The combination of lone-pair effects on Pb(2+) cations and the smaller electronegativity of I(-) anions into the pentaborate framework generates a phase-matchable material, Pb(2)B(5)O(9)I, with the largest powder SHG response among borates, about 13.5 times that of KDP (KH(2)PO(4)), and transparency over the near-UV to middle-IR region. DFT calculations on electronic structure and cutoff-energy-dependent SHG coefficients confirm these origins.

Three new copper iodobismuthates, red tetranuclear [n-Bu(4)N][Cu(2)(CH(3)CN)(2)Bi(2)I(10)] (1), dark-red infinite linear [Et(4)N](2n)[Cu(2)Bi(2)I(10)](n) (2), and black polymeric ladderlike [Cu(CH(3)CN)(4)](2n)[Cu(2)Bi(2)I(10)](n) (3), crystallize from solutions of BiI3 and CuI in the presence of different cations. A regular structural relationship from 0-D (1) to 1-D linear anion chains (2) to 1-D ladderlike anion chains (3) is observed. The self-assembly of the basic building unit Cu(2)Bi(2)I(10) as altered by different cations is proposed to be the driving force for their formation. The optical band gaps exhibit a structure-related decrease from 1 to 2/3, in agreement with their color changes and the density functional theory (DFT) calculation results. The electronic structures and the relationship with corresponding monobismuth analogues and the Ag-Bi isotypes are discussed on the basis of DFT calculations. In spite of their structural similarities, the compounds are distinctive thermally: 2 is stable to 230 degrees C, 1 undergoes a solvent loss at 85 degrees C to form a new phase that is thermally stable to 230 degrees C, and 3 releases a solvent molecule and decomposes at 80 degrees C into BiI(3) and CuI. The essential reasons for these differences are discussed.

Background Immunosuppressive microenvironment is a major cause of immunotherapeutic resistance in glioma. In addition to secreting compounds, tumor cells under programmed cell death (PCD) processes release abundant mediators to modify the neighboring microenvironment. However, the complex relationship among PCD status, immunosuppressive microenvironment and immunotherapy is still poorly understood. Methods Four independent glioma cohorts comprising 1,750 patients were enrolled for analysis. The relationships among PCD status, microenvironment cellular components and biological phenotypes were fully explored. Tissues from our hospital and experiments in vitro and in vivo were used to confirm the role of ferroptosis in glioma. Results Analyses to determine enriched PCD processes showed that ferroptosis was the main type of PCD in glioma. Enriched ferroptosis correlated with progressive malignancy, poor outcomes and aggravated immunosuppression in glioblastoma (GBM) patients. Enhanced ferroptosis was shown to induce activation and infiltration of immune cells but attenuated antitumor cytotoxic killing. Tumor-associated macrophages (TAMs) were found to participate in ferroptosis-mediated immunosuppression. Preclinically, ferroptosis inhibition combined with PD-1/L1 blockade generated a synergistic therapeutic outcome in GBM murine models. Conclusions This work provides a molecular, clinical and biological landscape of ferroptosis, suggesting a role of ferroptosis in glioma malignancy and a novel synergic immunotherapeutic strategy that combines immune checkpoint blockade (ICB) treatment with ferroptosis inhibition.