A macroporous Poly(2-Hydroxyethyl methacrylate-glycidyl methacrylate) [Poly(HEMA-GMA)] cryogel functionalized with Poly(L-lysine) (PLL) and Cu(II) ions was developed for the efficient removal of the anionic dye Acid Blue 113 from water. The cryogel was synthesized via free-radical cryopolymerization of HEMA and GMA at - 20°C, followed by covalent grafting of PLL through epoxy ring-opening reactions and subsequent coordination of Cu(II) ions with PLL amine groups. SEM analysis confirmed a highly interconnected macroporous structure, while BET analysis revealed specific surface areas ranging from 6.45 to 7.85m2 g-1 and average pore diameters between 36 and 41nm. Batch adsorption experiments demonstrated strong pH dependence, with maximum adsorption at pH 4.0. The Poly(HEMA-GMA)-PLL-Cu(II) cryogel exhibited a high adsorption capacity of 501.6mg g-1 and reached equilibrium within 30min, indicating rapid adsorption kinetics. Kinetic data were best described by the pseudo-second-order model, while equilibrium data fitted well to the Langmuir isotherm, suggesting monolayer adsorption on homogeneous active sites. Additionally, the Cu(II)-containing cryogel exhibited notable antibacterial activity against several Gram-positive and Gram-negative bacteria. These findings demonstrate that the developed cryogel combines high adsorption capacity, rapid kinetics, and antimicrobial functionality, making it a promising material for advanced wastewater treatment applications.

Multimodal targeted combination therapy that harnesses synergistic effects has emerged as a transformative paradigm in cancer therapy, progressively replacing traditional monotherapy. Herein, we report a tumor microenvironment (TME)-responsive multifunctional nanoplatform Cu-Ce6@DHA NPs (CCD NPs), which is self-assembled through the coordination of Cu²⁺, the antitumor drug dihydroartemisinin (DHA), and the photosensitizer chlorin e6 (Ce6). This nanoplatform enables the near-infrared-triggered combination of cuproptosis and ferroptosis for tumor treatment. Upon internalization by tumor cells, these nanoparticles undergo glutathione (GSH)-triggered disintegration, releasing their encapsulated payloads within the TME. The released Ce6 mediates potent photodynamic therapy (PDT) under laser irradiation, and DHA undergoes GSH-dependent activation to generate cytotoxic reactive oxygen species (ROS) and suppresses glutathione peroxidase 4 (GPX4), thereby amplifying ferroptotic cell death. Concurrently, the released copper ions deplete intracellular GSH and further inhibit GPX4, which exacerbates lipid peroxidation and promotes ferroptosis. Notably, the intracellular accumulation of copper ions disrupts mitochondrial metabolism by destabilizing iron-sulfur cluster (Fe-S) proteins and inducing oligomerization of lipoylated lipoylated dihydrolipoamide S-acetyltransferase (DLAT), ultimately triggering cuproptosis. Therefore, our findings establish a novel nanoplatform that simultaneously exploits metabolic vulnerabilities (via cuproptosis), redox imbalances (via ferroptosis), and photodynamic effects, providing a promising multimodal therapeutic strategy for cancer treatment.

Guanine-functionalized MWCNT-supported Cu(I) magnetic nanocatalyst for green synthesis of isoquinolines in PEG/H₂O

A biomimetic multifunctional dressing based on stratum corneum microstructure: integrating antibacterial barrier and breathability for enhanced wound healing.

Fluorine-activated and -directed allene cycloadditions with nitrile oxide: Exploration of selectivities, reactivities, energetic aspects, and molecular mechanism.

By creating tailor-made binding sites, molecularly imprinted polymers (MIPs) function as synthetic antibodies, offering comparable specificity with enhanced stability and lower cost. While molecular imprinting technology has achieved significant success with small molecules, its application to macromolecules such as proteins remains challenging. This is primarily due to the common use of aqueous solutions for protein imprinting, where key interactions like hydrogen bonding and electrostatic forces are significantly weakened. To address these limitations, this study reports the rational design of a Cu(II)-coordinated MIPs nanocavity for the efficient and selective adsorption of bovine serum albumin (BSA). The approach leverages the chelation between histidine residues on the surface of BSA and Cu(II), in conjunction with the primary monomer N-isopropylacrylamide (NIPAM) and various functional monomers, including acrylamide (AAM), dimethylaminoethyl methacrylate (DMAEMA), 4-vinylpyridine (4-Vpy), and methacrylic acid (MAA), to construct a shape memory characteristic imprinted nanocavity. Notably, polyglutamic acid peptide cross-linkers (PC) were employed in place of conventional cross-linkers, through a pH-induced helical-coil conformational change, they allow for the gentle yet complete extraction of the BSA template. Experimental results demonstrated that the incorporation of Cu(II) improved the imprinting effect, with the Cu(II)-containing hydrogel achieving an adsorption capacity of 757.5 mg/g and an imprinting factor (IF) of 5.28. Mechanistic analysis revealed that the coordination of Cu(II) synergistically combines the strength of covalent bonds with the flexibility of noncovalent interactions, while the dynamic structure of the PC enhances the specificity of the imprinted sites. Separation experiments conducted with actual serum samples validated the high selectivity of this material for BSA. This research introduces a strategy for protein molecular imprinting technology that integrates high adsorption performance with mild desorption conditions, suggesting significant potential applications in the fields of biomedicine and blood analysis.

The increasing resistance of bacteria and fungi to antimicrobial agents demands therapeutic strategies with higher target selectivity and a lower risk of rapid resistance development. The Biologically Active Metallopeptides (BAM) group develops an approach based on the controlled interaction of metal ions with peptides and pathogen-derived proteins. In our work, metal ions (including Cu(II)/Cu(I), Zn(II), and Ni(II)) are treated as functional modules: they stabilize peptide structure, induce defined conformations and aggregation states, conditionally activate antimicrobial activity, and modulate the pathogen’s access to essential micronutrients. We elucidate the mechanisms of metal uptake and homeostasis in pathogens (including Cu and Zn acquisition systems, zincophores, and metal chaperones), identifying protein fragments that can act either as therapeutic targets or as targeting domains for the selective delivery of antimicrobial agents (a “Trojan horse” strategy). In parallel, we investigate antimicrobial peptides and endogenous peptides in the presence of metal ions, demonstrating that coordination of Cu(II) and Zn(II) can markedly enhance their bactericidal or antifungal activity by enforcing active conformations, inducing aggregation (e.g. fibril formation), and promoting the generation of reactive oxygen species locally at the infection site. Building on these principles, we design selective targeted antimicrobial peptides (STAMPs, ang. specifically targeted antimicrobial peptides) and chemically stabilized peptide and glycopeptide constructs with improved biological stability and tissue selectivity. We show that metal ion coordination chemistry can serve as a platform for engineering a new class of selective antimicrobial therapeutics.

PTCDA/CuS cathode enabling stable sulfide-based all-solid-state batteries

Small organic molecule-based therapeutic systems that integrate near-infrared (NIR) photothermal activity with Cu²⁺-mediated functionality as an orthogonal therapy pathway remain scarce. Herein, we demonstrate that coordination of Cu²⁺ with a...

Copper ion (Cu(II)) contamination poses a serious threat to water quality and public health due to its high toxicity and nonbiodegradability. Herein, we develop for the first time high-density salicylaldehyde-hydrazone covalent organic frameworks (COFs) for ultrafast and highly efficient Cu(II) removal. The resulting DhaTGCl-COF exhibits excellent adsorption performance, achieving a record-high adsorption kinetics (k2 = 160.58 mg·g-1·min-1) and one of the highest capacities of 569 mg·g-1 among all adsorbents reported to date. Notably, the material also demonstrates the lowest residual Cu(II) concentration (0.01 ppm) within 30 min. The outstanding performance is attributed to the uniform distribution of high-density, strong-affinity tridentate N,N,O-chelating moieties derived from salicylaldehyde-hydrazone within the well-aligned two-dimensional pore channels, which facilitate rapid diffusion and coordination of Cu(II) to the binding sites and ensure exceptional adsorption efficiency even for trace-level Cu(II). This work not only sets a new benchmark for Cu(II) adsorbents but also opens a promising avenue for the design of high-performance COFs for heavy metal ion removal.

The search for development strategies that yield low κlat has become the focus of thermoelectrics and barrier coatings. Here, we propose a “forced bond ionization” strategy by integrating conflicting coordination environments (planar three coordination versus tetrahedral four coordination of Cu) to form pseudo-tetrahedral structures. This approach induces partial ionization of Cu─I bonds in Cu5TeS3I3 (CTSI), yielding a record-low κlat of 0.17 W/(m·K) for dense inorganic polycrystals. The pseudo-tetrahedral configuration triggers shear modes, markedly reducing the transverse speed of sound (νT = 839 m/s) and amplifying anharmonicity (Grüneisen parameter γ = 2.76). Theoretical analysis reveals that coordination preference competition provides Cu atoms a metastable site, promoting the disordered behavior. The corresponding vibrations of I atoms and disordered Cu atoms dominate the phonon scattering while the material having remarkable flexibility and certain thermoelectric potential. This work establishes a bond ionization–driven design paradigm for ultralow κlat materials, marking a leap toward potential flexible thermoelectric applications.

Polyoxometalate-based metal-organic complexes with dual-site synergy for catalytic synthesis of p-benzoquinone

Simple coordination of Cu and ZnO nanoparticles synergistically enhances the electromagnetic wave absorption performance of lignin-derived carbon

A nanocomposite sensor has been developed by integratinghalloysitenanotubes (HNTs), kojic acid (K), and Cu2+ ions (HNTK-Cu),marking a significant advancement in the field of dopamine detection.This cutting-edge sensor leverages the synergistic properties of itscomponents to deliver exceptional analytical performance with promisingimplications for biomedical diagnostics and food safety monitoring.This innovative sensor exploits the unique properties of halloysitenanotubes and kojic acid to achieve a superior performance. Amongits most notable features, the HNTK-Cu sensor exhibits exceptionalsensitivity, reaching a limit of detection (LOD) of as low as 68 nM,enabling the accurate quantification of even trace levels of dopamine.Furthermore, it demonstrates remarkable selectivity, effectively discriminatingdopamine from structurally similar or commonly interfering substances,a crucial requirement for reliable real-world applications. The sensoralso offers excellent operational stability, maintaining a consistentperformance across multiple detection cycles, which is critical forlong-term and repetitive reuse. From a synthetic standpoint, the fabricationof the HNTK-Cu nanocomposite is both straightforward and environmentallyfriendly, representing a sustainable and cost-effective alternativeto conventional dopamine sensors. Notably, the HNTK-Cu sensor hasdemonstrated the capability to perform electrochemical detection incomplex matrices, including food samples and fetal bovine serum, underscoringits immediate applicability in practical scenarios. The sensor’ssuperior performance arises from the unique synergy between its components:the high surface area and robust mechanical/thermal stability of halloysitenanotubes and the strong metal-chelating ability of kojic acid, whichenhances both the loading and coordination of Cu2+ ions,critical to the sensor’s electrochemical activity.

The efficient employment of chiral porous organic cages (POCs) for asymmetric catalysis is of great significance. In this work, we have synthesized a chiral N-rich organic cage constructed through chiral (S, S)-1,2-cyclohexanediamine and benzene-1,3,5-tricarbaldehyde utilizing dynamic imine chemistry according to the literature. Following reduction with NaBH4, the resulting amine-based POCs (RCC3) feature appended chiral diamine moieties capable of coordinating Cu2+ cations. This Cu2+ coordination provides RCC3 with excellent enantioselectivity as a supramolecular nanoreactor in asymmetric decarboxylative Mannich reactions, providing up to 94% ee of the product. We found that the spatial distribution of chiral amine sites and the coordination of Cu2+ in the RCC3 have a significant impact on catalytic activity, especially enantioselectivity. This work provides insights into the structure–function relationship within supramolecular catalytic systems

The article investigates the influence of intramolecular hydrogen bonding in the maleic acid molecule on the structure and stability of π-acidoaqua complexes of copper(I) using quantum-chemical modeling (DFT/B3LYP). A comparative analysis of geometric and energy parameters between π-acidoaquacomplexes with maleic acid of different structures with and without intramolecular hydrogen bonding was performed. The features of the coordination of Cu+ ions with the unsaturated C=C fragment of maleic acid, as well as the interaction with water molecules in the internal coordination sphere, are considered. It is shown that the presence of an intramolecular hydrogen bond in the acid molecule only partially affects the electronic energy of the system, but is able to stabilize some complexes, in particular [Cu(С4Н3О4)(H2O)2]0 and [Cu(С4Н3О4)(H2O)3]0, compared with the results of modeling without taking into account the intramolecular hydrogen bond. An analysis of the topology of the electron density was carried out, critical points were identified, which indicate the formation of six- and seven-membered rings in structures with an intramolecular hydrogen bond. It is shown that in complexes with intramolecular hydrogen bond for acids deprotonated by the first degree, a slight unfolding of the carboxyl group was observed. And it also significantly affects the distribution of the effective charge, in particular Cu+ ions. Calculations showed that intramolecular hydrogen bonding reduces the electron density that maleic acid transfers to the Cu+ ion, which affects the effective charge of the latter, as well as the dπ-pπ-binding energies. The obtained results complement the data of previous studies and allow a better understanding of the role of intramolecular interactions in the stabilization of π-complexes of Cu(I) with bifunctional ligands.

A novel pyrazole derivative, 3-(1,3-bis(4-bromophenyl)-1H-pyrazol-4-yl)-2-(4-bromophenyl) acrylonitrile (BPPBPA), has been successfully synthesized and investigated as a highly selective and sensitive chemosensor for the detection of Cu (II) ions. Both absorption and emission spectroscopic studies clearly demonstrate the sensing capabilities of BPPBPA. Upon interaction with Cu (II) ions, the absorption spectrum exhibited a noticeable red-shift in wavelength accompanied by a decrease in intensity, indicating complex formation. Concurrently, the emission spectrum showed significant quenching, attributed to the coordination of Cu (II) ions with the pyrazole ring nitrogen atoms and the inherent paramagnetic nature of Cu (II). Further experimental evidence from Vibrating Sample Magnetometry (VSM) studies corroborated the paramagnetic characteristics of the BPPBPA-Cu (II) complex. The successful formation of the BPPBPA-Cu (II) complex was definitively confirmed through X-ray Photoelectron Spectroscopy (XPS), ESR and VSM analysis. This work highlights BPPBPA as a promising candidate for the selective and sensitive optical detection of Cu (II) ions in various applications

Multifunctional porous organic polymer-based hybrid nanoparticles for sonodynamically enhanced cuproptosis and synergistic tumor therapy.

Structural rearrangements in metal-organic supramolecules constructed from the coordination of Cu(II) with m-xpt (m-xylylenebis(pyridyltriazole)) are investigated upon their interaction with 1,4-diazabicyclo[2.2.2]octane (dabco) and carbon dioxide-enriched air. The binuclear [Cu2(m-xpt)2]4+ complexes react with dabco to produce a carbonate-bridged trinuclear complex, [Cu3(m-xpt)3(µ-CO3)]4+, and an oxalate-bridged binuclear complex, [Cu2(m-xpt)2(µ-C2O4)]2+, where carbonate and oxalate likely originate from CO2 and dabco, respectively. The trinuclear complex reassembles the original dimer upon the removal of the carbonate ion. Similarly, polymeric [Cu(o-xpt)(PF6)]n, formed from Cu(I) and o-xpt (o-xylylenebis(pyridyltriazole)) coordination, undergoes oxidation in CO2-enriched air to yield a tetranuclear Cu(II) complex, Cu4(o-xpt)3(μ4-CO3)(μ2-OH)(μ2-OCOCH3)4+. The reaction progress is monitored by UV-Vis spectroscopy, and the major products are characterized by single-crystal X-ray diffraction.

Certain proteins and synthetic covalent polymers experience aqueous phase transitions, driving functional self-assembly. Herein, we unveil the ability of supramolecular polymers (SPs) formed by G4.Cu+ to undergo heating-induced unexpected aqueous phase transitions. For the first time, guided by Cu+, guanosine (G) formed a highly stable G-quartet (G4.Cu+)/G-quadruplex as a non-canonical DNA secondary structure with temperature tolerance, distinct from the well-known G4.K+. The G4.Cu+ self-assembled in water through π-π stacking, metallophilic and hydrophobic interactions, forming thermally robust SPs. This enhanced stability is attributed to the stronger coordination of Cu+ to four carbonyl oxygens of G-quartet and the presence of Cu+- - -Cu+ attractive metallophilic interactions in Cu+-induced G-quadruplex, exhibiting a significantly higher interaction energy than K+ as determined computationally. Remarkably, the aqueous SP solution exhibited heating-induced phase transitions-forming a hydrogel through dehydration-driven crosslinking of SPs below cloud temperature (Tcp) and a hydrophobic collapse-induced solid precipitate above Tcp, showcasing a lower critical solution temperature (LCST) behavior. Notably, this LCST behavior of G4.Cu+ SP originates from biomolecular functionality rather than commonly exploited thermo-responsive oligoethylene glycols with supramolecular assemblies. Furthermore, exploiting the redox reversibility of Cu+/Cu2+, we demonstrated control over the assembly and disassembly of G-quartets/G-quadruplex and gelation reversibly.