Metal Ion Coordination Research Articles

Characterization and Antimicrobial Studies of Cobalt(II) Complexes with Some Antibacterial Agents

Metal complexes of antibiotics have shown promising antimicrobial activities against some resistant strain of bacteria by inhibiting the growth or killing the microorganisms. This phenomenon has lot of impact when the pathogenic microorganisms develop continuous resistance to the available antibiotics via various cellular defense mechanisms. Therefore, the search for alternative drug-molecules is of prime importance to combat antimicrobial resistance microorganisms. Antibiotic complexes with metal ions have attracted the attention of scientists looking for new drugs and to increase the activity of currently available antibiotics. The bioactivity of antibiotics can be improved by coordination of metal ions. To do so, cobalt(II) complexes of different antibiotics have been prepared from reaction of cobalt(II) nitrate with the antibiotics viz. amoxicillin, cefpodoxime proxetil (CFP), gatifloxacin, metronidazole, sulfamethoxazole, ketoconazole and levofloxacin. The synthesized compounds were characterized by TLC, solubility testing, melting point determination, UV-spectrophotometry and FTIR analysis. The compounds were screened for antibacterial activity against Bacillus cereus, Pseudomonas aeruginosa, Salmonella typhi, Staphylococcus aureus, Escherichia coli and Salmonella abony, and it was found that the synthesized complexes exhibited potent antibacterial activity. Bangladesh Pharmaceutical Journal 28(1): 11-19, 2025 (January)

Selective On-Surface Metalation and Uncommon Reordering of Self-Assembled Macrocyclic Biquinazoline Ligands on Ag(111).

The macrocyclic biquinazoline ligand, H-Mabiq, presents a central and a peripheral site for the coordination of metal ions, making the adsorption on solid surfaces promising for the creation of self-assembled bimetallic two-dimensional platforms. Here, we apply an on-surface metalation strategy under ultra-high vacuum conditions to guide the synthesis of metalated species and study sequential metalation patterns. We find that cobalt (as well as iron) metalation on the Ag(111) surface preferentially occurs at the macrocyclic centre without further metal coordination to the peripheral site. Nevertheless, starting from a densely packed, self-assembled H-Mabiq monolayer, the modification of the central cavity by Co is accompanied by an unusual, metalation-induced phase transformation which gives evidence of modified lateral / interfacial interactions. The selective metalation of one molecular site opens up an on-surface route to create bimetallic networks incorporating select metal ions at different locations.

Enhancing Waterproof Food Packaging with Janus Structure: Lotus Leaf Biomimicry and Polyphenol Particle Technology for Vegetable Preservation.

With the increasing demand for improved food preservation, conventional waterproof food packaging has proven inadequate because of its limited functionality. Although incorporating features such as antibacterial and antioxidant properties into packaging enhances protection, it can compromise the hydrophobicity of the involved material, thereby increasing the risk of contamination from external sources. To address this challenge, a robust and reliable barrier capable of simultaneously integrating multiple protective functions is required. This research synthesizes polyphenol particles via metal ion coordination and multiple hydrogen bondings to enhance antioxidant and antimicrobial properties. In addition, inspired by the asymmetric wettability of Janus-structured lotus leaves, this study develops biomimetic multifunctional Janus electrospun fibers via electrostatic spinning. These fibers exhibit exceptional properties, including superhydrophobic, antifouling, ultraviolet-blocking, pH sensitivity, antioxidation, antimicrobial, and freshness retention properties. Experiments and mesoscopic capillary flow simulations elucidate the waterproofing ability and underlying mechanisms of the Janus electrospun fibers, demonstrating their function as hydrophobic shields for preventing water penetration. Overall, this study provides a reference for high-performance waterproof food packaging to enhance vegetable preservation.

Tunable Memory Performances of Hyperbranched Polyimides Functionalized with Metal-Porphyrins.

With the rapid advancement of information technology, the need to achieve ultra-high-density data storage has become a pressing necessity. This study synthesized three hyperbranched polyimides (HBPI-TAPP, HBPI-(Zn)TAPP, and HBPI-(Cu)TAPP) by polymerizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP), which features a cavity for metal ion coordination, with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), to systematically investigate the effect of metal ion species on storage performance. According to the results, memory devices based on HBPI-(Zn)TAPP exhibit volatile SRAM (static random-access memory) characteristics, whereas devices employing HBPI-TAPP and HBPI-(Cu)TAPP demonstrate non-volatile WORM (write-once, read-many) characteristics. Molecular simulations based on density functional theory (DFT) reveal that the storage behaviors of these polymers are governed by a charge-transfer mechanism, wherein electrons transfer from the porphyrin donor segment to the 6FDA acceptor segment, forming charge-transfer complexes that are not easily dissociated. The larger dipole moments of HBPI-TAPP and HBPI-(Cu)TAPP render the complexes difficult to dissociate, resulting in WORM-type memory behavior. In contrast, HBPI-(Zn)TAPP has the lowest threshold voltage, with a stronger electron binding that hinders the dissociation of the charge transfer complex, thereby enabling SRAM-type memory behavior.

Fabrication of alginate-based bio-tribopositive films via amine modification and metal ion coordination for high surface charge density

Fabrication of alginate-based bio-tribopositive films via amine modification and metal ion coordination for high surface charge density

Tuning the Duplex Stability of DNA Oligonucleotides Containing Metal-Mediated Base Pairs of Imidazole-Derived Nucleobases.

Two artificial imidazole-derived nucleobases, HQIm (3H-imidazo[4,5-f]quinolin-5-ol) and CaIm (imidazole-4-carboxylate), were introduced into short DNA duplexes to systematically investigate their thermal stability upon metal ion coordination. Metal-mediated base pairs are formed with the 3d metal ions CoII, NiII and ZnII, as well as with the lanthanoid ions EuIII and SmIII, which induce a thermal stabilization of up to 8 °C upon binding. The latter are the first lanthanoid-mediated base pairs involving only four donor atoms that result in a significant duplex stabilization. For the 3d metal ions, the increase in DNA melting temperature is in agreement with the trend in complex stability according to the Irving-Williams series. The duplex stabilization upon metal-mediated base pair formation depends on the identity of the artificial base pair, enabling discrimination between metal ions by systematic design of the duplex. Further, the influence of pH on the stability of selected duplexes was studied, revealing a linear relation between pH and the formation of HQIm-NiII-HQIm base pairs and allowing to induce a distinct stabilization between 1 °C and 28 °C. Regarding EuIII-mediated base pairs, an acidic pH can be utilized to disturb their formation, presumably by promoting the coordination of EuIII to the DNA backbone.

Proton Occupancies in Histidine Side Chains of Carbonic Anhydrase II by Neutron Crystallography and NMR - Differences, Similarities and Opportunities.

Histidine is a key amino-acid residues in proteins that can exist in three different protonation states: two different neutral tautomeric forms and a protonated, positively charged one. It can act as both donor and acceptor of hydrogen bonds, coordinate metal ions, and engage in acid/base catalysis. Human Carbonic Anhydrase II (HCA II) is a pivotal enzyme catalyzing the reversible hydration of carbon dioxide. It contains 12 histidine residues: sixsurface exposed, two buried, three active site zinc ion ligands, and one is a proton shuttle. Comparing results from NMR spectroscopy with previously determined neutron protein crystal structures enabled a side-by-side investigation of the proton occupancies and preferred tautomeric states of the histidine residues in HCA II. Buried and zinc coordinating histidines remain in one neutral tautomeric state across the entire pH range studied, as validated by both methods. In contrast, solvent-exposed histidines display high variability in proton occupancies. While the data were overall remarkably consistent between methods, some discrepancies were observed, shedding light on the limitations of each technique. Therefore, combining these methods with full awareness of the advantages and drawbacks of each, provides insights into the dynamic protonation landscape of HCA II histidines, crucial for elucidating enzyme catalytic mechanisms.

Cu/MOF-808 Catalyst for Transfer Hydrogenation of 5-Hydroxymethylfurfural to 2, 5-Furandimethanol with Formic Acid Mediation

Biomass platform compound 5-Hydroxymethylfurfural (HMF), with its low price and abundant source, can be used as a renewable resource to replace traditional petrochemicals. MOF-808(Zr) has tunable active sites and excellent stability under high temperatures and acidic as well as basic environments, and the unsaturated coordination of metal ions within its framework structure can exhibit Lewis acidity, facilitating catalytic transfer hydrogenation from HMF to 2, 5-Furandimethanol (BHMF). The hydrothermal–impregnation–reduction method was used to prepare Cu/MOF-808 catalysts with high catalytic performance. Formic acid was chosen as the hydrogen donor solvent. The selectivity and yield of BHMF were 75.65% and 71%, respectively, at 150 °C for 4 h. A reaction pathway for the catalytic hydrogen transfer of HMF to BHMF was proposed. The high activity and stability of the Cu/MOF-808 catalyst with dual active sites provide a viable method for feasible hydrogenation of HMF to high value-added compounds.

Energetics and Dynamics of Metal-Ion Coordination with Ionic Liquid Electrolytes: A Combined DFT and AIMD Investigation for Rechargeable Batteries

Energetics and Dynamics of Metal-Ion Coordination with Ionic Liquid Electrolytes: A Combined DFT and AIMD Investigation for Rechargeable Batteries

Structural and Functional Integration of Tissue-Nonspecific Alkaline Phosphatase Within the Alkaline Phosphatase Superfamily: Evolutionary Insights and Functional Implications.

Phosphatases are enzymes that catalyze the hydrolysis of phosphate esters. They play critical roles in diverse biological processes such as extracellular nucleotide homeostasis, transport of molecules across membranes, intracellular signaling pathways, or vertebrate mineralization. Among them, tissue-nonspecific alkaline phosphatase (TNAP) is today increasingly studied, due to its ubiquitous expression and its ability to dephosphorylate a very broad range of substrates and participate in several different biological functions. For instance, TNAP hydrolyzes inorganic pyrophosphate (PPi) to allow skeletal and dental mineralization. Additionally, TNAP hydrolyzes pyridoxal phosphate to allow cellular pyridoxal uptake, and stimulate vitamin B6-dependent reactions. Furthermore, TNAP has been identified as a key enzyme in non-shivering adaptive thermogenesis, by dephosphorylating phosphocreatine in the mitochondrial creatine futile cycle. This latter recent discovery and others suggest that the list of substrates and functions of TNAP may be much longer than previously thought. In the present review, we sought to examine TNAP within the alkaline phosphatase (AP) superfamily, comparing its sequence, structure, and evolutionary trajectory. The AP superfamily, characterized by a conserved central folding motif of a mixed beta-sheet flanked by alpha-helices, includes six subfamilies: AP, arylsulfatases (ARS), ectonucleotide pyrophosphatases/phosphodiesterases (ENPP), phosphoglycerate mutases (PGM), phosphonoacetate hydrolases, and phosphopentomutases. Interestingly, TNAP and several ENPP family members appear to participate in the same metabolic pathways and functions. For instance, extra-skeletal mineralization in vertebrates is inhibited by ENPP1-mediated ATP hydrolysis into the mineralization inhibitor PPi, which is hydrolyzed by TNAP expressed in the skeleton. Better understanding how TNAP and other AP family members differ structurally will be very useful to clarify their complementary functions. Structurally, TNAP shares the conserved catalytic core with other AP superfamily members but has unique features affecting substrate specificity and activity. The review also aims to highlight the importance of oligomerization in enzyme stability and function, and the role of conserved metal ion coordination, particularly magnesium, in APs. By exploring the structural and functional diversity within the AP superfamily, and discussing to which extent its members exert redundant, complementary, or specific functions, this review illuminates the evolutionary pressures shaping these enzymes and their broad physiological roles, offering insights into TNAP's multifunctionality and its implications for health and disease.

In Situ Preparation of MnO2 on the Catechol/Silane-Coated Polypropylene Nonwoven Fabrics for Effective Removal of Cationic Dyes.

Previous studies have confirmed that MnOx removes heavy metal ions and organic pollutants from water with dual effects of adsorption and oxidation coupling, significantly improving the ability to remove impurities. Nanometal oxides have a highly reactive surface but tend to agglomerate during preparation and are challenging to recycle after use. A common method is to combine nano-MnO2 with Fe3O4 to prepare magnetic materials for easy recycling. Our previous research has confirmed that catechol (CA) and (3-aminopropyl) triethoxysilane (KH550) can be co-deposited on the surface of polypropylene nonwovens to form a stable CK coating under alkaline conditions. In addition, the coating has many active groups, including hydroxyl groups, amino groups, etc. This study further investigates the secondary reactivity of CK coatings. The coordination of catechol groups and metal ions was used to anchor manganese ions to the coating. Meanwhile, the hydroxyl and amino groups were used to reduce manganese ions to Mn4+ in situ to prepare PP-(CK-MnO2). We found that the sample had an excellent decolorization effect on cationic dyes but was limited to anionic dyes. The decolorization mechanism of cationic dyes was further discussed. The results showed that the decolorization of cationic dyes had a dual effect of adsorption and oxidative degradation. Under acidic conditions, its oxidation properties were enhanced. It can be used as a highly effective decolorizing agent for cationic dyes, and the decolorization behavior is consistent with the first-order kinetics. As the pH increases, its oxidation properties gradually decrease. Although the electrostatic adsorption effect was enhanced, the overall decolorization performance was significantly reduced. Recycling experiments have proved that it can maintain >90% removal rate after five cycles. This study also demonstrated that the CK coating has dopamine-like properties, which can coordinate with metal ions to prepare metal-organic hybrid materials.

Enhanced plasticization resistance of hollow fiber membranes via metal ion coordination for advanced helium recovery

Plasticization can significantly impair the gas separation performance of gas separation membranes, especially for hollow fiber membranes (HFMs) with ultrathin skin layer. While conventional thermal crosslinking is an effective method to address this issue, it often leads to the transition layer collapse in HFMs, resulting in a significant decrease in gas permeance. Herein, we fabricate polyimide-cerium (PI–Ce) complex HFMs using a carboxylic group-containing 6FDA-mPDA0.65-DABA0.3-TFMB0.05 copolyimide through metal ion coordination to achieve plasticization-resistance helium recovery from natural gas. We optimized dope compositions and spinning conditions to produce defect-free hollow fiber membranes with a skin layer as thin as 300 nm. The coordination between carboxyl groups and cerium ions was characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The polymer-metal coordinated membranes exhibited enhanced gas selectivities compared to the pristine HFMs due to the tailored microporosity achieved through polymer-metal coordination. Furthermore, the PI-Ce HFMs demonstrated only a 10.8 % decline in mixed-gas He/CH4 selectivity, which is significantly lower than the 55.4 % decline observed in pristine HFMs when exposed to CO2-containing feed pressures below 400 PSIA. Molecular dynamics simulations confirmed that coordination confined molecular chain swelling, thereby suppressing plasticization caused by CO2. The exceptional plasticization resistance of the PI-Ce complex HFMs provides a novel strategy for recovering helium from aggressive natural gas environments.

Exploring divalent metal ion coordination. Unraveling binding modes in Staphylococcus aureus MntH fragments

Metal ion coordination is crucial in bacterial metabolism, while divalent metal ions serve as essential cofactors for various enzymes involved in cellular processes. Therefore, bacteria have developed sophisticated regulatory mechanisms to maintain metal homeostasis. These involve protein interactions for metal ion uptake, efflux, intracellular transport, and storage. Staphylococcus aureus, a member of the commensal flora, colonizes the anterior nares and skin harmlessly but can cause severe illness. MntH transporter is responsible for acquiring divalent metal ions necessary for metabolic functions and virulence. It is a 450-amino-acid protein analogous to Nramp1 (Natural Resistance-Associated Macrophage Protein 1) in mammals. Herein, the coordination modes of copper(II), iron(II), and zinc(II) ions with select fragments of the MntH were established employing potentiometry, mass spectrometry, and spectroscopic methods. Four model peptides, MNNKRHSTNE–NH2, Ac-KFDHRSS–NH2, Ac-IMPHNLYLHSSI–NH2, and Ac-YSRHNNEE–NH2, were chosen for their metal-binding capabilities and examined to determine their coordination properties and preferences. Our findings suggest that under physiological pH conditions, the N-terminal fragment of MntH demonstrates the highest thermodynamic stability with copper(II) and iron(II) ions. Furthermore, a comparison with other peptides from the S. aureus FeoB transporter indicates different binding affinities.

Spider Webs‐Inspired Aluminum Coordination Hydrogel Piezoionic Sensors for Tactile Nerve Systems

AbstractPiezoionics, a new frontier that employs mobile ions as energy and charge carriers, plays an important role in new energy and intelligent electronics. However, a significant challenge consists in balancing the structural design of metal ions coordination hydrogel (HG‐MI) piezoionics for current conduction, voltage generation, and especially mechanical adaptability. Herein, inspired by the spider webs' unique structure, a strategy by realizing the full potential of metal‐ligand ions ([(OH)Cl2]3−) to facilitate the keggin‐type structure AlOHAlOH generation together with activate functional carboxyls is introduced. Impressively, the whole property of the product HG‐AlPAC, especially the mechanical performance is improved. For example, the toughness of HG‐AlPAC is 2.75 MJ m−3, more than twofold that of traditional HG‐AlAS/AC/AN samples. Due to the stable fixation of ─Al─OH─ thus promoting Cl− separation upon external force, HG‐AlPAC achieves a piezoionic coefficient of 0.89 mV KPa−1 and energy conversion efficiency of 1.29%, promising for mechanical‐electrical conversion and sensing. Combined with the good mechanical performance with the excellent piezoionic properties, underscores its potential as a tactile nerve system of analgesia patients to prevent them from being injured. This work intends to provide a stride toward mechanically robust self‐powered piezoionic sensors and offer insights into ionotropic materials for energy harvesting, human‐machine interaction, and biointerface.

A smartphone-integrated bimetallic ratiometric fluorescent probe for specific visual detection of tetracycline antibiotics in food samples and latent fingerprinting

Designing and preparing highly sensitive and accurate fluorescent chemosensors for monitoring tetracycline antibiotics remains a challenge. Herein, a fluorescent chemosensor based on lanthanide metal-organic frameworks (Ln-MOFs) is proposed to realize high-precision monitoring by adjusting the ratio of lanthanide ions. Ln-MOFs with good aqueous stability were prepared by a solvothermal method using Eu3+, Tb3+ and the ligand 4,4′,4″-s-triazine-2,4,6-triyltribenzoic acid (H3TATB) in DMF/NMP/H2O. The Ln-MOFs could recognize oxytetracycline (OTC) and doxycycline (DOX), and the detection limits of OTC and DOX were as low as 8.6 and 4.8 nM, respectively. In particular, Eu(1.4 μM)-Tb-MOF sensors were used for visual detection of OTC and DOX in combination with smartphones with detection lines as low as 9.8 nM and 14.2 nM, respectively. Meanwhile, Eu-MOF, Tb-MOF and Eu(1.4 μM)-Tb-MOF can be used for latent fingerprint (LFP) visualization, demonstrating their potential applications in the field of criminal case investigation. The developed probes were successfully applied to determining OTC and DOX in milk, beef and pork with recoveries ranging from 92.0 % to 109.63 % and relative standard deviations (RSDs) ranging from 1.83 % to 4.56 %. Eu(1.4 μM)-Tb-MOF is believed to utilize its lanthanide metal ion coordination and photoinduced electron transfer (PET) mechanism to achieve highly selective and accurate OTC and DOX detection, which is supported by experimental and density functional theory (DFT) calculations.

Coordination-driven molecular switch on the base of an ESIPT-capable pyrimidine ligand: Synthesis, fine-tuning of emission by the halide anion and theoretical studies

ESIPT-based materials (ESIPT = Excited State Intramolecular Proton Transfer) find diverse applications in optoelectronics and biomedicine owing to the peculiarities of their luminescence properties. Here, an ESIPT-capable compound 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine (HL4,2,Me) featuring a short O–H⋅⋅⋅N intramolecular hydrogen bond and two N,N-sites for metal binding has been synthesized. HL4,2,Me is the first reported molecule which can act as an ESIPT molecular switch triggered by metal ion coordination without its deprotonation. Drastic changes in the HL4,2,Me conformation in the [Zn(HL4,2,Me)X2] (X = Cl, Br,I) complexes significantly alter the photoluminescence response compared to the free ligand. In the solid state, HL4,2,Me exhibits barrierless ESIPT and large Stokes-shifted yellow-orange emission due to the interplay of anti-Kasha S2 → S0 fluorescence and Kasha-like T1 → S0 phosphorescence radiative channels. The violation of Kasha’s rule for HL4,2,Me is justified by an extraordinarily large S2 – S1 energy gap (ca. 0.9 eV), slowing down the rate of S2 → S1 internal conversion. The photoluminescence behavior of the ESIPT–incapable zinc(II) coordination compounds strongly depends on the halide anion: the chlorido complex exhibits only fluorescence, the bromido complex displays a minor phosphorescence channel in addition to a major fluorescence channel, while the iodido complex exhibits predominantly phosphorescence. As a result, the emission color of the [Zn(HL4,2,Me)X2] complexes changes gradually from blue for X = Cl to orange for X = I, providing a platform for the fine-tuning of emission by the halide anion.

Synthesis of Sm‐TADDbBP@MCM‐41 as a Robust, Reusable, and Practical Nanocatalyst in the Homoselective [2 + 3] Cycloaddition Reaction

ABSTRACTSchiff‐base materials are known ligands for the coordination of metal ions and the synthesis of various stable and useful complexes. Therefore, herein, a novel Schiff‐base compound {2,2′‐((1E,11E)‐2,5,8,11‐tetra azadodeca‐1,11‐diene‐1,12‐diyl) bis (4‐bromophenol)} was introduced that formed from condensation of triethylenetetramine (TETA) and 5‐bromo‐2‐hydroxybenzaldehyde (5B2HB). This Schiff‐base ligand was labeled as TADDbBP. Besides, mesoporous MCM‐41 was synthesized using tetraethyl orthosilicate (TEOS), hydrolyzing cetyltrimethylammonium bromide (CTAB) and NaOH solution (2 M), followed by calcination at 550 °C, and further, the silanol sites on the MCM‐41's surface were modified by 3‐chloropropyltriethoxysilane (3Cl‐PTES), which modified MCM‐41 was labeled as 3‐Cl‐Pr@MCM‐41. In the next step, the synthesized TADDbBP (as Schiff‐base ligand) was grafted on 3‐Cl‐Pr@MCM‐41, which was labeled as TADDbBP@MCM‐41, and further, it was coordinated with samarium ions (which was labeled as Sm‐TADDbBP@MCM‐41 nanocatalyst) using Sm (CH3COO)3. This is the first report on the production of Sm‐TADDbBP@MCM‐41 nanocatalyst, this nanocatalyst was characterized by TEM, SEM, EDX, elemental mapping, BET method, ICP, XRD, and TGA techniques. In the final step, the catalytic performance of Sm‐TADDbBP@MCM‐41 nanocatalyst has been checked in the homo‐selective producing of tetrazoles through [2 + 3] cycloaddition of benzonitriles and sodium azide (NaN3) in PEG‐400 as available, nontoxic, green, and safe solvent. This nanocatalyst provides excellent selectivity in the synthesis of tetrazoles. In addition, Sm‐TADDbBP@MCM‐41 nanocatalyst can be separated and recycled for several cycles without significant reactivation or metal leaching.

Development of Recoverable Magnetic Bimetallic ZIF-67 (Co/Cu) Adsorbent and Its Enhanced Selective Adsorption of Organic Dyes in Wastewater.

In the critical domain of wastewater treatment, the development of cost-effective, durable, and recyclable adsorbents with high adsorption capacities remains a significant challenge. This study introduces a novel magnetic bimetallic Metal-Organic Framework (MOF) adsorbent, MZIF-67-Co/Cu, doped with copper ions. The MZIF-67-Co/Cu adsorbent was successfully synthesized and structurally characterized, demonstrating remarkable selectivity for removing methyl orange (MO) from water. This high selectivity is attributed to the adsorbent's high porosity and Lewis base properties at the coordinating metal ion center. The incorporation of Cu ions significantly enhances the porous architecture and increases the number of metal adsorption sites, leading to an impressive maximum MO adsorption capacity of 39.02 mg/g under optimized conditions (0.5 g/L adsorbent concentration, pH 3.0, 250 rpm agitation speed, adsorption time > 10 min). The adsorption kinetics closely follow the pseudo-second-order model, and the isotherm data fit well with the Langmuir model. The primary adsorption mechanisms involve electrostatic attraction and mesoporous interaction. This study highlights MZIF-67-Co/Cu as a highly efficient adsorbent with magnetic recovery capabilities, positioning it as a promising candidate for addressing critical issues in wastewater treatment.

The influence of Fe2+ on the self-assembly of a bipyridine containing homopolymer: From bowl-shaped nanoparticles to vesicles

Metal ion coordination has critical influence on the self-assembly behavior of amphiphilic polymers and the morphology of the obtained assemblies. Herein, an amphiphilic homopolymer with 2,2′-bipyridine (BPy) as side chain is synthesized (noted as PBPyAA), which can self-assemble into bowl-shaped nanoparticles (BNPs) in tetrahydrofuran (THF)/water. Taking advantage of the coordination interaction between BPy and metal ions, Fe2+ is chosen to regulate the self-assembly behavior and the morphology of the assemblies of PBPyAA in two pathways. (Ⅰ) The aqueous solution of Fe2+ with various concentrations is added to the THF solution of PBPyAA during self-assembly. (Ⅱ) Fe2+ is added into the THF solution of PBPyAA before self-assembly, followed by the addition of deionized water to promote the self-assembly. The results show that the pathway Ⅰ facilitates the coordination of BPy and Fe2+. With the increase of the concentration of Fe2+ aqueous solution, the coordination efficiency of BPy increases from 0.419 % to 7.789 %, leading to the transformation of BNPs to vesicles. Though the coordination efficiency of BPy also increases with the concentration of Fe2+ in pathway Ⅱ, which is still quite low of 0.274 % to 0.366 %, and the morphology of the BNPs barely changes. In addition, ethylene diamine tetraacetic acid (EDTA), a strong chelating agent, is also added to promote the competitive complexation with BPy, resulting in the dissociation of BPy and Fe2+ and the reversible transformation from vesicles to BNPs. Overall, the effect of Fe2+ coordination on the self-assembly behavior of PBPyAA in two pathways is investigated and the reversible transformation of BNPs to vesicles is also achieved.

Construction of One-Dimensional Covalent-Organic Framework Coordinated with Main Group Metals for Selective Electrochemical Synthesis of H2O2.

Covalent-organic frameworks (COFs) are promising electrocatalysts for the selective synthesis of H2O2 through the two-electron oxygen reduction reaction (2e- ORR). However, the design and synthesis of efficient and stable COF-based electrocatalysts is still challenging. In this work, a predesigned 1,10-phenanthroline-based one-dimensional COF (PYTA-PTDE-COF) was constructed to anchor main group metal (In, Sn, and Sb) as electrocatalysts toward 2e- ORR. The catalysts are featured with fully exposed metalated side chains. Structural characterization revealed that PYTA-PTDE-M's (M = In, Sn, and Sb) are all quite similar, except for the coordinated metal ions with the maintenance of good crystallinity. They all exhibited satisfying activity and selectivity toward 2e- ORR under alkaline conditions. Among them, PYTA-PTDE-Sb exhibited the best performance (Eonset is 0.765 V, the H2O2 selectivity is 96%, and the yield rate is 209.2 mmol gcat-1 h-1). Moreover, it also delivered superior stability with almost no attenuation of current density during the long-time test. Theoretical calculations revealed that the Sb metal site in the COFs has the lowest adsorption strength of *OOH, which could be the main reason for its superior selectivity. The PYTA-PTDE-Sb assembled zinc-air battery realizes not only the supply of clean energy but also the production of green chemicals, showing it is highly promising in practical applications. This work offers an example for designing main group metal-coordinated 1D COFs and reveals fundamental structure-activity relationship toward 2e- ORR.