, the speciation of metal(loid)s has not been accounted for in the design and application of SERS sensors. In this Perspective, we examine the potential of SERS for metal(loid) speciation analysis and highlight the advantages, progress, opportunities, and challenges of this application.

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The emergence of calixarenes as versatile compounds in recent years marks a significant advancement in scientific research. In the area of analytical chemistry, calixarenes have garnered attention for their utility as selective chemosensors, enabling the sensitive and specific detection of metal ions through colorimetric and fluorimetric methods. Moreover, calixarenes have found applications in bioimaging, where they serve as effective probes for visualizing biological structures and processes with high resolution and sensitivity. Additionally, recent studies have explored the anticancer properties of calixarenes, unveiling their potential as therapeutic agents for cancer treatment. This comprehensive review explores recent advancements in calixarenes chemistry, emphasizing their significance in the colorimetric and fluorimetric detection of metal ions. Additionally, it highlights the mechanisms involved in chemosensor design, providing insights into the underlying principles driving their efficacy. Furthermore, the application of calixarenes in bioimaging, particularly for visualizing cellular structures and processes, is discussed, showing their potential in biomedical research and diagnostics. The anticancer activity of calixarenes and their derivatives is also explored, shedding light on their promising role as therapeutic agents. Through an extensive examination of recent literature, this review provides valuable insights into the multifaceted applications of calixarenes and offers perspectives for future research directions.

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Peroxymonosulfate (PMS) is an eco-friendly disinfectant gaining attention. This study examined the influence of metal ions (Co(II), Cu(II), Fe(II)) on PMS disinfection with chloride ions (Cl-) against waterborne microorganisms, encompassing both bacteria and fungal spores. The findings elucidated that metal ions augment the inactivation of bacteria in the PMS/Cl- system while concurrently impeding the inactivation of fungal spores. Specifically, the PMS/Co(II)/Cl- process increased E. coli inactivation rates by 2.25 and 2.75 times compared to PMS/Co(II) and PMS/Cl-, respectively. Conversely, PMS/Me(II)/Cl- generally exhibited a diminished inactivation capacity against the three fungal spores compared to PMS/Cl-, albeit surpassing the efficacy of PMS/Me(II). For instance, the inactivation levels of A. niger by PMS/Cl-, PMS/Cu(II)/Cl-, and PMS/Cu(II) are 4.47-log, 1.92-log, and 0.11-log, respectively. Notably, fungal spores demonstrated a substantially higher resistance to disinfectants compared to bacteria. Differences in microbial susceptibility were linked to cell wall structure, composition, antioxidant defenses, and reactive species generation, such as hydroxyl radicals (•OH), sulfate radicals (SO4•-), and reactive chlorine species (RCS). This study demonstrated the novel and unique phenomenon of metal ions' dual role in modulating the PMS/Cl- disinfection process, which has not been reported before and has important implications for the field of water treatment.

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Herein, we propose the production of 5-keto-D-gluconic acid (5KGA) by fermentation using Gluconobacter oxydans (G. oxydans) as the starting strain, from an initial concentration of 100 g/L glucose as substrate and the chemical conversion of 5KGA to L-(+)-tartaric acid (L-TA). The results show the efficacy and feasibility of two-stage pH (5.50→natural) linkage ventilation (0.5 vvm and 1.0 vvm, L/L/min) control of batch fermentation for 5KGA production. The final 5KGA yield of 100.2 g/L of 1.0 vvm is much higher than 0.5 vvm with an average productivity of 1.95 g/L/h. Changing the method of fermentation from batch to fed-batch can efficently prolong the high activity of G. oxydans for 5KGA production with an increased average productivity of 3.10 g/L/h, and the conversion rate of glucose to 5KGA is 92.50 %. The chemical conversion of 5KGA to L-TA catalyzed by metal ions in vitro indicates that the optimal catalyst is Cu2+ with a conversion rate of 35.09 % of 5KGA to L-TA. Our method can provide a practical and effective alternative for the industrial production of 5KGA and its conversion to L-TA.

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Pseudomonas aeruginosa, a common cause of morbidity in cystic fibrosis, chronically infects the patient's lungs by forming an alginate-containing biofilm. Alginate lyases are polysaccharide lyases that lyse alginate and are, therefore, potential biofilm-disruptive agents. However, cystic fibrosis sputum contains high levels of metals such as iron and zinc. The efficacy of alginate lyases under these conditions of elevated metal concentrations has not been categorically determined. Here, we have assessed the enzyme activity of two exolytic and five endolytic alginate lyases in the presence of metal ions (Fe2+, Zn2+, Mn2+, Mg2+, Ca2+, Ni2+, Cu2+) elevated in the cystic fibrosis lung milieu. Several of these alginate lyases exhibited increased activity in the presence of Ca2+, and the polysaccharide lyase family 7 members studied here exhibited decreased activity in the presence of Zn2+. The enzyme activity of the PL7 alginate lyases from Cellulophaga algicola (CaAly/CaFLDAly) and Vibrio sp. (VspAlyVI) was not affected in the presence of a mix of all the above-mentioned metal ions at the elevated concentrations found in the cystic fibrosis lung milieu. Specific alginate lyases might, therefore, retain the ability to degrade the alginate-containing Pseudomonas biofilm in the presence of metal ions elevated in the cystic fibrosis lung milieu.

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Rational construction of high-performance ionic conductors is a critical challenge in the field of energy storage. In this study, a series of 1D anionic titanium-based covalent organic frameworks (COFs) containing abundant alkali metal ion migration sites, namely, COF-M-R (M = Li, Na, K; R = H, Me, Et), is constructed. The integration of negative TiO6 2- sites on 1D anionic COFs allows alkali metal cations to migrate directly through the channels. Meanwhile, the π-π stacking of 1D chain-to-chain allows the distribution of ion-migration sites in 2D planes. In view of this, multidimensional ionic transport in COFs is realized to achieve high ionic conductivity. COF-M-Rs exhibit an increased ionic conductivity as the counterions change from Li+ to Na+ to K+. Notably, COF-Na-Et has an impressive ionic conductivity as high as 0.81 × 10-3 S cm-1. The different decorated groups (H, Me, and Et) on the skeleton influence the dissociation of the cation from the polyanion. This study offers deep insights into the design of COF-based solid-state electrolytes to achieve high ionic conductivity by increasing the ionic transport dimensions.

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Fast, accurate, and reliable techniques for marine toxic heavy metal ions (HMI) detection are critical for the ecological environment and human health. One of the fatal drawbacks of traditional ion selective electrochemical sensors is that the modification of electrode cannot be accurately quantified, resulting in poor repeatability of the detection electrode and large error between the multi-electrode detection results. In order to tackle this challenge, this study presents ultra-fine micro-droplet printed electrodes for the in-situ detection of Cd2+, a carcinogenic and toxic HMI commonly found in the ocean. The ion selective membrane casting liquid was dispersed into tiny droplets with a diameter of micron through microfluidic technology, and the microdroplets were precisely arranged on the electrode surface. As a result, the modification error of electrode was reduced to pL level (accurate to 10 pL), which greatly improved the repeatability between electrodes prepared in different batches. The results of experiments with pure electrolyte, interference ions and artificial seawater indicated that the micro-droplet printed sensors possessed excellent properties of accuracy, precision, repeatability, and anti-interference. This novel micro-droplet printed sensor has the potential to capture an accurate picture of nearshore HMI in heterogeneous environments under shock conditions.

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Grafted chitosan materials show the characteristics of high stability, easy separation and recovery, and good heavy metal adsorption capacity, and have received much attention in the adsorption process. Therefore, in this work, novel grafted chitosan-based adsorbent CS-EHBSB@F-AE was prepared by a one-pot reaction of chitosan (CS), 3-ethoxy-4-hydroxybenzaldehyde (EHB), formaldehyde (F) and aminoethanol (F). The microstructure and morphology of the as-prepared composite CS-EHBSB@F-AE were characterized by FT-IR, TGA, DSC, FE-SEM, and BET analyses. The adsorption performance of the as-prepared CS-EHBSB@F-AE composite on Pb(II), Hg(II), and Cu(II) ions from aqueous was investigated using batch experiment and the effects of the initial pH of the solution, contact time, and initial metal ions concentration and temperature on the adsorption efficiency were investigated and discussed. At the best conditions, CS-EHBSB@F-AE exhibited remarkable adsorption capacity of 246.7 mg/g, 203.9 mg/g, and 234.4 mg/g in absorbing Pb(II), Hg(II), and Cu(II), respectively. The adsorption equilibrium and the kinetic studies confirmed that the ions adsorption process fits well with the Langmuir isotherm and pseudo-second-order (PSO) models. Additionally, the adsorption efficiency of Pb(II), Hg(II), and Cu(II) metal ions by the composite CS-EHBSB@F-AE was reduced by increasing the temperature from 298 K to 318 K. In addition, after the sixth ads/des cycles, the as-prepared adsorbent still exhibited high removal efficiency with a decrease in adsorption efficiency of Pb(II) (5.53 %), Hg(II) (15.43 %) and Cu(II) (8.27 %). Finally, we proposed that the ions adsorption by CS-EHBSB@F-AE has happened using the coordination of active groups containing nitrogen and oxygen atoms on the surface of the adsorbent with the Pb(II), Hg(II), and Cu(II) metal ions.

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In environmental matrices, the migration and distribution of contaminants at water-solid interfaces play a crucial role in their capture or dissemination. Scientists working in environmental remediation and wastewater treatment are increasingly aware of metal-contaminant coordination; however, interfacial behaviors remain underexplored. Here, we show that trivalent metal ions (e.g. Al3+ and Fe3+) mediate the migration of pollutant ligands (e.g. tetracycline (TC) and ofloxacin) to the organic solid interface. In the absence of Al3+, humic acid (HA) colloids (50 mg/L) capture 26.1 % of the TC in water (initial concentration: 10 mg/L) via weak intermolecular interactions (binding energy: -5.71 kcal/mol). Adding Al3+ (2.5 mg/L) significantly enhances the binding of TC to an impressive 94.2 % via Al3+ mediated coordination (binding energy: -84.89 kcal/mol). The significant increase in binding energy results in superior interfacial immobilization. However, excess free Al3+ competes for TC binding via direct binary coordination, as confirmed based on the unique fluorescence of Al3+-TC complexes. Density functional theory calculations reveal the intricate process of HA-Al3+ binding via carboxyl and phenolic hydroxyl sites. The HA-Al3+ flocs then leverage the remaining coordination capacity of Al3+ to chelate with TC. As well as providing insights into the pivotal role of metal ion on the self-purification of natural water bodies, our findings on the interfacial behavior of metal-contaminant coordination will propel coagulation technology to the capture of microscale pollutants.

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Given the significant global concern about heavy metal pollution, the development of effective adsorbents to capture pollutants has become an urgent issue. In this work, thiol-functionalized defective Zr-MSA-DMSA was designed by mixing 2,3-dimercaptosuccinic acid and mercaptosuccinic acid, which was applied for the rapid and efficient removal of M(II) (i.e., Pb(II), Hg(II), Cd(II)) from wastewater. Zr-MSA-DMSA exhibited excellent adsorption performance, and the maximum adsorption capacities for Pb(II), Hg(II), and Cd(II) were 715.2 mg g-1, 862.7 mg g-1, and 450.5 mg g-1. In actual wastewater, Zr-DMSA-MSA exhibited up to 97 % M(II) removal efficiency and excellent anti-interference ability. It also maintained good structural stability after five adsorption/regeneration cycles. Thus, the abundant oxygen vacancies and unsaturated adsorption sites on Zr-MSA-DMSA significantly improved the adsorption performance of M(II). Spectral analysis and DFT calculations confirmed that Zr-MSA-DMSA mainly relied on the coordination of sulfur and oxygen atoms, electrostatic attraction and a large number of defective sites to achieve the adsorption of M(II). Fixed bed experiments showed that Zr-MSA-DMSA exhibited a depletion time of 10500 min and a volume of 7.0 L. In summary, Zr-MSA-DMSA holds significant potential for treating heavy metal wastewater and provides potential applications for defect engineering.

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Modern molecular microbiology elucidates the organizational principles of bacterial biofilms via detailed examination of the interplay between signaling and gene regulation. A complementary biophysical approach studies the mesoscopic dependencies at the cellular and multicellular levels with a distinct focus on intercellular forces and mechanical properties of whole biofilms. Here, motivated by recent advances in biofilm research and in other, seemingly unrelated fields of biology and physics, we propose a perspective that links the biofilm, a dynamic multicellular organism, with the physical processes occurring in the extracellular milieu. Using Bacillus subtilis as an illustrative model organism, we specifically demonstrate how such a rationale explains biofilm architecture, differentiation, communication, and stress responses such as desiccation tolerance, metabolism, and physiology across multiple scales-from matrix proteins and polysaccharides to macroscopic wrinkles and water-filled channels.

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Scanning ion microscopy applications of novel focused ion beam (FIB) systems based on ultracold rubidium (Rb) and cesium (Cs) atoms were investigated via ion-induced electron and ion yields. Results measured on the Rb+ and Cs+ FIB systems were compared with results from commercially available gallium (Ga+) FIB systems to verify the merits of applying Rb+ and Cs+ for imaging. The comparison shows that Rb+ and Cs+ have higher secondary electron (SE) yields on a variety of pure element targets than Ga+, which implies a higher signal-to-noise ratio can be achieved for the same dose in SE imaging using Rb+/Cs+ than Ga+. In addition, analysis of the ion-induced ion signals reveals that secondary ions dominate Cs+ induced ion signals while the Rb+/Ga+ induced signals contain more backscattered ions.

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A bimetallic cobalt/nickel-based metal-organic framework (MOF), [Co/Ni(µ3-tp)2(µ2-pyz)2], denoted as Co/Ni-MOF, has been successfully prepared by a hydrothermal method. The MOF was prepared by incorporating mixed O- and N- donor ligands, specifically terephthalic acid (tp) and pyrazine (pyz). The Mesoporous Co/Ni-MOF was comprehensively characterized using various analytical methods such as XRD, BET, FT-IR, TGA (23 % char yields), SEM, and EDS analyses. The synthesized mesoporous Co/Ni-MOF was then used to absorb Co (II) from aquatic areas efficiently. Several critical parameters, such as the beginning Co (II) concentration (25-150 mg/L), the effect of pH (2-10), the duration of time (5-30 min), and the amount of adsorbent (0.003-0.02 g), were systematically investigated. Remarkably, the Mesoporous Co/Ni MOF displayed a significant adsorption capacity of 372.66 mg g-1 in the optimum conditions, including pH = 6, amount of adsorbent = 0.003 g, duration of time = 25 min, and beginning Co (II) concentration = 150 mg/L. Adsorption data from the experimental studies of the mesoporous Co/Ni MOF are matched based on the non-linear pseudo-first-order (PSO) kinetic model (R2 = 0.9999), and a chemical process is suggested for chemisorption. Furthermore, the adsorption isotherms of Co (II) heavy metal ions (HMIs) are an excellent fit with the non-linear Temkin, indicating that they explain the sorbent/sorbate interactions concerning the heat of adsorption. It is evident from the thermodynamic parameters that adsorption is a spontaneous and favorable exothermic process. These results highlight the promising adsorption performance and potential applications of the mesoporous Co/Ni-MOF as an effective adsorbent for Co (II) elimination from aquatic areas. Four-cycle regeneration studies were the most effective for the Co (II) under study.

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Pearls are deeply cherished for their rich color and gorgeous luster, and their quality directly affects their value. Currently, the evaluation of pearl quality is mainly based on four aspects: color, shape, size and smoothness. The quality of pearls is influenced by a variety of factors, categorized into internal factors, such as the structural composition of the nacreous layer and genetic factors of the mussels, and external factors, including the aquaculture environment. Existing research results indicates that genetic factors are the dominant factor controlling the pearl quality. However, the macromolecules such as metal ions, organic pigments and various physical and chemical factors in the aquaculture water environment will also significantly impact pearl quality. Among these, matrix proteins are organic macromolecules found in the nacreous layer that play an important role in pearl quality. They participate in the deposition of calcium carbonate and the construction of the organic framework, affecting the pearls' size and shape. The color of pearls is influenced by the deposition of metal ions, the transport of organic pigments and the regulation of microstructure.

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Mercury is known as a highly toxic metal that is poisonous even if present in a trace amount. Generally, it enters in the food chain (especially fish) and water resources via different pathways and leads to harmful effects. Owing to the detrimental nature of the metal, traditionally several methods were employed by researchers for regular monitoring of the mercury metal ions. However, these methods are associated with many limitations like high cost of technical expertise, and intricacy of the detection procedure. So, using these methods to detect mercury ions in real time is challenging. Therefore, in recent years fluorescent-based analytical tools emerged rapidly. Among the various fluorescent organic scaffolds, coumarin has been scorching, owing to quick response, light stability, high sensitivity, good selectivity, excellent fluorescence intensity, and fluorescence quantum yield. This review provides a deep dive into the coumarin-derived chemo-sensors development throughout 2015-2023. We anticipate that the review will assist to broad scientific community as a reference document to design more interesting sensors.

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This review explores the intricate roles of metal ions-iron, copper, zinc, and selenium-in glioma pathogenesis and immune evasion. Dysregulated metal ion metabolism significantly contributes to glioma progression by inducing oxidative stress, promoting angiogenesis, and modulating immune cell functions. Iron accumulation enhances oxidative DNA damage, copper activates hypoxia-inducible factors to stimulate angiogenesis, zinc influences cell proliferation and apoptosis, and selenium modulates the tumor microenvironment through its antioxidant properties. These metal ions also facilitate immune escape by upregulating immune checkpoints and secreting immunosuppressive cytokines. Targeting metal ion pathways with therapeutic strategies such as chelating agents and metalloproteinase inhibitors, particularly in combination with conventional treatments like chemotherapy and immunotherapy, shows promise in improving treatment efficacy and overcoming resistance. Future research should leverage advanced bioinformatics and integrative methodologies to deepen the understanding of metal ion-immune interactions, ultimately identifying novel biomarkers and therapeutic targets to enhance glioma management and patient outcomes.

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By examining and analyzing bran-free fermented Baijiu (BFB) with varying storage periods (0-20 years), it was observed that the overall concentration of volatile compounds initially increases and subsequently decreases over time. Furthermore, BFB exhibited more kinds of long chain esters, higher concentration of acetals, and reduced furfural content. The process of cellaring can enhance the aged, sweet, and fruity aroma of BFB. 16 flavor compounds, including 1,1-diethoxyethane, ethyl dodecanoate, and ethyl hexadecanoate, can be used as markers for vintage BFB, and electronic sensory technology was capable of discerning BFB in different years. The results of redundancy analysis (RDA) showed a positive correlation between metals and aldehydes, esters, and ketones, while indicating a negative correlation with acids and alcohols. Al, Fe, and Ca underwent the most significant changes during storage period, and they were positively correlated with differential substances, such as benzaldehyde, vanillin, ethyl isovalerate, and ethyl palmitate (P < 0.01).

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The development of innovative multi-emission sensors for the rapid and accurate detection of contaminants is both vital and challenging. In this study, utilizing two rigid ligands (H3ICA and H4BTEC), a series of water-stable bimetallic organic frameworks (EuTb-MOFs) were synthesized. Luminescent investigations have revealed that EuTb-MOF-1 exhibits prominent multiple emission peaks, attributed to the distinctive fluorescence characteristics of Eu(III) and Tb(III) ions. Therefore, EuTb-MOF-1 efficiently recognized various metal ions and pharmaceutical compounds through 2D decoded maps. Fe3+ and Pb2+ exhibited significant quenching effects on the luminescence of EuTb-MOF-1, which were attributed to the internal filtering effect and the interaction between Lewis basic sites within EuTb-MOF-1 and Pb2+ ions, respectively. Furthermore, EuTb-MOF-1 demonstrated high sensitivity to sulfonamide antibiotics, with detection limits of 0.037 µM for SMZ and 0.041 µM for SDZ, respectively. In addition, EuTb-MOF-1 was immobilized to prepare MOF-based test strips, enabling direct visual detection of sulfonamides as a portable sensor. With excellent water stability, multi-responsive recognition capabilities, and high sensitivity to specific analytes, EuTb-MOF-1 is a promising candidate for environmental contaminant detection in aquatic systems.

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Identifying and characterizing metal-binding sites (MBS) within macromolecular structures is imperative for elucidating their biological functions. CheckMyMetal (CMM) is a web based tool that facilitates the interactive validation of MBS in structures determined through X-ray crystallography and cryo-electron microscopy (cryo-EM). Recent updates to CMM have significantly enhanced its capability to efficiently handle large datasets generated from cryo-EM structural analyses. In this study, we address various challenges inherent in validating MBS within both X-ray and cryo-EM structures. Specifically, we examine the difficulties associated with accurately identifying metals and modeling their coordination environments by considering the ongoing reproducibility challenges in structural biology and the critical importance of well annotated, high-quality experimental data. CMM employs a sophisticated framework of rules rooted in the valence bond theory for MBS validation. We explore how CMM validation parameters correlate with the resolution of experimentally derived structures of macromolecules and their complexes. Additionally, we showcase the practical utility of CMM by analyzing a representative cryo-EM structure. Through a comprehensive examination of experimental data, we demonstrate the capability of CMM to advance MBS characterization and identify potential instances of metal misassignment.

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Layered double hydroxides (LDHs) have attracted significant attention due to their compositional and structural flexibility. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional LDHs with synergistic effects to increase the electrical conductivity of LDHs and promote the intrinsic activity. Herein, 3D hollow NiCo-LDH nanocages decorated porous biochar (3D NiCo-LDH/PBC) has been synthesized by using ZIF-67 as precursor, which was utilized for constructing electrochemical sensing platform to realize simultaneous determination of Cu2+ and Hg2+. The 3D NiCo-LDH/PBC possessed the characteristics of hollow material and three-dimensional porous material, revealing a larger surface area, more exposed active sites, and faster electron transfer, which is beneficial to enhancing its electrochemical performance. Consequently, the developed sensor displayed good performance for simultaneously detecting Cu2+ and Hg2+ with ultra-low limit of detection (LOD) of 0.03 µg L-1 and 0.03 µg L-1, respectively. The proposed sensor also demonstrated excellent stability, repeatability and reproducibility. Furthermore, the sensor can be successfully used for the electrochemical analysis of Cu2+ and Hg2+ in lake water sample with satisfactory recovery, which is of great feasibility for practical application.