搜索结果：Inorganic chemistry

Controlled generation and regulation of reactive oxygen species (ROS) remains challenging when photochemical and redox processes are combined for cancer-related applications. Photothermal regulation of metal-centred redox kinetics provides a route to amplified ROS (1O2, ˙OH, O2˙-, etc.) generation in hybrid inorganic systems. In such systems, transition metal-mediated ROS generation is intrinsically governed by local coordination environments, redox kinetics, and energy-transfer pathways. Herein, we report a stepwise-assembled Ti3C2@UCNP@Cu-TCPP@LA system in which the redox chemistry of Cu(II)-tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) is kinetically regulated by plasmon-assisted photothermal activation of Ti3C2 MXene under near-infrared (808 nm) irradiation. Ti3C2 nanosheets were integrated with aminated NaYF4:Yb3+/Er3+/Nd3+ upconversion nanoparticles (UCNPs) through interfacial hydrogen bonding. UCNPs serve as NIR-to-visible photonic intermediates for activating spatially segregated Cu-TCPP moieties covalently attached to the UCNP surface. This architecture suppresses π-π aggregation-induced ROS quenching, preserves the excited-state dynamics of Cu-TCPP, and facilitates efficient Förster resonance energy transfer (FRET) from the UCNPs. Under 808 nm irradiation, the integrated Ti3C2 component exhibits pronounced plasmon-derived photothermal behaviour (photothermal conversion efficiency ≈57%), which kinetically accelerates singlet oxygen (1O2) generation from photoexcited Cu-TCPP. Simultaneously, photothermal heating promotes intracellular Cu2+/Cu+ redox cycling and accelerates glutathione depletion and Fenton-like hydroxyl radical (˙OH) production, collectively amplifying chemodynamic reactivity. Ti3C2-mediated photothermal activation yields ∼4-fold higher 1O2 and ∼3-fold greater ˙OH generation than the UCNP@Cu-TCPP@LA system. Beyond photothermal activation, Ti3C2 serves as a conductive support that facilitates interfacial charge and energy transfer processes under NIR irradiation. Functionalisation with lactobionic acid (LA) improves aqueous dispersibility and enables receptor-mediated cellular uptake. In vitro studies confirm pH-responsive behaviour, efficient intracellular ROS generation, and significant cancer cell apoptosis (∼78%) under 808 nm excitation, highlighting the functional relevance of plasmon-assisted photothermal amplification of Cu-porphyrin redox chemistry on Ti3C2.

The urgency of climate mitigation has shifted CO2 management from isolated capture or utilization to integrated carbon cycling. In situ CO2 methanation offers a chemically coherent route by converting captured CO2 into methane through hydrogenation with renewable hydrogen, eliminating intermediate purification and compression. Inorganic dual-functional materials (DFMs), which integrate CO2 adsorption and catalytic hydrogenation functions within a single matrix, are central to enabling this concept by synchronizing capture and conversion. This review begins with a systematic overview of CO2 capture, with a focus on inorganic solid-state materials and their inherent performance trade-offs. It then examines the conceptual framework and latest advances in integrated carbon capture and conversion (iCCC) over DFMs, focusing on mechanistic understanding, interfacial synergy, intermediate speciation, and material design strategies. Subsequently, the review explores process intensification strategies for in situ methanation, from reactor configurations to system integration. This review focuses on inorganic DFMs as the key enabler, delivering mechanistic understanding and intensification strategies to advance efficient integrated CO2 capture and methanation.

The development of microbial communities within granular-activated carbon (GAC) transforms it into a highly effective biofilter, integrating adsorption and biodegradation processes for contaminant removal. This study evaluated the performance of an O3-biological-activated carbon (BAC)-O3 system for removal of inorganic contaminants and secondary effluents disinfection. The BAC column was packed with 50 cm of commercial GAC, reaching biological stability after approximately 45 days of operation. System efficiency was assessed based on the removal of sodium (Na), calcium (Ca), magnesium (Mg), chloride (Cl-), and boron (B). A central composite design (CCD) was employed to the treatment process, generating mathematical models, statistically validated, to determine optimal treatment conditions, leading to the selection of an O3 dosage of 4 mg L-1 before and after the BAC stage. The system effectiveness was further tested through the removal of nine metals and microbial disinfection. Results confirmed that the O3-BAC process efficiently removed inorganic contaminants, while the additional post-BAC ozonation step was essential for achieving effluent disinfection. The final treated effluent achieved quality standards suitable for non-potable restricted reuse, and its successful application in hydroponic lettuce cultivation demonstrates a promising avenue for sustainable water reuse in controlled agricultural environments.

We report the synthesis of two-dimensional conjugated organic frameworks-based organic-inorganic Z-scheme heterojunction (2D c-COFs/WO3) for photocatalytic hydrogen (H2) production. Under the optimal conditions, the H2 production rate reaches 80.9 mmol g-1 h-1, ∼27 times that of pristine 2D c-COFs. The interfacial interaction of the W-N bond, according to hard-soft acid-base theory, effectively accelerates charge separation and prolongs charge-separation lifetime, thus enhanced H2 production activity.

Nanocrystals (NCs) serve as versatile building blocks for the creation of functional materials with NC self-assembly offering opportunities to enable novel material properties. Here, we demonstrate that PbS NCs functionalized with strongly negatively charged metal chalcogenide complex (MCC) ligands, such as Sn2S64- and AsS43-, can self-assemble into all-inorganic superlattices with both long-range superlattice translational and atomic-lattice orientational order. Structural characterizations reveal that the NCs adopt an unexpected edge-to-edge alignment, and numerical simulation clarifies that orientational order is thermodynamically stabilized by many-body ion correlations originating from the dense electrolyte. Furthermore, we show that the superlattices of Sn2S64--functionalized PbS NCs can be fully disassembled back into the colloidal state, which is highly unusual for orientationally attached superlattices with atomic-lattice alignment. The reversible oriented attachment of NCs, enabling their dynamic assembly and disassembly into effectively single-crystalline superstructures, offers a pathway toward designing reconfigurable materials with adaptive and controllable electronic and optoelectronic properties.

In this study, a combination of experimental and theoretical methods was applied to rigorously characterize the factors controlling the stereochemistry of three novel adducts: VO(acac)2(trans-quinoline) (1), VO(acac)2(trans-isoquinoline) (2), and VO(acac)2(cis-isoquinoline) (3). Based on X-ray measurements, spectroscopic analysis (IR and UV-Vis) and density functional theory (DFT) calculations, it was demonstrated that the coordination mode is predominantly governed by steric factors. While the trans isomer is favoured both kinetically and thermodynamically in most cases, the cis isomer becomes viable when the favourable geometry of the ligand offsets the inherent steric and entropic penalties, as shown for isoquinoline. Electronic structure analysis revealed that cis coordination enhances σ-donation to the vanadium center, resulting in a stronger, more polarized V-N bond, a red-shifted VO stretching frequency, and a blue-shifted d-d transition. These findings establish clear structure-property relationships linking ligand architecture to coordination geometry, electronic structure, and thermal stability. The insights gained provide a predictive framework for the rational design of VO(acac)2-based complexes with tailored stereochemistry and optimized properties for applications in catalysis, materials science, and bioinorganic chemistry.

All-inorganic gold halide perovskites exhibit excellent stability and tunable bandgaps, positioning them as environmentally sustainable alternatives to organic-inorganic lead halide perovskites in photovoltaics. A mechanistic understanding of how crystal phase and composition engineering regulates multi-level structural and electronic properties-thereby determining charge recombination dynamics and overall performance-requires systematical investigation. In this study, we synthesized Rb2Au2I6via hydrothermal methods, identifying a previously unreported monoclinic primitive (mP) phase, which is distinct from the known monoclinic C-centered (mC) phase. Additionally, we designed six partially chloride-substituted derivatives of Rb2Au2I6 with distinct space groups to facilitate bandgap tunability and optimize charge carrier dynamics. We employed multiscale simulations, combining first-principles calculations (HSE06 functional with spin-orbit coupling) and device-scale continuum models, to clarify the relationships among different crystal phases, compositional engineering, charge-carrier transport, and device performance. Our analysis identified mC-Rb2Au2Cl4I2 and mP-Rb2Au2Cl2I4 as optimal compositions, demonstrating superior thermal stability and optoelectronic properties. Device-scale modeling incorporating cross-scale parameter transfer reveals the kinetic mechanisms linking non-radiative recombination and charge transport imbalance. This approach directly predicts a power conversion efficiency of 20.42% for mC-Rb2Au2Cl4I2 under operating conditions. This study establishes a comprehensive, mechanism-guided roadmap for the rational design of high-efficiency, stable, all-inorganic gold halide perovskite materials through synergistic crystal phase and composition engineering.

Although this work deals with well-established methods and a well-known model system, it demonstrates innovative findings. These groundbreaking findings will be of interest to chemists, biologists, and medical professionals alike. This investigation is pure and provides a dataset for gaining an in-depth understanding of the interactions of the MS2 bacteriophage with inorganic and organic ions. The nanoparticle surface can be viewed as an unstructured continuum characterized by a zeta potential that governs interspecies interactions and depends on the ionic composition of the aqueous medium. Interactions with inorganic and organic ions should involve considering the surface as a discontinuum. Recently, empirical evidence has led to a patch-like model of the surface of MS2 with discrete positive and negative values of surface charge density. This work involves concepts of the solvatochromism of malachite green as a polarity-dependent factor, the metachromasia of crystal violet as an association-dependent factor, and the chemical kinetics of alkaline fading of these dyes to investigate interparticle interactions and ion exchange. Such combined techniques provide broadly applicable data for studying bacterial interactions with various charged species or other biological interfaces.

Artificial intelligence is rapidly permeating modern technology, but its growth is increasingly constrained by the costs of delivering power and removing heat. Neural computation offers a striking counterpoint, for it achieves sophisticated information processing at exceptionally low energy by exploiting ionic flows and adaptive conductance. Inspired by the Hodgkin-Huxley view that function emerges from ion-transport dynamics, recent work has begun to implement memory and learning directly in fluids, where ions simultaneously carry signals and encode the internal device state. This Review charts the emerging landscape of fluidic ionic memristors, from soft, bioinspired materials to manufacturable solid-state nanofluidic architectures. In lipid bilayers, droplet networks, tissues and ionic polymers, electrical activity is intrinsically coupled to chemistry and mechanics, enabling plasticity across multiple timescales. In rigid nanopores, nanochannels and angstrom-scale slits, the softness is transferred from the scaffold to the ionic degrees of freedom, where electric double-layer dynamics, concentration polarization and confinement-driven effects produce history-dependent transport in robust inorganic frameworks. Hybrid approaches integrate gels, brushes, particles, or biomolecules within microfabricated structures to combine stability with rich analogue dynamics. We conclude by outlining the key requirements for translation from reproducibility to scalable integration towards ionic intelligence technologies.

Iridium(III) polypyridyl and cyclometalated complexes have emerged as highly versatile coordination compounds with applications spanning photocatalysis, optoelectronics, bioimaging, and photodynamic therapy. Whilst ruthenium(II) polypyridyl complexes have historically dominated nucleic acid recognition studies, iridium(III) systems possess distinct physicochemical advantages arising from strong spin-orbit coupling, tuneable metal-to-ligand charge-transfer (MLCT) states, long-lived triplet emission, and exceptional photostability. Despite these favourable features, their development as DNA-targeting agents remains comparatively underexplored, and mechanistic understanding lags behind that of ruthenium(II) counterparts. This review provides a structured overview of the recent advances in Ir(III) polypyridyl and cyclometalated complexes for DNA binding, luminescent sensing, and light-activated cytotoxicity. Particular emphasis is placed on structure-activity relationships, excited-state processes governing DNA-responsive luminescence, and photocleavage mechanisms. Comparisons with ruthenium(II) systems are drawn throughout to highlight iridium-specific design logic. Finally, current challenges and future research directions are identified to guide the rational development of multifunctional iridium(III) complexes for medicinal inorganic chemistry and therapeutic applications.

We employed first-principles calculations and molecular dynamics simulations to reveal atomic-scale mechanisms governing carboplatin interactions with magnesia (MgO) films. We demonstrated MgO functions as a synergistic drug delivery platform through three key actions: (i) high-affinity adsorption (binding energy of -2.24 eV) via dual N-H⋯Os hydrogen bonding and carbonyl oxygen coordination to Mg2+ sites; (ii) enhanced hydrolysis activation (reaction energy of -0.84 eV) that cleaved the dicarboxylate ligand to form bioactive [Pt(NH3)2(H2O)2]2+; (iii) efficient DNA targeting with strong guanine N(7) binding (-2.03 eV). Electronic structure analysis (charge transfer, ELF, DOS/pCOHP) confirmed that MgO maintained electronic integrity while polarizing carboplatin to weaken Pt-O bonds. Molecular dynamics further revealed stable Mg2+-carboxylate coordination (radial distribution peak at 2.23 Å), indicating the dual-action capability of MgO as a drug carrier and magnesium supplement. These atomic-level insights establish a theoretical framework for developing lower-toxicity platinum nanotherapeutics using inorganic oxide carriers.

While birefringence is determined by both the structural units and spatial arrangement within a crystal, the design of the latter remains highly challenging, largely due to the difficulty in controlling microscopic packing. Molecular crystals feature host-guest architectures, which offer an effective means of structural design by enabling the spatial arrangement of the host framework through the guest molecules. Herein, the molecule S8, characterized by its homoatomic bonding and planar-like configuration, exhibits significant polarizability anisotropy; then, by employing a new guest-symmetry modulation strategy, a series of guest molecules, including quasi-spherical SnI4, triangular pyramidal AsI3 and SbI3, and mixed-anion CHI3 that were successfully incorporated into the S8 host lattice, serves as structural directors that switch the S8 arrangement from an offset to a parallel alignment. Such control yields tunable birefringence, from a suppressed 0.182 (SnI4·(S8)2) to enhanced large values of 0.333 (S8), 0.596 (AsI3·(S8)3), 0.641 (SbI3·(S8)3), and finally giant 0.711 (CHI3·(S8)3) @546 nm, the last of which is the largest among known inorganic molecular crystals. The specific directionality of host S8 molecules is achieved via self-assembly, which is driven by the electrostatic potential of the incorporated guest molecules. These results not only validate the effectiveness of the guest-symmetry modulation strategy but also underscore its potential for the design of birefringent materials.

A novel cost-effective and resource-efficient sample introduction system was developed by combining mini-computer numerical control (mini-CNC) with a negative pressure (NP) approach to enable automated sample manipulation, low-volume sample introduction, and eluent delivery for operation in a low pressure open tubular capillary ion chromatography (OTIC). The developed OTIC system was applied for the separation of water-soluble inorganic anions (Cl-, NO2-, Br-, and NO3-) on AS-18-coated fused silica capillary (25 or 50&#x202f;&#x3bc;m i.d.) with a capacitively coupled contactless conductivity detector (C4D) to improve accessibility to ion analysis in low-resource settings. A single line micro-flow injection analysis (&#x3bc;-FIA) format was used to evaluate the basic injection system, and provided a signal repeatability of 4.3% RSD (n&#x202f;=&#x202f;19) as a proof-of-concept. The repeatability of the entire process, including sample solution introduction and ion separation, was 5.6% RSD (n&#x202f;=&#x202f;9). A sample loading volume of 20&#x202f;&#x3bc;L in a small vial was sufficient for multiple injections with an injected volume of <10&#x202f;nL per injection, reducing reagent use and analytical waste. The linear calibration for quantification of the four anions was achieved in the range of 0.1 - 10&#x202f;mg&#x202f;L-1. The novel mini-CNC-NP system coupled with OTIC was applied for the determination of water-soluble small inorganic anions in PM2.5 extracted solution samples. The accuracy of the device was validated by comparing the analytical results with a standard packed column ion chromatograph (IC); a statistical t-test showed acceptable agreement. The recoveries of samples spiked with standard anions ranged from 90.9% to 102.5%. The novel mini-CNC-NP system could benefit automated sample manipulation/injection in other capillary scale separation systems.

Elucidating the pathway by which RNA efficiently emerged and persisted under prebiotic conditions remains a fundamental challenge in origin-of-life research. Molecules capable of bridging the gap between prebiotic precursors (such as ribonucleosides and inorganic phosphates) and the spontaneous formation of RNA chains within the thermodynamic barriers of a plausible early-Earth environment still remain unclear. Here, we demonstrate that metal ions play a crucial role in promoting the regioselective formation of 2',3'-cyclic ribonucleotides, which are often considered as competent components for RNA chain growth. By adding Ni2+ or Co2+ to a mixture of ribonucleosides, water-soluble inorganic phosphate, urea, and ammonium formate and exposing this to wet-dry cycles, we observed a four-fold increase in the formation of 2',3'-cyclic ribonucleotides compared to assays without metal ions. Dinucleotide formation was also detected in the same assay solutions. The formation of different regioisomers of mononucleotides was primarily confirmed by HPLC-based analysis, along with MALDI-ToF mass spectrometry and 31P NMR spectroscopy. Our current findings could help in bridging the gap between how reactive RNA precursors could have formed and how those precursors eventually emerged as the RNA chains needed for the origin of life.

Constructed wetland-microbial fuel cell (CW-MFC) is a promising technology for wastewater treatment with concurrent resource and energy recovery. However, its power generation capacity and mercury (Hg) removal efficiency are significantly limited by the insufficient electron transfer of anode materials. In this study, CW-MFCs were developed using zero-valent iron and siderite as anode materials. The incorporation of iron-based substrates significantly enhanced Hg removal, with total Hg removal efficiencies increasing by 22.9&#x202f;% and 18.4&#x202f;%, respectively, compared to conventional CW-MFCs. The integration of iron-based materials increased the availability of organic/inorganic electron donors by 9.1-350.0&#x202f;%, thereby enhancing power generation performance by 17.9-34.9&#x202f;%. This enhancement promoted the reduction of Hg(II) and inhibited the formation of methylmercury. Additionally, the electricity generated by the MFC facilitated Fe(III)/ Fe(II) redox cycling, which supported continuous corrosion and electron release from the iron anode. Metagenomic and electrochemical analyses demonstrated that the use of iron-based materials in CW-MFCs improved both extracellular and intracellular electron transfer efficiencies, and strengthened the synergistic interaction between the iron-based anode and electroactive bacteria. The genes that related to Hg(II) reduction, including merA, were also improved. Generally, this study highlights the potential of iron-based anodes to enhance Hg removal and power generation in CW-MFCs, providing a sustainable and energy-recovering strategy for wastewater treatment.

Iron complexes with antioxidant activity have garnered significant interest for both general and medical applications, yet few studies have yielded functional nonheme iron-based mimics for H2O2 mitigation in aqueous environments. Here, we investigate water-soluble nonheme iron complexes derived from 12-membered pyridinophanes (CF3PyN3, PyN3, NMe2PyN3, and Py2N2) to evaluate the impact of ligand scaffolds on H2O2 decomposition activity both in vitro and in a cellular model. Speciation and kinetic analyses reveal that both electronic and geometric modulation of the macrocyclic ligand framework govern H2O2 disproportionation activity. Electron-donating substituents accelerate turnover but reduce stability, while electron-withdrawing groups enhance robustness at the expense of rate. The unsubstituted Fe(PyN3)3+ complex achieves the optimal balance, exhibiting the highest catalytic efficiency (k = 1.45 M-1 s-1) and turnover number (TON = 33) under physiological conditions. Crystallographic characterization of the Fe(Py2N2)3+ complex, reported here for the first time, revealed a &#x3bc;-oxo-bridged dimeric structure that rationalizes its diminished reactivity. Collectively, these findings define key design parameters for constructing stable, Fenton-resistant nonheme iron catalysts. Extending this chemistry to a biological context, Fe(PyN3)3+ was shown to mitigate H2O2-induced oxidative stress in HeLa cells by catalytically reducing intracellular ROS levels and improving cell viability. The integration of molecular, mechanistic, and cellular data demonstrates that well-defined iron-pyridinophane frameworks can translate homogeneous catalytic behavior into complex biological systems, offering a foundation for the design of therapeutic antioxidant catalysts.

Sulfur-containing wastes are typical pollutants generated from oil and gas extraction, petroleum refining, and fossil fuel combustion, with annual global emissions reaching tens of millions of tons. Traditional treatment technologies rely on end-of-pipe control, suffering from high energy consumption, substantial carbon emissions, severe secondary pollution, and low resource utilization efficiency. Electrocatalytic conversion driven by renewable electricity enables the directional valorization of sulfur-containing pollutants under mild conditions, providing an alternative route for the green upgrading of sulfur resources. This review systematically summarizes the research progress in electrocatalytic valorization technologies for waste sulfur-containing species. Starting from the fundamental reaction principles, we elaborate the electrocatalytic conversion routes, reaction mechanisms, catalyst design, and system optimization strategies for four typical sulfur-containing substrates, including inorganic sulfides, sulfur oxides, organosulfur wastes, and metal sulfide minerals. It highlights the core technological innovations of direct interfacial electrocatalysis, redox mediator-mediated indirect electrocatalysis, and paired electrolysis. Moreover, the key challenges in anti-sulfur-passivation electrodes, reactor scale-up, reaction process design, and adaptation to complex industrial systems are outlined, and future perspectives are proposed. This review aims to provide theoretical and technical guidance for the green and low-carbon valorization of industrial sulfur-containing pollutants.

We report a drastic difference in stacking behavior of oleic acid-stabilized 4-monolayer (4 ML) CdSe nanoplatelets (NPLs) in toluene and methylcyclohexane (MCH), two nonpolar solvents that differ in the conformational flexibility of their molecules. Using liquid cell transmission electron microscopy (TEM) and small angle scattering (SAXS) techniques, we show that NPLs form microns-long ribbons consisting of 4 ML CdSe NPLs in toluene, the solvent widely used to form stable colloidal solutions of a broad range of quasi-spherical nanoparticles. In contrast, 4 ML CdSe NPLs are well dispersed in MCH. The difference in stacking behavior of NPLs in toluene and MCH suggests that the conformational flexibility of the solvent molecules, such as the ability to adopt multiple chair conformations, modulates nanoplatelet interactions. Molecular dynamics (MD) simulations reveal that solvent molecules subtly alter the structure of the organic ligand shell. These solvent-dependent changes propagate to the inorganic core, modulating the degree of CdSe nanoplatelet (NPL) twisting and, consequently, the properties of the nanoparticles. We show that toluene better solvates oleate ligands while MCH induces a bimodal oleate span distribution, which can lead to increased solubility of CdSe NPLs. In addition, the solvent can also influence the inorganic core, which, in turn, can modify the nanoparticle properties. We demonstrate that destabilization of toluene solution containing ribbons of 4 ML CdSe NPLs without CdS shells results in the formation of NPL assemblies with amplified spontaneous emission (ASE) with a low threshold of 14 &#xb5;J cm-2 that is comparable with that of CdSe/CdS core/shell NPLs. Our results emphasize that the solvent plays a major role in mediating interactions between NPLs and hence their processability for fabrication of functional structures.

This study aimed to biosynthesize silver nanoparticles using Elaeagnus angustifolia flower buds-an Iranian medicinal plant extract rich in bioactive phytochemicals and evaluate their antimicrobial potential through complementary broth microdilution (MIC/MBC) and agar well diffusion assays, alongside an assessment of their anticancer and biomolecular interaction properties. The synthesis leverages natural reducing and capping agents (phenols, flavonoids, tannins) to produce stable, spherical AgNPs (FEA@AgNPs), characterized by UV-vis (&#x3bb; max&#x2009;=&#x2009;439&#x2009;nm), XRD (&#x223c;10&#x2009;nm, face-centered cubic), FESEM, TEM (6.61&#x2009;nm), and FT-IR. A zeta potential of -32.68&#x2009;mV confirmed colloidal stability. The nanoparticles were stable for over a month, indicating that E. angustifolia flower aqueous extract is suitable for their preparation and stabilization. FEA@AgNPs showed moderate activity against S. aureus (12 vs. 24&#x2009;mm for gentamicin) and no agar diffusion inhibition against E. coli, despite a MIC of 37.5&#x2009;&#x3bc;g/mL in the broth assay. The antioxidant results show 55% DPPH radical scavenging at 160&#x2009;&#x3bc;g/mL. Notably, they induced dose- and time-dependent cytotoxicity in PC3 and AGS cancer cells, with IC50 values of 7.49 and 5.33&#x2009;&#x3bc;g/mL, respectively, after 72&#x2009;h (p < 0.05). Spectroscopic analyses revealed a strong binding affinity to calf thymus DNA and human serum albumin, suggesting biomolecular interaction capacity relevant to drug delivery. This work provides a green, efficient route to multifunctional AgNPs, bridging traditional herbal knowledge and bioinorganic nanomedicine for potential applications in infection control and oncology.