The first examples of covalently linked, β-meso-phenyl ethyne bridged dyads 1-6 containing 14π triphyrin(2.1.1)/metallotriphyrin, and 18π porphyrin/metalloporphyrin subunits were synthesized in decent yields. The free base 14π triphyrin(2.1.1)-18π porphyrin(1.1.1.1) dyad 1 was prepared by Sonogashira cross coupling of β-monobromo triphyrin(2.1.1) 7 and 5-[4-ethynylphenyl]-10,15,20-tri(p-tolyl) porphyrin 8 in toluene/TEA at 40°C for 12 h. The triphyrin(2.1.1)-metalloporphyrin dyads 2, 3, and 4 were obtained by treating free base dyad 1 with NiCl, CuCl, and Zn(CHCOO) salts, respectively, in CHCl/CHOH at reflux, whereas metallotriphyrin-metalloporphyrin dyads 5 and 6 were synthesized by reacting dyads 2 and 4, respectively, with Re(CO)Cl in toluene/TEA under refluxing conditions. Dyads 1-6 are very unique and contain two different types of aromatic conjugated macrocycles, such as contracted 14π triphyrin(2.1.1) and regular 18π porphyrin(1.1.1.1), having different properties. The absorption and the electrochemical studies supported weak interactions between the subunits in dyads 1-6. The density functional theory (DFT) studies revealed that in dyads 1-6, the triphyrin(2.1.1)/metallotriphyrin and porphyrin/metalloporphyrin units were oriented with a dihedral angle in the range of 24°-65° with respect to each other.

In this study, a hierarchical porous (HP) AlO/HP-UiO-66 composite was prepared via a facile template and solvothermal strategy. The material exhibits a high adsorption capacity for phosphate, with a maximum theoretical value of 303 mg/g based on the Langmuir model-eight times greater than that of the original UiO-66. It also displays excellent selectivity for phosphate over common ions in domestic wastewater, along with a wide pH stability range (2-10) and rapid adsorption equilibrium, reaching saturation within 90 min. Moreover, the composite maintains over 85% of its adsorption efficiency after six cycles. These results demonstrate that AlO/HP-UiO-66 possesses enhanced adsorption capacity, faster kinetics, improved acid-base resistance, and superior selectivity, highlighting its potential for effective phosphate removal from wastewater.

An efficient Rh(III)-catalyzed pivaloyl-directed strategy has been developed for the C7-(acyl)alkylation of tryptophans with substituted and unsubstituted allyl alcohols, delivering tryptophan-based unnatural amino acids without compromising their chirality. The disclosed methodology showcased high tolerance of neutral, acidic, and basic amino acids, including Gly, Ala, Val, Leu, Phe, Pro, Asp, Lys, and Thr units, enabling regioselective late-stage functionalization of tryptophan units in a variety of tryptophan-containing dipeptides, tripeptides in reasonable yields.

Bifunctional electrocatalysts for overall water splitting (OWS) is critical for sustainable hydrogen production but remains challenging due to the sluggish kinetics and leaching of metal ions. Herein, we present a kind of phosphorus and molybdenum codoped ruthenium and ruthenium oxides heterostructure (P,Mo-Ru/RuO) as a highly efficient bifunctional electrocatalyst for alkaline OWS. The incorporation of P facilitates the electron transfer from P to Ru, leading to the partial reduction of RuO to metallic Ru. Moreover, the reduced oxidation of Ru suppresses the dissolution of RuO, favoring the structural stability. In alkaline media, P,Mo-Ru/RuO demonstrates enhanced hydrogen evolution and oxygen evolution activities, requiring overpotentials of only 61 and 230 mV, respectively, to achieve a current density of 10 mA cm . When employed as anode and cathode for OWS, the P,Mo-Ru/RuO catalyst enabled a low cell voltage of 1.50 V at 10 mA cm , along with an enhanced electrochemical stability. These results highlight the synergistic effect of anion and cation codoping in enhancing electrocatalytic performance, offering a promising strategy for the design of advanced bifunctional catalysts for sustainable hydrogen production.

Electrocatalytic oxidation of biomass molecules such as ethanol in hybrid alkaline water electrolysis is more thermodynamically favorable and techno-economic attractive to replace conventional pure water electrooxidation to produce green hydrogen. Herein, the flexible and binder-free hollow microtube catalyst arrays of CoS/CC, NiCoS/CC, FeNiCoS/CC, and FeNiCoS/CC were derived from metal-organic framework arrays anchored on carbon cloth (CC). These arrays exhibited favorable performance in electrochemical water oxidation, ethanol oxidation, and hydrogen evolution processes, because of their obvious advantages in high conductivity and long-term stability. The optimized self-supporting FeNi CoS/CC electrode composed of a 3D hollow porous microtube structure only needs a low potential of 1.412 and 1.267 V (vs. RHE) to deliver 10 mA cm current density for alkaline water and ethanol oxidation reactions, respectively. Simultaneously, the pure CoS/CC electrode presents excellent alkaline hydrogen production property among the series self-supporting electrodes with a low overpotential of 188 mV at 10 mA cm. In this work, it is proved that the hybrid water splitting system, using FeNiCoS/CC and CoS/CC as anode and cathode, respectively, can effectively reduce the cell voltage to 1.479 V to deliver 10 mA cm with high pure hydrogen generation and high valued potassium acetate generation.

In order to increase the photocatalytic activity of TiO-anchored meso-tetrakis(4-carboxyphenyl)porphyrin (HTCPP), TiO@HTCPP, in the aerobic oxidation of sulfides in water, KBr has been used as a source for the formation of the secondary oxidant, bromine. The change in the nature of reactive oxidant from superoxide anion radical to molecular bromine led to a significant increase in the efficiency of oxidation of the sulfide as well as the oxidative stability of the porphyrin photosensitizer. The contribution from different reactive oxygen species, hole and electron in the formation of sulfone as the sole product, has been studied using the scavengers of hydroxyl radical, superoxide anion radical, hole, electron, and singlet oxygen, and accordingly, a mechanism was proposed. Using sodium bromate instead of KBr led to a similar increase in the photocatalytic activity of TiO@HTCPP, which was attributed to the reduction of bromate to bromide under the reaction conditions.

Lithium-sulfur batteries are promising for meeting growing global energy needs and supporting sustainable development. However, the shuttle effect is a key barrier to their wide use. Reducing Li⁺ ion solvation is an effective solution. In this study, adiponitrile (ADN), featuring two highly electronegative cyano groups, forms a stable [Li(ADN)]⁺ complex that contracts the solvation shell of Li⁺. Its moderate molecular size also helps form a denser interfacial protective film on the sulfur cathode, boosting surface stability. Density functional theory (DFT) simulations show ADN's cyano groups bind strongly to Li⁺, forming stable local structures that suppress polysulfide migration and improve cycle stability. Experimentally, batteries with ADN retain 75% of initial capacity after 120 cycles at 0.2 C and have a 744 mAh g discharge capacity at 2 C. X-ray photoelectron spectroscopy (XPS) confirms ADN-Li⁺ interaction and reveals ADN's role in regulating the electrolyte's solvation environment. This work provides new insights for electrolyte design in next-generation Li-S batteries.

Reductive hydrofunctionalization of 1,3-dienes by transition-metal/SiH catalysis has emerged as a promising strategy for the rapid construction of molecular complexity from simple precursors. However, previous reports have predominantly focused on branched-selective 1,2-hydrofunctionalization pathways. Herein, we describe a reductive 1,2-hydrovinylation of 1,3-dienes with vinyl triflates that proceeds with exclusive linear selectivity. This transformation establishes a new selectivity paradigm in transition-metal/SiH catalysis, wherein a Ni-C insertion pathway overrides the classical Ni-H insertion process, enabled by the synergistic cooperation between NiBr and a CF-substituted PyrOX ligand. The reaction features a broad substrate scope, encompassing a wide range of aryl and heteroaryl 1,3-dienes as well as both cyclic and acyclic vinyl triflates.

Under the catalysis of p-TsOH immobilized on silica (PTS-Si), the iso-Nazarov reaction of (E)-(2-stilbenyl)methanol/(E)-(2-stilbenyl)imine tosylate bearing a styrene moiety forged the corresponding [5/6] systems with the exclusive trans relationship at the two newly formed adjacent stereogenic centers. The ensuing "interrupted" nucleophilic addition by the pendent styrenyl olefin furnished the dihydro-11H-benzo[a]fluorene with the exclusive cis stereocontrol at the two-carbon ring junction. Thus, from non-chiral starting materials, the interrupted iso-Nazarov reaction formed two rings and provided the olefin moiety, which can be functionalized to other groups/systems possessing one to two additional chiral centers. Up to five contiguous stereogenic centers on the tetrahydrobenzo[a]fluorene could be constructed efficiently.

A neutral Fe(II) sandwich complex bearing a π-phenol ligand with a trifluoroborate substituent [Cp*Fe(η-2-Bu-6-BF-CHOH)] is designed and prepared, which affords the corresponding anionic Fe(I) sandwich complex [Cp*Fe(η-2-Bu-6-BF-CHOH)] with an effective O-H bond dissociation free energy at 40.7 kcal/mol in tetrahydrofuran on treatment with KC. The anionic complex acts as a proton-coupled electron transfer reagent for the reduction of organic substrates such as acetophenone and anthracene, whereas the reaction with a Mo(IV) nitride complex leads to the stoichiometric formation of ammonia.

The selective hydrogenation of aromatic N-heterocycles is an important transformation in synthetic chemistry, as the resulting partially saturated derivatives are widely found in pharmaceuticals and bioactive molecules. In this context, quinolines are especially important, with 1,2,3,4-tetrahydroquinolines serving as the privileged scaffolds in various drugs. To achieve such selective hydrogenation, we herein describe the synthesis and characterization of a series of NHC-derived heteroditopic bidentate ligands, including a combination of imidazole-based N-heterocyclic carbene (ImNHC) with a triazole-derived "mesoionic" NHC (TzNHC) donor, supported by well-defined Co(III)-complexes. Among them, the mixed-NHC-based Co(III) catalyst enables efficient, additive-free transfer hydrogenation (TH) of diverse quinoline derivatives with excellent selectivity and tolerance to diverse functional groups. Mechanistic studies indicate that a cobalt-hydride intermediate is the active species, with the mixed donor carbene environment enhancing the hydride donor capability, enabling selective reduction.

Azo dyes such as Tartrazine (Tz) and Sunset Yellow (SY) are extensively used in food and consumer products, but their overuse poses significant health and environmental risks. Developing simple and reliable detection methods for dyes is, therefore, crucial. In the present study, Samarium-doped zinc oxide (Sm-ZnO) nanorods anchored on graphitic carbon nitride (gCN) sheets were synthesized via a hydrothermal route and further applied as a fluorometric sensor for Tz and SY. The gCN/Sm-ZnO hybrid showed strong blue fluorescence, which underwent pronounced quenching upon interaction with the dyes through a combination of the inner filter effect (IFE) and static quenching mechanisms. The probe showed excellent photostability and long-term thermal stability, retaining its fluorescence intensity even after prolonged irradiation and storage under varied temperature conditions. The sensor exhibited remarkable sensitivity, achieving detection limits of 0.164 µM for Tz and 0.305 µM for SY. To exemplify its practical utility, the probe was successfully applied to real-world matrices such as turmeric powder, soft drinks, cosmetics (face wash), and jellies, yielding high recovery rates of 93.33%-105.42% with good reusability. The synergistic combination of Sm-ZnO nanorods and gCN sheets enhanced charge transfer and amplified the fluorescence quenching response, offering a cost-effective and robust approach for monitoring synthetic colorants in complex samples.

Glycerol, the byproduct of a multi-ton biofuel industry, is a cheap and useful feedstock for value-added chemical transformations. The conversion of glycerol to lactic acid has been realized using pincer complexes, mainly based on 4d and 5d transition metals. Herein, a well-defined, nonsymmetrical PNP-Fe complex (Fe-1) was synthesized and characterized. Single-crystal x-ray diffraction (SC-XRD) revealed a distorted square pyramidal geometry, while spectroscopic analysis and the Evans method confirmed a high-spin Fe(II) center. The complex Fe-1 performed glycerol to lactate transformation with an excellent yield and selectivity of up to 87%. Furthermore, a series of control experiments demonstrated the molecular nature of the transformation and elucidated the role of the catalyst in the organic cascade.

Multicomponent reactions (MCRs) are powerful tools for the rapid construction of complex molecules, as they enable the assembly of diverse functional fragments into a single skeleton. Herein, we report an efficient and practical copper-catalyzed multicomponent radical process that couples readily available Togni's reagent II, alkenes, and alkynes to afford β-trifluoromethyl propynes with high regioselectivity. Under mild copper-catalyzed conditions, this strategy enables chemoselective and regioselective radical trifluoromethylalkynylation of alkenes while suppressing undesired copper-catalyzed or radical-mediated side reactions. The method exhibits a broad substrate scope for both alkenes and alkynes, with excellent functional group compatibility.

The development of metal-organic gels as chemosensors for detecting metal ions has gained significant attention due to their critical roles in biological and environmental systems. Among these, the detection and quantification of Cu⁺ ions are particularly important, given the widespread industrial applications and the toxicity of its salts at elevated concentrations. Coumarin-based fluorescent chemosensors have emerged as promising candidates due to their low toxicity and ease of functionalization. In this study, we report the synthesis and characterization of N-(7-hydroxy-4-methyl-8-coumarinyl)-leucine (Hmuleu) and its metal complexes. Remarkably, the Ca⁺ complex forms a coordination polymeric (CP) gel, with gelation being highly specific to the choice of metal salt, ligand, and solvent. The resulting metal-organogel exhibits intense blue fluorescence at 455 nm, with significantly enhanced emission compared to the free Hmuleu ligand. Both Hmuleu and its Ca⁺ complex demonstrate high selectivity and sensitivity as fluorescent chemosensors for Cu⁺ ions, especially as nitrate ions in aqueous media, with low detection limits. Notably, the fluorescence is completely quenched upon interaction with Cu⁺ ions, enabling naked-eye detection under UV light. This work introduces a rare water-soluble, highly selective, and sensitive chemosensor system for Cu⁺ ions, with potential applications in biological and environmental monitoring.

A facile and efficient approach for the halospirocyclization of N-benzylpropiolamides has been developed. Employing N-halosuccinimides (NXS) as halogenating reagents, this reaction proceeds smoothly at room temperature without the need for photochemistry, electrochemistry, or metal reagents. A diverse array of halogenated azaspiro[5.5]undecanones was obtained in moderate to excellent yields, displaying excellent functional group tolerance. The gram-scale reaction and the synthesis of brominated 2-oxaspiro[5.5]undecanone further underscore the scalability and practicality of this method.

The chemical modification and self-assembly capability of fullerenes offer advantageous conditions for tailoring Fe/N-doped carbon-based catalysts. However, their strong π-π stacking tendency may partially restrict metal loading and the generation of active Fe species. Therefore, how to utilize the distinctive features of fullerenes to precisely regulate and optimize Fe-N active sites along with their local coordination environment remains challenging. In this work, water-soluble C (wsC) was synthesized via a facile interfacial oxidation process. The presence of -OH on the C cage may strengthen its binding affinity with Fe ion and effectively modulate the incorporation of Fe/N into the C-derived carbon electrodes. By varying the wsC/Fe mixing ratios followed by pyrolysis under NH, we obtained Fe/N-doped carbons (FeN@wsC-900) with distinct Fe/N-doping states, including FeN, O-FeN/Fe cluster, and FeN/Fe cluster. The abundant -OH in wsC also promoted the formation of a highly porous network, enhancing active site accessibility. The resultant FeN@wsC-900 exhibited excellent oxygen reduction reaction (ORR) activity, outperforming both conventional C-derived carbons and commercial Pt/C. Structural characterizations and density functional theory (DFT) simulations revealed that the O-coordinated Fe-N with adjacent Fe cluster could optimize the coordinate geometry and adsorption energies of key ORR intermediates.

A metal-free selective selenylation and sulfonylation of 1,7-dienes with selenosulfonates for divergent synthesis of seleno-/sulfonyl-benzoxepines has been developed. This reaction was conducted under mild conditions without any catalysts, oxidants, or additives. The choice of solvent plays a crucial role in determining the formation of seleno-/sulfonyl-benzoxepines. Preliminary mechanistic studies suggest that both the selenylation and sulfonylation are accomplished through a selenyl radical and a sulfonyl radical cyclization process.

Nanosponges (NSPs), a class of porous, tunable, and high-surface-area materials, have emerged as next-generation platforms for chemo- and bio-sensing applications, enabling enhanced detection sensitivity, selectivity, and real-time responsiveness. Their unique architecture, engineered through metal-based, metal-oxide, and hybrid frameworks, offers controlled porosity, flexibility in functionalization, and high analyte-binding affinity. Over the past decade, NSPs have been progressively integrated into optical, electrochemical, and enzymatic sensor systems, targeting environmental toxins, toxic gases, metal ions, and biological markers. This review systematically discusses the structural fundamentals of NSPs, including polymeric backbones, crosslinking chemistry, and active sites responsible for molecular recognition. A critical analysis of NSP functionalization strategies, fabrication factors, and performance limitations is presented to guide material optimization. Applications are explored across chemosensing (heavy metal ion detection, toxic gas analysis) and biosensing (glucose, enzyme activity, and pathogen identification), highlighting the integration of NSPs into field-deployable diagnostic platforms. Furthermore, the review outlines the key challenges in NSP-based sensor technology, such as stability, reusability, and multiplexed detection, and provides a future outlook on their role in intelligent, miniaturized, and sustainable sensing devices for environmental and healthcare diagnostics.

Zirconium phosphates are stable under thermal and acidic conditions, making them useful ion exchangers for recovering rare earth elements from bauxite residues. This study evaluates the selective uptake of Sc by α-disodium zirconium phosphate (α-NaZrP) and α-magnesium zirconium phosphate (α-MgZrP), both prepared via a minimalistic mechanochemical route that uses only the water present in the reactants for homogenization and employs stoichiometric or close-to-stoichiometric reactant ratios. Both crystalline materials show high selectivity for scandium in the presence of other rare earth ions and iron which shares similar chemical properties and occurs at much higher concentrations. α-MgZrP displays a high uptake at low Sc concentrations compared with α-NaZrP. However, its overall capacity is only 0.56 versus 1.2 mmol/g for α-NaZrP, illustrating differences in their low-concentration uptake efficiency and total loading. Stripping the Sc-loaded ion exchangers with HPO results in pure α-zirconium phosphate (α-ZrP; Zr(HPO)∙HO), indicating complete removal of the exchanged Sc.

A concise synthetic route to the difluorinated para-quinone monoacetals (p-QMAs) and their reactivity is described. Featuring a cross-conjugated dienone core and an acetal unit, these compounds undergo diverse nucleophilic additions at the enone moiety and cycloadditions at the C═C bond. Such distinctive reactivity renders the β,β'-difluoro p-QMA a versatile building block for the rapid assembly of complex molecular architectures, highlighting its promise in natural product synthesis and material sciences.