Peter R. Taylor

Inflammatory bowel disease (IBD) is exacerbated by the excessive accumulation of reactive oxygen species (ROS). To overcome the insufficient catalytic activity of conventional cerium-based nanozymes, we designed an ultrasound-activated Bi@BTC heterojunction nanozyme. The ultrasound-activated carriers generated by bismuth core undergo effective electron-hole separation in the Janus Bi@BTC heterojunction. The holes are enriched in the valence band of the BTC shell, catalyzing the oxidation reaction of Ce3+. Benefiting from the proton-coupled electron transfer (PCET) effect of tannic acid and the electronic coupling at the heterointerface, Bi@BTC accelerates the Ce3+/Ce4+ redox cycling, enabling a highly efficient and stable superoxide dismutase (SOD)−catalase (CAT)-like catalytic cycle and thus robust elimination of multiple ROS in the IBD microenvironment. Density functional theory (DFT) calculations elucidate the catalytic pathways and cyclic mechanisms underlying the dual enzyme-mimetic activities, revealing key intermediates, transition states, and corresponding energy profiles. In vitro and in vivo assays confirmed that Bi@BTC alleviates intestinal inflammation by eliminating excess ROS, upregulating tight-junction proteins, promoting mucosal barrier repair, and restoring gut microbiota homeostasis. This work presents a boosted ROS-elimination strategy via ultrasound-activated heterojunction-mediated effect and PCET-driven cerium redox cycling, establishing a multifunctional paradigm that integrates ROS scavenging, anti-inflammation, mucosal repair, and gut microecological regulation.

Nanocatalytic medicine has emerged as a promising strategy for tumor therapy, where the rational design of photocatalytic nanoscale heterostructures plays a pivotal role. Herein, an organic–inorganic core–shell nanoreactor (Bi@COF) is designed as a wobble‐scheme heterojunction with responsiveness to the tumor microenvironment (TME). In the acidic TME, the COF shell undergoes reversible enolimine‐ketoenamine tautomerization, enabling dynamic switching between reduction/oxidation (RP/OP) junctions. Under near‐infrared irradiation (NIR), the reconfigured heterojunction efficiently catalyzes in situ H ₂ O ₂ generation, while the photothermal effect further promotes its decomposition into hydroxyl radicals (·OH). This process establishes an intracellular self‐sufficient reactive oxygen species (ROS) system for synergistic photothermal and photodynamic tumor therapy. Experimental and theoretical analyses demonstrate that COF tautomerization reconstructs the conjugated framework, modulates band alignment, and reverses the type of RP/OP junction. Structurally, the dual donor–acceptor (D‐C = N‐A) structure of COF‐H facilitates charge transfer, while protonated imine groups provide active sites for proton transfer. These features synergistically promote proton‐coupled electron transfer (PCET) under acidic TME conditions, thereby lowering the catalytic energy barrier and facilitating the generation of H ₂ O ₂ . In this work, the wobble‐scheme heterojunction‐mediated ROS self‐supply system disrupts intracellular redox homeostasis and induces cancer cell apoptosis, offering a promising paradigm for integrating dynamically regulated heterojunctions with nanocatalytic medicine.

In this work, highly accurate ab initio calculations have been employed to predict the spectroscopic properties of protonated acrolein (both cis- and trans-isomers) and methylketene. These C₃H₅O⁺ systems are of astrochemical interest owing to their neutral analogues having already been detected in the interstellar medium. In total, we have characterized six species: syn and anti conformers of both O-protonated cis- and trans-acrolein, O-protonated gauche-methylketene and C-protonated methylketene. Specifically, the CCSD(T) method (coupled-cluster with all single and double substitutions and a quasiperturbative treatment of triple excitations) has been used in conjunction with extrapolation to the complete basis-set limit, and corrections for core-valence effects. To support experimental spectroscopy measurements aiming at guiding astronomical observations, we have focused on determining best theoretical estimates of rotational and vibrational spectroscopic parameters. The V₃ barriers to internal methyl rotation for both protonated methylketene species (O- and C-) have additionally been computed, and an estimate of the reduced rotation constant for internal rotation, F₀, has been deduced.

What most of us thought we knew about acetamide, and thus generalized to larger amides, turns out to be wrong. Here's the plain (but slightly distorted) truth.

Carbon clusters containing between 10 and 30 atoms predominantly exist as rings, a structure that persists for clusters containing up to at least 60 carbon atoms. Although carbon rings were once regarded as fleeting entities, only observable as charged species via mass spectrometry, their recent synthesis and atomic-scale imaging on surfaces have reignited interest in their extraordinary properties. Here, we present infrared spectra of charged cyclocarbons (C_4n⁺, n = 5-11) showing that they exhibit intense infrared resonances over the 550-1800 cm^-1 range that are at least 50 times stronger than infrared transitions of coexisting fullerene and bi-ring isomers, and which, density functional theory calculations suggest, are associated with a localized Kekulé-type distortion oscillating back and forth across the ring. The resonances should serve as distinctive spectroscopic signatures for cyclocarbon cations in terrestrial and extraterrestrial environments, and may expedite radiative cooling of isolated charged cyclocarbons, facilitating their formation through bimolecular association reactions in low pressure environments, including in interstellar space.

The quantitative calculation of the magnetizability tensor of fluorine-containing molecules has been a longstanding challenge for quantum chemistry. We report a benchmark study on the effect of fluorine substitution on the magnetizability (both isotropic and anisotropic) of 24 small closed-shell molecules using coupled-cluster (CCSD(T)) theory, large basis sets, and London atomic orbitals. By extrapolation to a complete basis set (CBS) result, we establish the CCSD(T)/CBS limit and take the opportunity to assess the performance of various density functional theory approximations. Correcting for zero-point vibration further allows us to directly compare theory with (gas-phase) experimental data. We revisit Flygare's hypothesis on molecular magnetizabilities, which relates the successive replacement of hydrogen by fluorine atoms to changes in the magnetizability anisotropy. Some exceptions to this hypothesis are documented, and we rationalize these observations on the basis of hybridization on carbon.

Fungal azaphilones are a broad class of naturally‐occurring pigments with diverse applications. Among the azaphilone pigments, mitorubrins are well recognized for their antiviral, antibacterial, antifungal, antiprotozoal, antidiabetic, and antiaging activities in addition to their well‐known yellow‐orange color. This makes these pigments interesting candidates for use in foods, as cosmetics, and as medicines. In particular, if it is desired to modify the properties of mitorubrin‐based pigments, for example by derivatization, it is essential to have an understanding of the electronic spectra of the parent molecules. We have therefore undertaken a computational study of a series of mitorubrins, comparing our computed results with experimental UV/visible spectra. Both density‐functional theory (DFT) and coupled‐cluster (CC2) methods have been used, and in general, the results are in very good agreement with observation. In order to provide a simple and useful picture of the spectra we analyze the stronger transitions in terms of natural transition orbitals (NTOs).

Linker installation is a potent strategy for integrating specific properties and functionalities into metal-organic frameworks (MOFs). This method enhances the structural diversity of frameworks and enables the precise construction of robust structures, complementing the conventional postsynthetic modification approaches, by fully leveraging open metal sites and active organic linkers at targeting locations. Herein, we demonstrated an insertion of a d-camphorate linker into a flexible Zr-based MOF, PCN-700, through linker installation. The resultant homochiral MOF not only exhibits remarkable stability but also functions as a highly efficient luminescent material for enantioselective sensing. Competitive absorption and energy/electron transfer processes contribute to the sensing performance, while the difference in binding affinities dominates the enantioselectivity. This work presents a straightforward route to crafting stable homochiral MOFs for enantioselective sensing.

Electronic transitions are observed for the O2+–Ar and O2+–N2 complexes over the 225–350 nm range. The transitions are not associated with recognized electronic band systems of the respective atomic and diatomic constituents (Ar+, Ar, O2+, O2, N2+, and N2) but rather are due to charge transfer transitions. Onsets of the O2+–Ar and O2+–N2 band systems occur at 3.68 and 3.62 eV, respectively, corresponding to the difference in the ionization potentials of Ar and O2 (3.69 eV), and N2 and of O2 (3.51 eV), suggesting the band systems arise from intramolecular charge transfer transitions to states correlating with O2(X3Σg−) + Ar+ (2Pu) and O2(X3Σg−) + N2+(X2Σg+) limits, respectively. The dominant vibronic progressions have ωe values of 1565 cm−1 for O2+–Ar and 1532 cm−1 for O2+–N2, reasonably close to the value for the neutral O2 molecule in its X3Σg− state (1580 cm−1). Higher energy band systems for O2+–Ar and O2+–N2 are assigned to transitions to states correlating with the O2 (a1Δg) + Ar+ (2Pu) and O2 (a1Δg) + N2+(X2Σg+) limits, respectively.