Wireless nanopore electrodes (WNEs) exploit bipolar electrochemistry to provide stable and reproducible nanoscale electrochemical interfaces. The conductive material at the nanopore tip serves as a well-defined sensing interface. This feature enables high spatial and temporal resolution while eliminating the need for traditional wire sealing and thereby avoiding noise or instability arising from the contacted electrode. Therefore, the WNE has become a powerful tool in nanoelectrochemistry with broad applications across electroanalysis and electrocatalysis. This perspective outlines the fabrication of closed-type and open-type WNEs and discusses their applications in monitoring the growth of catalytic materials, assessing electrocatalytic activity, and performing intracellular measurements. Special emphasis is placed on their integration with mass spectrometry and optical spectroscopy to achieve multidimensional insights. Finally, we highlight future research directions, focusing on enhancing stability, precise surface functionalization, and the development of miniaturized, portable devices for practical use.

Metabolic analysis of tumor cells is crucial for understanding tumor metabolic reprogramming, and single-cell metabolic accumulation studies provide precise insights into tumor biology. In this work, we established a microfluidic assay for single-cell metabolic accumulation analysis by combining droplet-generated hydrogel microspheres for single-cell encapsulation with a microchamber culture chip for microsphere isolation and 3D cultivation. This system enables efficient accumulation of secreted metabolites from individual cells for downstream analysis. Coupled with mass spectrometry, this system revealed metabolic accumulation heterogeneity among individual cells of the same tumor type. Moreover, metabolic profiling of different tumor types, including A549, HepG2, and HCT116, demonstrated distinct metabolic patterns, enabling cell classification based on accumulation differences. The method supports high-throughput, multiplexed, and dynamic metabolic analysis in a 3D single-cell context, offering a scalable strategy for decoding tumor heterogeneity with potential application in cell-state characterization and advancing oncology research.

Interest in photosensitive molecules has increased significantly over the past decade, with particular attention given to photoswitchable systems. Among these, azobenzene stands out as a reference compound due to its broad range of applications, in particular for solar energy storage. While the trans-to-cis photoisomerization has been relatively well characterized, the reverse cis-to-trans isomerization remains a complex process potentially involving multi-state physics. In this study, we compile recent theoretical advances aimed at modeling this process and introduce, through the spin-flip time-dependent density functional theory (SF-TDDFT) approach combined with the semi-classical Marcus equation, a fast and efficient method to investigate the mechanisms of thermal back-isomerization of azo derivatives. By comparing various exchange–correlation functionals with CASPT2 reference data, we demonstrate that the PBE0(D3BJ) functional provides an accurate description for the non-adiabatic rotational pathway. We successfully reproduce the experimental values (88.6 vs. 88.3 kJ mol−1 for the experimental enthalpy of activation, and −53.0 vs. −50.2 J mol−1 K−1 for the experimental entropy of activation) for azobenzene, thus motivating the extension of this methodology to other azo derivatives. This approach can be further generalized to a broader class of azo-based photo-switches in future studies.

Anisotropic hierarchically porous metal–organic frameworks (MOFs) with asymmetric morphologies hold great promise for improving the utilization efficiency of the MOF matrix, thereby expanding their applicability. However, imparting MOFs with precisely controlled porous architectures and morphologies remains challenging. Here, an ingenious soft/hard matter phase transition co-mediated assembly strategy is developed to mimic the biomineralization process for synthesizing anisotropic UiO-66-NH2 mesoporous nanobowls (UiO-66-NH2 mesoNBs). This process relies on in situ generated amorphous lamellar anionic surfactant/Zr-oxo cluster complexes as metal sources and templates. This is followed by the slow decomposition of complexes and the co-assembly of ternary mixed micelles and MOF precursors on their surfaces, creating crystalline UiO-66-NH2 mesoNBs with cylindrical mesochannels. The phase transition from lamellar to cylindrical mesophases is co-driven by changes in the packing parameters caused by the “soft” surfactant reorganization and variations in the charge density of the “hard” framework during crystallization from amorphous Zr-oxo clusters to the crystalline MOF matrix. By varying the surfactant ratios, UiO-66-NH2 can form diverse novel nanostructures and achieve well-tailored pore sizes within the small mesoporous range. This work provides fundamental insights into the transformation processes in amphiphilic molecule-directed MOF biomimetic mineralization and offers a promising strategy for constructing anisotropic hierarchically porous MOFs with high structural tunability.

Achieving tunable full-color emission and high-efficiency circularly polarized luminescence (CPL) from a single type of nanocluster remains a major challenge due to weak dissymmetry factors and aggregation-induced quenching. This study reports a breakthrough synthesis of full-color-emitting gold nanoclusters via heterometallic ion doping. By reducing HAuCl4 with 4-amino-2-mercaptopyrimidine (AMP) in the presence of Cr3+, Mg2+, or Ag+, blue (400 nm), green (495 nm), and red (700 nm) emissive NCs were obtained with respective quantum yields of 13.2%, 2.46%, and 3.34%. Structural analysis confirmed compositions of Au7(AMP)5Cr2, Au6(AMP)4Mg2, and Au6(AMP)3Ag, all <1.1 nm. Density functional theory calculations further reveal that b-NCs, g-NCs and r-NCs regulate emission energy through local coordination, electronic coupling, and structural rigidity of the Au(i)-SR framework. In summary, dopant ions serve as cross-linkers in surface Au(i)-thiolate motifs, with motif length determining emission color. Co-assembly with chiral lipid gelators induced full-color CPL (g lum = 10-2) via structural rigidification within helical nanotubes. The NCs showed low cytotoxicity and enabled multicolor bioimaging. Anti-counterfeiting gels with dual-level encryption were developed using UV-triggered fluorescence and CPL-handedness. The materials remained stable over one month. This work establishes a metal-ion-directed strategy for emission tuning in Au NCs, linking structures to photophysical properties and offering a flexible platform for chiral optoelectronics.

We report the first wavelength-dependent quantum yields of a [2 + 2] photocycloaddition generating the heterodimers of 7-hydroxycoumarin (7HCou) and styrene via a photochemical action plot. The wavelength-dependent heterodimer quantum yields are quantified at a constant number of photons at each wavelength between 310 and 370 nm. The resulting wavelength-dependent quantum yields demonstrate that the heterodimer is most efficiently generated at 345 nm, red-shifted by close to 25 nm compared to the absorption maximum of 7HCou at 320 nm. We subsequently translate these findings to photochemical surface functionalization by exploiting heterodimer formation between a surface bound coumarin derivative and para-styrene perfluoroalkyl ether (StyPFA) on surfaces under 345 nm irradiation to reversibly modulate surface hydrophobicity. The reversibility of the surface heterodimerization is demonstrated by removing StyPFA under UVC irradiation, and re-functionalization on the same surface. Functional heterodimer formation and the reversibility of the reaction on surface are followed via surface-sensitive X-ray photoelectron spectroscopy (XPS) and contact angle measurements. We subsequently apply our photochemical surface functionalization strategy to a dual cure photoresin based on a polyurethane-acrylate interpenetrating network, without deterioration of its mechanical properties, thereby confirming the feasibility of a photocycloaddition-based functionalization strategy for photoresins.

Understanding the sodium-storage mechanism in hard carbon (HC) anodes is crucial for advancing sodium-ion battery (SIB) technology. However, the intrinsic complexity of HC microstructures and their interactions with sodium remain not fully elucidated. We present a multiscale methodology that integrates grand-canonical Monte Carlo (GCMC) simulations with a machine-learning interatomic potential based on the Gaussian approximation potential (GAP) framework to investigate sodium insertion mechanisms in hard carbons with different levels of porosity, achieved by simulating structural models with densities ranging from 0.7 to 1.9 g cm-3. Structural and thermodynamic analyses reveal the interplay between pore size and accessibility and the relative contributions of adsorption, intercalation, and pore filling to the overall storage capacity. Low-density carbons favor pore-filling, achieving extremely high capacities at near-zero voltages, whereas high-density carbons primarily store sodium through adsorption and intercalation, leading to lower but more stable capacities. Intermediate-density carbons (1.3-1.6 g cm-3) provide the most balanced performance, combining moderate capacity (480 and 310 mAh g-1), safe operating voltages, and minimal volume expansion (<10%). These findings establish a direct correlation between carbon density and electrochemical behavior, providing atomic-scale insight into how hard carbon morphology governs sodium storage. The proposed framework offers a rational design principle for optimizing HC-based SIB anodes toward high energy density and long-term cycling stability.

Recent advances in isolating and characterizing reactive aluminylenes and aluminyl anions have redefined the landscape of low-valent aluminum chemistry. Study of these molecules that span a wide range of structures and ligand environments have helped established new paradigms in main-group metal bonding and reactivity; however, their controlled access remains limited by aggregation, disproportionation, and oxidation of reactive Al(i) intermediates. Herein, we establish aluminylation as a generalizable redox-neutral synthetic route to low-valent aluminum complexes. By circumventing the use of external reductants through metathesis reactions between Al(i) precursors and alkali metal ligand salts, we can access novel heteroleptic clusters as well as known aluminyl complexes with improved yields or under more mild conditions. We demonstrate that the equilibrium of the Al(i) precursor between monomeric or oligomeric cyclopentadienyl aluminum species directly governs reaction outcomes and enables selective formation of products across multiple ligand classes.

Triflate salts of phosphito-phosphanides [LCP-P(OR)3]+ (1[OTf], R = alkyl, LC = N-heterocyclic carbene) were obtained via nucleophilic fragmentation of the tetraphosphetane [(LC)4P4][OTf]4 (3[OTf]4) with organophosphites P(OR)3. The salts 1[OTf] act as versatile reagents in the cationic Phospha-Wittig reaction, converting aldehydes into imidazoliumyl-substituted phosphaalkenes 2[OTf] and, via a competing pathway, into diphosphiranes 4[OTf]2. The product distribution is governed by the aldehyde substituent, enabling selective access to isolable derivatives of both compound classes. The resulting phosphaalkenes 2[OTf] serve as precursors to diverse phosphorus heterocycles, undergoing expected [2 + 2] dimerisation to 1,3-diphosphetanes syn/anti-(2)2[OTf]2 and trapping reactions with 1,3-dienes to yield the tetrahydrophosphinine 8[OTf] and bicyclic derivative 9[OTf]. Most notably, an unprecedented annulative [4 + 2] dimerisation pathway for cationic C-aryl phosphaalkenes is uncovered that furnishes benzannulated tetrahydro-1,2-diphosphinines 7[OTf]2. Computational studies reveal that the operative mechanism of this transformation involves a Phospha-Diels-Alder step followed by an acid-base-catalytic proton transfer, which is calculated to be energetically more accessible than the classical [2 + 2] dimerisation.

Although single-atom Fe-N-C catalysts exhibit outstanding oxygen reduction reaction (ORR) activity, their stability presents challenges due to the oxidation and destruction of Fe-N x active sites by Fenton-like reactions, severely restricting their application in energy storage and conversion technologies. Here, we construct a dual-atom oxygen electrocatalyst (FeMo/NC) with FeMoN7 active sites, which demonstrates excellent bifunctional oxygen electrocatalysis performance. The FeMo/NC-based zinc-air battery (ZAB) can operate continuously for over 200 h without significant activity decay, making it superior to the Fe/NC-based ZAB. In situ X-ray absorption spectroscopy (XAS) and Raman characterizations reveal the formation of the *Fe-O-O-Mo* intermediate with an oxygen bridge bond, which synergistically enables adsorption or desorption of O2 through the Fe-Mo dual-atom sites, avoiding the limitations of the linear scaling relationship and thereby accelerating the oxygen electrocatalysis process. Density functional theory calculations reveal that the bridged oxygen adsorption mode on the Fe-Mo dual-atom sites exhibits lower energy barriers compared to that on single Fe/Mo sites, favoring the oxygen electrocatalysis.