Kline Marcus (bathjelly1)

The efficiency of photodynamic therapy (PDT) is severely constrained due to the innate hypoxic environment, besides the elevated level of glutathione (GSH). To get rid of the hypoxic environment and higher concentrations of GSH in the solid tumors, we propose an approach of oxygen self-sufficient multimodal imaging-guided nanocomposite CaO2-MnO2-UCNPs-Ce6/DOX (abbreviated as CaMn-NUC), in which CaO2 nanoparticles in the hydrophobic layer were seated on the hydrophilic MnO2 sheet and conjugated with chlorin e6 (Ce6) loaded upconversion nanoparticles (UCNPs-Ce6) via the click chemistry approach. CaMn-NUC was presented to overcome hypoxia and GSH-associated photodynamic resistance due to in situ oxygen generation and GSH reduction of MnO2 upon endocytosis, and a bulk amount of Mn2+ ions generated in the process under acidic tumor environment acts as the MRI contrast agent. Moreover, the MnO2 sheet protects Ce6 from self-degradation under irradiation; thus, it can be used to switch control of cellular imaging. Afterwards, in a regulated and targeted manner, the chemotherapeutic drug (doxorubicin hydrochloride, DOX) can be released with the degradation of CaMn-NUC in the acidic tumor microenvironment (TME). Thus, we testify a competent nanoplatform employing 808 nm-excited UCNPs-Ce6 for concurrent imaging and PDT in consideration of the large anti-Stokes shifts, deep penetration into biological tissues, narrow emission bands, and high spatial-temporal resolution of the UCNPs. Thus, our proposed nanoplatform postulates a strategy to efficiently kill cancer cells in a concentration- and time-dependent manner via the in situ oxygenation of solid tumor hypoxia to enhance the efficiency of multimodal imaging-guided chemo-photodynamic therapy.Domain-based local pair natural orbital (DLPNO) coupled cluster single and double (CCSD) with triple perturbation (T) correction methods were performed to elucidate the relative stabilities of ten different intermediate structures of the CaMn4Ox cluster in the S0 state of the oxygen evolving complex (OEC) of photosystem II (PSII). Full geometry optimizations of all the S0 intermediates were performed by the UB3LYP-D3/Def2-TZVP methods, providing the assumed geometrical structures and starting natural orbitals (UNO) for DLPNO-CCSD(T)/Def2TZVP calculations. The effective exchange integrals (J) for the spin Hamiltonian models for the ten intermediates were obtained by the UB3LYP/Def2-TZVP calculations followed by the general spin projections. DLPNO-CCSD(T) calculations followed by the CBS extrapolation procedure elucidated that the (II, III, IV, IV) and (III, III, III, IV) valence states in the CaMn4O5 cluster of the OEC of the PS II were nearly degenerated in energy in the S0 state, indicating an important role of dynamical electron correlation effects for the valence and spin fluctuations in strongly correlated electron systems (SCESs) consisting of 3d transition metals.ABO3-δ perovskites are utilized in many applications including optical gas sensing for energy systems. Understanding the opto-electronic properties allows rational selection of the perovskite-based sensors from a diverse family of ABO3-δ perovskites, associated with the choices of A and B cations and range of oxygen concentrations. Herein, we assess the impact of oxygen vacancies on the electronic structure and optical response of pristine and oxygen-vacant ABO3-δ (A = La, Sr; B = Cr, Mn) perovskites via first-principles calculations. The endothermic formation energy for oxygen vacancies shows that the generation of ABO3-δ defect structures is thermodynamically possible. LaCrO3 and LaMnO3 have direct and indirect ground-state band gaps, respectively, whereas SrCrO3 and SrMnO3 are metallic. In the presence of an oxygen mono-vacancy, however, the band gap decreases in LaCrO3-δ and vanishes in LaMnO3-δ. In contrast to the decrease in the band gaps, the oxygen vacancies in ABO3-δ are found to increase optical absorption in the visible t