New Insights into Photo-Fenton Chemistry: The Overlooked Role of Excited IronIII Species.

Direct photoreduction of FeIII is a widely recognized route for accelerating FeIII/FeII cycle in photo-Fenton chemistry. However, most of the wavelengths covering the full spectral range are insufficient to supply enough photon energy for the direct reduction process. Herein, the hitherto neglected mechanism of FeIII reduction that the FeIII indirect reduction pathway initiated by light energy-dependent reactivity variation and reactive excited state (ES) was explored. Evolution of excited-state FeIII species (*FeIII) resulting from metal-centered charge excitation (MCCE) of FeIII is experimentally verified using pulsed laser femtosecond transient absorption spectroscopy with UV-vis detection and theoretically verified by quantum chemical calculation. Intense photoinduced intravalence charge transition was observed at λ = 380 and 466 nm, revealing quartet 4MCCE and doublet 2MCCE and their exponential processes. Light energy-dependent variation of *FeIII reactivity was kinetically certified by fitting the apparent rate constant of the radical-chain sequence of photo-Fenton reactions. Covalency is found to compensate for the intravalence charge separation following photoexcitation of the metal center in the MCCE state of Fenton photosensitizer. The *FeIII is established as a model, demonstrating the intravalence hole delocalization in the ES can be leveraged for photo-Fenton reaction or other photocatalytic schemes based on electron transfer chemistry.

Effects of synthesis methods and different concentrations of Eu3+ ions on the emission properties of Sr2 SiO4 phosphors.

Sr2-x SiO4 -xEu (x = 0.01, 0.02, 0.035, and 0.05) phosphors were synthesized at 1000-1,300°C for 2 h in two different processes, the solid-state reaction (SSR) method and a two-step (TS) method, and these results revealed three important findings. The secondary Sr3 SiO5 phase was observed in 1,300° C-TS-synthesized Sr2-x SiO4 -xEu powder, but no raw materials or secondary phases were observed in the SSR-prepared Sr2-x SiO4 -xEu powders. The concentration quenching effect of Eu3+ ions was really observed in TS-prepared Sr2-x SiO4 -xEu phosphors, which was not observed in SSR-prepared Sr2-x SiO4 -xEu phosphors. High emission intensity of charge transition state (CT) band was observed in the photoluminescence excitation spectra, for that the 265 and 393 nm were used as the excitation wavelengths of Sr2-x SiO4 -xEu phosphors. Sr2-x SiO4 -xEu phosphors under different synthesis processes and excitation wavelengths would have different main emission peaks in the photoluminescence emission spectra. In this study, we also well discussed and explored the relationships of photoluminescence properties with the dipole transitions (electric or magnetic) of Eu3+ ions and the different coordination structures of Sr+2 ions.

Extrapolated Defect Transition Level in Two-Dimensional Materials: The Case of Charged Native Point Defects in Monolayer Hexagonal Boron Nitride.

Defect formation energy as well as the charge transition level (CTL) plays a vital role in understanding the underlying mechanism of the effect of defects on material properties. However, the accurate calculation of charged defects, especially for two-dimensional materials, is still a challenging topic. In this paper, we proposed a simplified scheme to rescale the CTLs from the semilocal to the hybrid functional level, which is time-saving during the charged defect calculations. Based on this method, we systematically calculated the formation energy of four kinds of intrinsic point defects in two-dimensional hexagonal boron nitride (2D h-BN) by uniformly scaling the supercells by which we found a time-saving method to obtain the "special vacuum size" (Komsa, H.-P.; Berseneva, N.; Krasheninnikov, A. V.; Nieminen, R. M. Phys. Rev. X, 2014, 4, 031044). Native defects including nitrogen vacancy (VN), boron vacancy (VB), nitrogen atom anti-sited on boron position (NB), and boron atom anti-sited on nitrogen position (BN) were calculated. The reliability of our scheme was verified by taking VN as a probe to conduct the hybrid functional calculation, and the rescaled CTL is within the acceptable error range with the pure HSE results. Based on the results of CTLs, all the native point defects in the h-BN monolayer act as hole or electron trap centers under certain conditions and would suppress the p- or n-type electrical conduction of h-BN-based devices. Our rescale method is also suitable for other materials for defect charge transition level calculations.

Charge Transition of Oxygen Vacancies during Resistive Switching in Oxide-Based RRAM.

Resistive random-access memory (RRAM) devices have attracted broad interest as promising building blocks for high-density nonvolatile memory and neuromorphic computing applications. Atomic level thermodynamic and kinetic descriptions of resistive switching (RS) processes are essential for continued device design and optimization but are relatively lacking for oxide-based RRAMs. It is generally accepted that RS occurs due to the redistribution of charged oxygen vacancies driven by an external electric field. However, this assumption contradicts the experimentally observed stable filaments, where the high vacancy concentration should lead to a strong Coulomb repulsion and filament instability. In this work, through predictive atomistic calculations in combination with experimental measurements, we attempt to understand the interactions between oxygen vacancies and the microscopic processes that are required for stable RS in a Ta2O5-based RRAM. We propose a model based on a series of charge transition processes that explains the drift and aggregation of vacancies during RS. The model was validated by experimental measurements where illuminated devices exhibit accelerated RS behaviors during SET and RESET. The activation energies of ion migration and charge transition were further experimentally determined through a transient current measurement, consistent with the modeling results. Our results help provide comprehensive understanding on the internal dynamics of RS and will benefit device optimization and applications.

Active Tumor Permeation and Uptake of Surface Charge-Switchable Theranostic Nanoparticles for Imaging-Guided Photothermal/Chemo Combinatorial Therapy.

To significantly promote tumor uptake and penetration of therapeutics, a nanovehicle system comprising poly(lactic-co-glycolic acid) (PLGA) as the hydrophobic cores coated with pH-responsive N-acetyl histidine modified D-α-tocopheryl polyethylene glycol succinate (NAcHis-TPGS) is developed in this work. The nanocarriers with switchable surface charges in response to tumor extracellular acidity (pHe) were capable of selectively co-delivering indocyanine green (ICG), a photothermal agent, and doxorubicin (DOX), a chemotherapy drug, to tumor sites. The in vitro cellular uptake of ICG/DOX-loaded nanoparticles by cancer cells and macrophages was significantly promoted in weak acidic environments due to the increased protonation of the NAcHis moieties. The results of in vivo and ex vivo biodistribution studies demonstrated that upon intravenous injection the theranostic nanoparticles were substantially accumulated in TRAMP-C1 solid tumor of tumor-bearing mice. Immunohistochemical examination of tumor sections confirmed the active permeation of the nanoparticles into deep tumor hypoxia due to their small size, pHe-induced near neutral surface, and the additional hitchhiking transport via tumor-associated macrophages. The prominent imaging-guided photothermal therapy of ICG/DOX-loaded nanoparticles after tumor accumulation induced extensive tumor tissue/vessel ablation, which further promoted their extravasation and DOX tumor permeation, thus effectively suppressing tumor growth.