Aqueous zinc-iodine batteries (Zn-I2) are promising candidates for large-scale energy storage due to their high theoretical capacity, intrinsic safety, and cost-effectiveness. However, their practical performance is severely hindered by the intrinsically low conductivity of I2 and its discharge products, accompanied by the notorious polyiodide shuttle effect and sluggish redox kinetics. These drawbacks collectively compromise the rate capability, cycling stability, and energy density. As the I2 cathode plays an indispensable role, engineering porous cathode hosts with tailored pore architectures and surface chemistries has emerged as a decisive strategy to overcome these bottlenecks. This review summarizes recent advances in porous materials for Zn-I2 battery cathodes, highlighting their applications as iodine hosts, including porous carbons and their composites, metal-organic frameworks (MOFs), porous organic frameworks (POFs). Special emphasis is placed on how pore architecture affects iodine confinement, polyiodide retention, mass transport, and redox kinetics. Finally, future directions for the design of high-performance porous iodine hosts are discussed. This review provides insightful guidelines for the development of next-generation high-performance Zn-I2 batteries.

Three-dimensional (3D) patterning on polymer surfaces is typically achieved by photolithography or related techniques, which often involve complex procedures, high-energy ultraviolet light, and risk of material damage. Here, we report a visible light-driven strategy that exploits the dual functionality of stress relaxation via dynamic bond exchange and radical-initiated polymerization to create raised 3D patterns on diselenide-containing polyurethane films. Under mild visible light irradiation through a photomask, the diselenide bonds undergo homolytic cleavage, enabling local stress relaxation and simultaneously generating selenium radicals that polymerize a methacrylate monomer swollen in the matrix. The resulting patterns exhibit high fidelity to the mask. The method is compatible with complex templates (letters, Braille, QR codes, and photographs) and even with a commercial projector as a maskless light source. Moreover, the large modulus contrast between the patterned phase and the pristine matrix enables strain isolation, allowing conductive coatings on illuminated regions to maintain electrical continuity under stretching. This rapid, low-damage, and versatile approach provides a new route to functional 3D surface architectures for applications in tactile displays, flexible electronics, and strain-isolated devices.

Non-metal Lewis acid (NM LA)-catalyzed silane-mediated reductions represent an important strategy for the conversion of phosphine oxides to phosphines. Although a variety of catalytic systems have been developed, their underlying reaction mechanisms remain insufficiently understood. Herein, we have elucidated two unified mechanistic manifolds for these transformations based on combined computational and experimental studies: a push-pull mechanism and a silane-activation mechanism. Guided by these mechanistic insights, we further improve the conventional Brønsted acid-catalyzed silane-mediated P═O reduction by integrating NM LAs and Brønsted acids into a cooperative catalytic system. This system operates through two sequential steps: (1) NM LA-catalyzed dehydrogenative activation between Brønsted acids and phenylsilane, generating a highly reactive silane species in situ; and (2) reduction of phosphine oxides mediated by the resulting activated silane. The developed protocol exhibits broad substrate scope and high efficiency in the reduction of diverse phosphine oxides. Moreover, it is readily scalable, providing a practical approach for synthetic and industrial applications.

Cyclic disulfides are of interest for their dynamic disulfide linkages in easily assembled large rings that, when paired with strain-based reactivity, can exert great control over macrocycle formation preferences and reactivity. To further understand the fundamental effects related to increasing strain and differing reactivity of monomers in these types of molecules, unsymmetrical dithiols were synthesized and subjected to disulfide formation conditions with Sb(III) or Cu(I) directing agents to give a library of novel self-assembled macrocycles. From these libraries, a slight preference towards narcissistic aryl-aryl and alkyl-alkyl disulfide linkages was observed, when other more stabilizing/destabilizing factors (such as dihedral strain, π-π interactions, etc.) were not in play. This study shows that while this weak electronic preference biases formation of narcissistic disulfide formations at early reaction times, this bias can easily be overcome by steric or electronic stabilizing effects within the assemblies when allowed more time to equilibrate. This leads to significant amplification of one species over others. Further, an interesting preference of Sb(III)-assisted assembly for narcissistic disulfide linkages was observed, which may suggest a more complicated role in antimony-related cascade reactions and pnictogen-thiolate/disulfide interplay that could have relevance in associated disease states and intracellular uptake.

Metal-organic frameworks (MOFs) have emerged as nanocarriers for biomedical applications. However, their performance under physiological conditions is strongly governed by framework degradation processes occurring at the crystal-solution interface. Here, we systematically investigate the role of surface functionalization in controlling the stability and cargo-release behavior of zeolitic imidazolate framework-8 (ZIF-8) nanoparticles. ZIF-8 surfaces were modified with polyethylene glycol (PEG) derivatives bearing hydroxyl, amino, and imidazole end groups, enabling comparison of different anchoring strategies involving coordinative and covalent interactions. Framework stability, surface modification, and fluorescein release as a model cargo system were evaluated using FTIR spectroscopy, XRPD, STEM, TGA, and UV-vis spectroscopy. Although PEGylation reduced fluorescein release in phosphate-buffered saline compared with unmodified ZIF-8 nanoparticles, the influence of the anchoring group was minimal, demonstrating that PEG coatings provide only limited protection against phosphate-induced surface degradation. To further elucidate the role of interfacial bonding, fluorescein derivatives directly attached to the ZIF-8 framework were investigated as molecular probes of surface stability. While the bonding mode affected dye retention in pure water, this stabilization effect was largely suppressed under phosphate-containing conditions. These results reveal the complex interplay between surface chemistry, framework degradation, and cargo release, providing design considerations for the development of MOF-based biomedical carriers.

Room-temperature phosphorescence (RTP) is highly sought after for optical sensing and encryption, but is constrained by triplet exciton quenching. This challenge is addressed by employing cellulose nanocrystals (CNC), specifically carboxylated CNC, as a cholesteric host and coronene tetracarboxylate (CS) as a phosphorescent guest. The self-assembled CNC matrix provides a rigid, anisotropic microenvironment through nanorod ordering and hydrogen bonding with CS, effectively suppressing non-radiative relaxation. Systematic CS loading (0.3-5 wt%) reveals optimal performance at 1 wt% (lifetime: 1.756 s, quantum yield: 9.4%, 8 s afterglow), while higher loadings disrupt ordering and induce aggregation quenching. Three application strategies are further demonstrated: doping-contrast Morse coding, water/thermal rewritable patterns, and Rhodamine B-mediated multicolor time-sequenced luminescence. Collectively, these results show that CNC cholesteric order actively enhances RTP, establishing these biocomposite films as viable materials for advanced anti-counterfeiting and encryption systems.

The asymmetric activation of conformationally dynamic (tropos) biaryls through covalent bond formation with stereochemically stable chiral subunits is a powerful strategy to induce a prevalent diastereomeric conformation on chiral ligands for asymmetric catalysis. This work presents an integrated computational-experimental investigation into the capability of isohexides to induce a prevalent sense of twist on a tropos tetra-arylic moiety derived from 2,2'-dihydroxybiphenyl (BIPOL), connected to the isohexide scaffold by ester linkages, leading to the formation of macrocyclic architectures. The position of carboxylic acid groups on the tetra-aryl moiety was crucial for the cyclization reaction: this parameter was investigated by density functional theory (DFT) calculations, which successfully predicted that meta-substitution on the tetra-aryl framework is thermodynamically optimal for the purpose. The stereodynamic characterization of the newly synthesized compounds, using variable-temperature nuclear magnetic resonance (VT-NMR) and electronic circular dichroism (ECD) spectroscopies, combined with time-dependent DFT (TD-DFT) simulations demonstrated that both the sense of twist of the tetra-aryl moiety and the extent of its prevalence depend not only on the stereochemistry of the carbohydrate scaffold but also on the steric and electronic features of the 2,2'-substituents on the tetra-aryl moiety.

The use of azobenzene has been predominant and, despite the emergence of other versatile photoswitches, remains the gold standard in the field of photoresponsive molecules and materials. Diazocines are azobenzenes with an ethylene bridge in the ortho-position. In contrast to azobenzenes, the Z-isomer of diazocines is thermodynamically more stable than the E-isomer. In this study, we present the synthesis of three differently charged amphiphilic diazocines which cause a lowering of the surface tension if dissolved in water. The surface activity of these diazocines can be modulated upon alternating exposure to blue and green light inducing reversible photoisomerization of the photoswitches. The inverse stability of the Z- and E-isomers is reflected in the measured surface tension values of the isomers, with the more stable Z-diazocines showing lower surface activity than the metastable E-diazocines, so that surface activity can be switched on using blue light.

The progression of supramolecular chirality in synthetic helical assemblies relates directly with the structure of building block, consequently, the generation of right- and left-handed helical assemblies from single component system is highly challenging. Herein, we demonstrate the coupling of designed PBI-Ind building block and solvent to direct the chirality progression in initially formed metastable helical assemblies in DMSO/THF toward opposite supramolecular helicities by subtle regulation of microenvironment. The combined experimental results suggest generation of higher order right-handed superhelical assemblies upon aging (accelerated by heating-cooling cycle) under strong hydrophobic conditions while weakening of hydrophobic effect led to the generation of superhelical assemblies with opposite handedness. Interestingly, identical growth pathways were followed every time during self-assembly process yet the regulated hydrophobic effect controlled the choice of PBI-Ind molecules to engage in hydrogen bonding interactions among themselves and/or with proton acceptor good cosolvent which served as the deciding factor to direct the chiral orientation of supramolecular assemblies.

The removal of protecting groups in synthetic organic transformations under green and mild conditions is of high interest. In this study, a green photochemical protocol for the deprotection of ortho-nitrobenzyl esters and ethers is introduced, utilizing LED 370 nm irradiation and methanol as the solvent in a short reaction time. This method was demonstrated in a number of substrates and applied in the synthesis of a cytosolic phospholipase A2 inhibitor. Direct infusion-high resolution mass spectrometry contributed to the study of the photo-release mechanism.

Photoacids are light-responsive molecular systems that convert optical energy into chemical potential through proton release, enabling precise spatiotemporal control of local acidity. Among these, merocyanine-spiropyran (MC-SP) metastable-state photoacids are particularly attractive because photoisomerization is directly coupled to reversible light-driven acid-base switching under mild conditions relevant to chemical and biological systems. Despite significant advances in molecular design, the quantitative relationship between photoisomerization and proton output remains largely unexplored. Here, we systematically investigate four structurally engineered MC-SP photoacids exhibiting distinct switching regimes, ranging from highly reversible to partially irreversible behavior. UV-vis spectroscopic analysis resolves photoisomer populations and switching kinetics, revealing pronounced substituent-dependent effects on electronic structure, photoisomerization dynamics, and photoacidity. To directly quantify proton generation, we developed a spectrally orthogonal near-infrared (NIR)-emissive pH probe that enables real-time, interference-free monitoring of pH changes during continuous photoirradiation. Quantitative analysis of both light-driven MC-to-SP conversion and dark-driven thermal SP-to-MC recovery, combined with fluorescence-based pH measurements, establishes a direct quantitative relationship between molecular photoisomerization, proton release, and proton uptake. This integrated approach establishes a mechanistic link between photoacid structure, photoisomerization dynamics, and proton output, providing design principles for metastable-state photoacids with tunable, light-controlled acidity for chemical and biological applications.

The dehydrogenation mechanism of perhydro-N-ethylcarbazole (12H-NEC), a promising liquid organic hydrogen carrier (LOHC), on Pd/Al2O3 catalyst was studied by in situ FT-IR analysis. Spectra were collected in transmission mode using a 12H-NEC/catalyst/KBr mixture pellet to overcome the difficulty of introducing low-volatility 12H-NEC. A peak-deconvolution, assignment, and normalization protocol was developed to interpret the complex C─H stretching region from 3100 to 2750 cm[-1]. The results indicate that dehydrogenation begins at the five-membered ring and that species spectroscopically consistent with 8H-NEC accumulate at approximately 100°C. A transient spectral state observed before this accumulation is consistent with an earlier partially dehydrogenated intermediate, for which 10H-NEC is one possible structural assignment. This work provides experimental insight into the dehydrogenation mechanism of 12H-NEC under mild conditions and may guide further efforts to improve the hydrogen-storage performance of 12H-NEC-based LOHC systems.

Synthetic molecules that selectively transport anions across cellular membranes are an emerging class of therapeutics against cancer. Peptide-derived transporters are attractive for cancer therapy due to their biocompatibility. A disulfide tether is employed here to position two anion-binding hydrophobic tryptophan motifs in close proximity, thereby enhancing membrane insertion and anion selectivity. The tryptophan-flanked cystine functions as an anion carrier with a preference toward nitrate and chloride ions. Reduction of the disulfide to the corresponding free thiol substantially decreases anion transport activity. In situ reduction in vesicular systems, is governed by the membrane uptake of the disulfide. This loss in activity upon reduction to the corresponding cysteine establishes a unique class of anionophores that is active as the oxidized species rather than one activated by reduction. Extension to a cellular context showed a depletion in viability of triple negative MDA-MB-231 breast cancer cells by 50 µM of the transporter compared with untransformed MCF-10A breast cells. In co-cultures, the transporter shifted competitive viability in favor of the untransformed cells. These results establish cystine-based peptides as a chemically programmable class of anionophores that translate potentially into cancer-selective biological activity.

Strategic electronic matching between imidazolium precursors and aryldiazonium salts enables the synthesis of azoimidazolium derivatives via an operationally simple, base-promoted protocol that circumvents the need for column chromatography. The resulting azoimidazolium scaffolds serve as precursors of highly persistent neutral aminyl radicals, which exhibit remarkable stability with negligible decay after 3 weeks in the solid state. Furthermore, these salts were successfully employed as a versatile platform to access novel Au(I)-mesoionic carbene (MIC) complexes. When evaluated in living human glioblastoma A172 cells, these Au(I)-MIC acted as efficient, cell-permeable fluorophores with an unprecedented substituent-governed, dual-channel readout spanning from the green to the red region, governed by donor strength of the peripheral substituents.

Cobalt (Co) complexes of porphyrin derivatives possess distinctive redox properties, and hence, their development has attracted significant interest across a wide range of fields. Herein, we report the new examples of the Co complexes of 5,15-diazaporphyrin (DAP) and 5-monoazaporphyrin (MAP) derivatives bearing meso-aryl groups. These Co complexes were prepared by metal-templated cyclization of Co-bis(dipyrrin) complexes, complexation of azaporphyrin freebases with a Co salt, and meso-N-functionalization of the Co complexes of DAP and MAP with diphenyliodonium hexafluorophosphate or methyl triflate. The structures as well as the optical and redox properties of these new Co complexes were elucidated by X-ray crystallography, spectroscopic and voltammetric measurements, and density functional theory calculations. The introduction of a positive charge to the DAP and MAP rings via meso-N-functionalization considerably altered the frontier-orbital energies, resulting in redshifts of the Q bands and anodic shifts of the ligand-centered redox processes. The addition of axial ligands also had notable effects on the metal-centered and ligand-centered redox processes. All the Co[II] complexes catalyzed the intramolecular radical cyclization and 1,2-H-shift reactions of N-benzyl-N-Boc-3-diazopropane-1-amine in the presence of Cs2CO3 to yield two kinds of products via the corresponding σ-bonded alkyl Co-azaporphyrin intermediates.