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Fenton or Fenton‐like reactions are ubiquitous in nature, and the hydroxyl radicals (·OH) generated in these reactions are accountable for a plethora of oxidation processes both in the environment and in vivo. Among these oxidation reactions, lipid oxidation initiated by ·OH radicals has long been oversimplified as a peroxidation mechanism, but in reality, it is a highly complicated process that can result in a large variety of products. Using the unique field‐induced droplet ionization mass spectrometry (FIDI‐MS) methodology that is capable of selective sampling of amphiphilic molecules that reside at the air–water interface, here, we show distinct mechanisms from the ultraviolet (UV)‐enhanced Fenton oxidations of two phospholipids, POPC and POPG, even though these two lipids possess the same functional groups that are vulnerable to ·OH attack. We postulate that it is the different packing densities that determine the permeability of ambient NO molecules into the monolayers, resulting in highly distinct reaction pathways and products. We anticipate that this work will be a wake‐up call that the lipid peroxidation mechanism is sometimes taken for granted and that lipid oxidation can be subtly affected by various factors that deserves deeper investigations. [ABSTRACT FROM AUTHOR]

While Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home‐built field‐induced droplet ionization mass spectrometry (FIDI‐MS) method that selectively samples molecules at the air–water interface, here we show the facile determination of both Type I and II mechanisms of a poster‐child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI‐MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms. [ABSTRACT FROM AUTHOR]

The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2 electronic configurations, consequently, a dicationic prototype is often utilized to design the M+ −M+ single bond. Existing studies generally use sterically bulky organic ligands L− to synthesize the compounds in the L− −M+ −M+ −L− manner. However, here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters, Mg2B7− and Zn2B7−, using density functional theory methods. The global minima of both of the clusters are in the form of M22+(B73−), where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety. Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters, which are driven by the unusually stable B73− moiety that is both σ and π aromatic. Vertical detachment energies of Mg2B7− and Zn2B7− are calculated to be 2.79 eV and 2.94 eV, respectively, for the future comparisons with experimental data. [ABSTRACT FROM AUTHOR]

Until now, all B≡B triple bonds have been achieved by adopting two ligands in the L→B≡B←L manner. Herein, we report an alternative route of designing the B≡B bonds based on the assumption that by acquiring two extra electrons, an element with the atomic number Z can have properties similar to those of the element with the atomic number Z+2. Specifically, we show that due to the electron donation from Al to B, the negatively charged B≡B kernel in the B2Al3− cluster mimics a triple N≡N bond. Comprehensive computational searches reveal that the global minimum structure of B2Al3− exhibits a direct B–B distance of 1.553 Å, and its calculated electron vertical detachment energies are in excellent agreement with the corresponding values of the experimental photoelectron spectrum. Chemical bonding analysis revealed one σ and two π bonds between the two B atoms, thus confirming a classical textbook B≡B triple bond, similar to that of N2. [ABSTRACT FROM AUTHOR]

Even though the general mechanism of photodynamic cancer therapy is known, the details and consequences of the reactions between the photosensitizer‐generated singlet oxygen and substrate molecules remain elusive at the molecular level. Using temoporfin as the photosensitizer, here we combine field‐induced droplet ionization mass spectrometry and acoustic levitation techniques to study the "wall‐less" oxidation reactions of 18:1 cardiolipin and 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phospho‐(1′‐rac‐glycerol) (POPG) mediated by singlet oxygen at the air–water interface of levitated water droplets. For both cardiolipin and POPG, every unsaturated oleyl chain is oxidized to an allyl hydroperoxide, which surprisingly is immune to further oxidation. This is attributed to the increased hydrophilicity of the oxidized chain, which attracts it toward the water phase, thereby increasing membrane permeability and eventually triggering cell death. [ABSTRACT FROM AUTHOR]

The discovery of homodinuclear multiple bonds composed of Group 13 elements represents one of the most challenging frontiers in modern chemistry. A classical triple bond such as N≡N and HC≡CH contains one σ bond and two π bonds constructed from the p orbitals perpendicular to the σ bond. However, the traditional textbook triple bond between two Al atoms has remained elusive. Here we report an Al≡Al triple bond in the designer Na3Al2− cluster predicted in silico, which was subsequently generated by pulsed arc discharge followed by mass spectrometry and photoelectron spectroscopy characterizations. Being effectively Al2− due to the electron donation from Na, the Al atoms in Na3Al2− undergo a double electronic transmutation into Group 15 elements, thus the Al2−≡Al2− kernel mimics the P≡P and N≡N molecules. We anticipate this work will stimulate more endeavors in discovering materials using Al2−≡Al2− as a building block in the gas phase and in the solid state. [ABSTRACT FROM AUTHOR]

Abstract: Potassium‐ion batteries (KIBs) are of interest for large‐scale electrical energy storage, owing to the abundance of K resources and potential high energy density. Low‐cost cathodes with high performance are crucial for KIBs. Herein, K4Fe(CN)6 is shown to be a low‐cost and high‐voltage cathode for KIBs. It can deliver a high voltage of approximately 3.6 V and a discharge capacity of 65.5 mAh g−1 with a lifespan of 400 cycles of discharge and charge. This is attributed to the strong σ bonds between C atoms and Fe and to the reduced particle size and good contact with conductive carbon brought about by ball milling, which benefit both the K+ ion and the electronic conduction. The [Fe(CN)6]3−/4− redox couple is found to be responsible for charge compensation upon reversible extraction/insertion of K+ from/into K4Fe(CN)6. The high voltage and stability of K4Fe(CN)6 will make it a promising low‐cost cathode for KIBs and encourage more investigations into high‐performance cathode materials. [ABSTRACT FROM AUTHOR]

Abstract: Potassium‐ion batteries (KIBs) are plagued by a lack of materials for reversible accommodation of the large‐sized K+ ion. Herein we present, the Bi anode in combination with the dimethoxyethane‐(DME) based electrolyte to deliver a remarkable capacity of ca. 400 mAh g−1 and long cycle stability with three distinct two‐phase reactions of Bi↔ KBi2↔K3Bi2↔K3Bi. These are ascribed to the gradually developed three‐dimensional (3D) porous networks of Bi, which realizes fast kinetics and tolerance of its volume change during potassiation and depotassiation. The porosity is linked to the unprecedented movement of the surface Bi atoms interacting with DME molecules, as suggested by DFT calculations. A full KIB of Bi//DME‐based electrolyte//Prussian blue of K0.72Fe[Fe(CN)6] is demonstrated to present large energy density of 108.1 Wh kg−1 with average discharge voltage of 2.8 V and capacity retention of 86.5 % after 350 cycles. [ABSTRACT FROM AUTHOR]