ChemistryEurope最新文献

The Cover Feature shows a skeletal-editing strategy that transforms pyridines into anilines through carbene insertion followed by nitrogen isomerization. By externalizing the original pyridine nitrogen to the ipso or ortho position without changing the ring size, this method enables direct pyridine-to-aniline conversion and provides a new platform for nitrogen scanning, scaffold remodeling, and late-stage diversification of bioactive molecules. For more details, see the Research Article by Y. Luo, J. Dai, Y. Wei and C. Min (DOI: 10.1002/ceur.202500410).

The Cover Feature shows how molecular engineering of an active copper surface by click chemistry creates a unique environment that excludes water while enabling proton transport through its framework, thereby profoundly influencing the CO₂ electrolysis process. Layer adsorption stabilizes copper surfaces with distinct morphologies, leading to markedly different CO₂ reduction products and significantly suppressing hydrogen evolution. More information can be found in the Research Article by A. Kuzume, S. Kume and co-workers (DOI: 10.1002/ceur.202500330).

The Front Cover depicts the formation of pentalene, visualized as a Cuneane flower arrangement being unfolded by rhodium (Rh) while a nucleophile “flower” is inserted into it. This scene symbolizes the scaffold editing of cuneane. More information can be found in the Research Article by H. Takebe and S. Matsubara (DOI: 10.1002/ceur.202500225). Artwork by H.T.

The Cover Feature illustrates the adsorption of PFOA from contaminated water. Graphene sheets were functionalized with a positive charge and a polyfluorinated alkyl chain, enabling efficient capture of PFOA. Notably, the removal efficiency of shorter-chain PFAS was also enhanced. Further details are provided in the Research Article by R. Haag, I. Donskyi, and co-workers (DOI: 10.1002/ceur.202500240).

Copper(I)-catalyzed azide–alkyne cycloaddition between (1R, 2R)- or (1S, 2S)−1,2-diazidocyclohexane and 1,3-diethynylbenzene resulted in cyclic polymer and linear–cyclic mixture polymer bearing 1,2,3-triazole units in the main chain, respectively, at a lower and higher monomer concentrations in feed. The polymers showed circularly dichroism (CD) spectra in solution and in film reflecting their conformational chirality where sign and intensity were modulated by protonation of 1,2,3-triazole units with CH₃SO₃H. Films composed of the polymers and pyrene exhibited efficient CD signals as well as circularly polarized luminescence (CPLm) arising from pyrene through chirality transfer from the polymers to pyrene where anisotropy factor (g_lum) was as high as of 10⁻² order. The cyclic polymer showed more efficient transfer. The sign of CPLm was unexpectedly reversed by protonation of 1,2,3-triazole units both for cyclic and linear–cyclic mixture polymers. Chirality transfer was confirmed for cyclic polymer even in solution by CD and CPLm but not for linear–cyclic mixture polymer. Thus, the chain topology, cyclic or linear, and the charge state were demonstrated to remarkably affect the chirality functions.

The capacious and rigid mausolate ligand [1]²⁻ has the capacity to adaptively coordinate some of the largest metal cations on the periodic table, such as those which are utilized in targeted alpha-particle therapy. One such ion, Ra²⁺, has proven challenging to keep securely contained by other chelators. Here we investigate the binding behavior of Ba²⁺ (≈96% the size of Ra²⁺ but conveniently nonradioactive) with the mausolate [1]²⁻ along with Mg²⁺, Ca²⁺, and Sr²⁺, principally utilizing real-time electrospray ionization mass spectrometry monitoring. We also report the syntheses of several functionalized mausolate derivatives, [3–5]²⁻, and compare their binding abilities with previously reported variants. We find that the mausolates display a distinct preference for larger alkaline earth metals, with Ba²⁺ showing extremely rapid uptake and promising stability in a number of physiologically relevant conditions. We also demonstrate a thermodynamic preference of Ba²⁺ for the mausolate over some other well-known chelators. The incorporation of a reactive bromine atom in the 4-pyridine position of the mausolate ([3]²⁻) can be utilized to introduce further functionalization through a nucleophilic substitution pathway without compromising coordination ability.

A new molecular nanographene, adamanphene, has been designed and synthesized by integrating an adamantane core with four peripheral hexa-peri-hexabenzocoronene (HBC) units, thus combining structural motifs reminiscent of two carbon allotropes, diamond (3D) and graphene (2D). The synthetic route enables the construction of this hybrid architecture with full control over the spatial arrangement of the HBC fragments. Single-crystal X-ray diffraction confirms a rigid tetrahedral framework that assembles into an open, highly porous packing supported by intermolecular π–π interactions. The electrochemical behavior of adamanphene reveals features of electronically decoupled HBC chromophores, while spectroscopic studies show absorption and emission profiles closely related to those of reference HBC derivatives. Notably, adamanphene exhibits distinct fluorescence behavior in solution and in the aggregated state, displaying a clear change in the color and shape of the emission upon increasing the proportion of poorly solubilizing solvent (e.g., water). TD-DFT calculations reproduce the main experimental features and provide insight into the nature of the electronic transitions involved. The combination of a three-dimensional sp³ carbon core with multiple extended sp² π-surfaces defines adamanphene as a unique molecular platform for exploring the interplay between dimensionality, supramolecular organization, and photophysical response in carbon-based nanostructures.

Developing highly efficient electrocatalysts for the oxidation of ethylene glycol to produce high-value-added chemicals is crucial for enhancing electrocatalytic performance of direct fuel cells and achieving high-value utilization of waste resources. This study successfully synthesized ultrathin, highly branched gold–copper nanodendrites (AuCu NDs) via a one-pot synthesis strategy using surfactant templates. Systematic characterization revealed that carboxyl-functionalized surfactants are crucial for forming the two-dimensional dendritic structure, while the doping of Cu effectively modulates the electronic structure of Au crystals. When applied to EGOR, AuCu NDs exhibited outstanding catalytic performance with a mass activity of 7.93 A mg_Au⁻¹, ≈6.54 times as that of commercial Pd/C catalysts, while maintaining excellent stability after 5000 s of constant current testing. NMR analysis confirmed the simultaneous presence of formic acid and glycolic acid in the electrolytic products, indicating that this catalyst possesses both efficient CC bond cleavage and a certain degree of CC bond retention capability, thereby achieving control over the reaction pathway. This work provides a universal synthetic strategy for designing high-performance gold-based bimetallic electrocatalysts for the high-value conversion of polyethylene terephthalate (PET) waste.

Phosphorus-based anodes are gaining attention for high energy/power density lithium-ion batteries (LIBs) due to their high theoretical capacity and moderate operating potential. Recent studies indicated the possible dissolution of lithium phosphide intermediates (LiPIs) in organic solvents, raising concerns about whether phosphorus anodes in LIB systems might face similar dissolution issues as sulfur cathodes in lithium-sulfur batteries. We investigated the dissolution property of LiPIs in ester electrolytes with different lithium salts, using semi-quantitative liquid nuclear magnetic resonance for analysis. Our results indicate that no polyphosphide anions such as P₅⁻, P₇³⁻, P₁₆²⁻, and P₂₁³⁻ were detected in the cycled ethylene carbonate (EC)-based electrolyte, only F₂PO₂Li and OPF₂(OC₂H₅) were present. Further X-ray photoelectron spectroscopy shows no phosphorus element detected on the counter electrode when using EC-based electrolyte. These suggest that the LiPIs have very low solubility in EC-based electrolytes, below 0.1 mM, thus preventing shuttle effects similar to those in lithium-sulfur batteries. Our study addresses concerns from academia and industry about LiPIs dissolution, confirming the stability and safety of phosphorus-based anodes for high-performance LIBs.

A modular family of gold(I) complexes containing the thiopurine bases 6-mercaptopurine (6-MP) or 6-thioguanine (6-TG), phosphine or N-heterocyclic carbene ligands, and appended chromophores (dansyl or nitrobenzoxadiazole, NBD) has been synthesized to develop multimodal chemotherapeutic and photodynamic agents. Whereas gold–thiopurine complexes have been previously explored for dark cytotoxicity, their photodynamic activity and chromophore-engineered photoresponse remain unreported. The dansyl derivatives display dual emission arising from intramolecular ligand-to-ligand energy transfer, while the NBD conjugate exhibits a single band with enhanced photoresponsiveness. All complexes show good stability and moderate lipophilicity, supporting efficient uptake. Cytotoxicity studies in A549 cells reveal clear trends: 6-TG increases intrinsic cytotoxicity, whereas 6-MP provides lower dark toxicity and superior performance upon irradiation. The PPh₃ ligand affords the highest phototoxicity indices, and NBD incorporation delivers the strongest photoenhancement, improving IC₅₀ values by up to an order of magnitude. Mechanistic analyses demonstrate a unified, redox-mediated apoptotic pathway involving thioredoxin reductase inhibition, reactive oxygen species overproduction, mitochondrial depolarization, partial DNA intercalation, and S-phase arrest. The photoresponse exhibits clear chromophore dependence, with the NBD–functionalized complex producing singlet oxygen, while the dansyl-based derivatives favor enhanced hydrogen peroxide generation. These findings establish chromophore-functionalized gold–thiopurine complexes as a novel and tunable platform for next-generation multimodal gold-based anticancer agents.