We report in situ synthesis of the first CF(3) oxonium salts, thermally unstable O-(trifluoromethyl)dibenzofuranium salts, which furthermore have different counteranions (BF(4)-, PF(6)-, SbF(6)-, and Sb(2)F(11)-) and ring substituents (tert-butyl, F, and OCH(3)), by photochemical decomposition of the corresponding 2-(trifluoromethoxy)biphenylyl-2'-diazonium salts at -90 to -100 degrees C. The yields markedly increased in the order of BF(4)- < PF(6)- < SbF(6)- < Sb(2)F(11)-. The CF(3) oxonium salts were fully assigned by means of (1)H and (19)F NMR spectroscopy at low temperature. The CF(3) salts decomposed to form CF(4) and dibenzofurans. The half-life times at -60 degrees C of the 2-tert-butyl salts having different counteranions were 29 min for BF(4)- salt 2d, 36 min for PF(6)- salt 2c, 270 min for SbF(6)- salt 2a, and 415 min for Sb(2)F(11)- salt 2b. Those at -60 degrees C of the Sb(2)F(11)- salts having different 2-substituents were 13 min for F salt 3b, 63 min for H (unsubstituted) salt 1b, and 415 min for tert-butyl salt 2b. Thus, the stability of the CF(3) oxonium salts increased in the order of BF(4)- < PF(6)- < SbF(6)- < Sb(2)F(11)- and F < H < tert-butyl, which is in accord with the increasing orders of the non-nucleophilicity of counteranions and the electron-donating effect of ring substituents. 2-tert-Butyl-O-(trifluoromethyl)dibenzofuranium hexafluoroantimonate (2a) was thus chosen and successfully applied as a real CF(3)+ species source to the direct O- and N-trifluoromethylations of alcohols, phenols, amines, anilines, and pyridines under very mild conditions. The thermal decomposition method with a mixture of diazonium salt 17a and aryl- or alkylsulfonic acids, pyridine, or pyridines having an electron-withdrawing group also afforded CF(3)O or CF(3)N products. The trifluoromethylation mechanism is discussed and an S(N)2 mechanism containing the transient formation of free CF(3)+ is proposed. Thus, the present study has demonstrated that the exceedingly reactive CF(3)+ species can be generated much easier than the CH(3)+ species, contrary to the common sense that CF(3)+ is extremely difficult to generate in solution.

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Homogeneous dispersions of reduced tungsten oxide and tungsten bronze nanoparticles with ternary additives Na, Tl, Rb, and Cs have been prepared in the wet process and examined for optical properties. The dispersions of reduced tungsten oxide and tungsten bronze nanoparticles are found to show a remarkable absorption of near infrared light while retaining a high transmittance of visible light. This property is highly suitable for solar control filters in automotive and architectural windows.

Nanosize homogenous rod-like tungsten bronze Cs x WO 3 with excellent NIR shielding ability was successfully synthesized by a novel and facile water controlled-release solvothermal process (WCRSP).

Optical absorption and scattering behaviors of lanthanum hexaboride (LaB6) nanoparticulate dispersion coatings with various particle sizes have been investigated in the ultraviolet to near-infrared (NIR) wavelengths for application to solar control filters. Large characteristic near-infrared absorption is introduced as the decreased particle size falls into nanoscale, and its origin is discussed in terms of a localized surface plasmon resonance (LSPR) of conduction electrons. Optical constants of LaB6 have been measured and Mie scattering theory analysis was conducted. The theory was found to generally replicate the optical characteristics, and variations of absorbed and scattered wave fractions as well as the LSPR wavelength have been discussed with varying particle size. The absorption peaks are found as shaped narrower and located at shorter wavelength in theory than in experiment, which is suggested as ascribed mainly to the nonspherical distorted shape of LaB6 nanoparticles.

Agonistic antibodies targeting CD137 have been clinically unsuccessful due to systemic toxicity. Since conferring tumor selectivity through tumor-associated antigen limits its clinical use to cancers that highly express such antigen, we exploited extracellular adenosine triphosphate (exATP), which is a hallmark of the tumor microenvironment and highly elevated in solid tumors, as a broadly tumor selective switch. We generated a novel anti-CD137 switch antibody, STA551, which exerts agonistic activity only in the presence of exATP. STA551 demonstrated potent and broad anti-tumor efficacy against all mouse and human tumors tested and a wide therapeutic window without systemic immune activation in mice. STA551 was well tolerated even at 150 mg/kg/week in cynomolgus monkeys. These results provide a strong rationale for the clinical testing of STA551 against a broad variety of cancers regardless of antigen expression, and for the further application of this novel platform to other targets in cancer therapy.

The low-energy optical absorption mechanism of tungsten oxides and tungsten bronzes is unresolved, with the primary models reported involving free-electron and polaron excitations. Herein, a new mechanism is proposed, based on a systematic and detailed analysis of optical profiles in Cs-doped hexagonal tungsten bronze nanoparticles with varied amounts of oxygen vacancy (VO) and Cs dopant. The Drude–Lorentz analysis of absorption bands, incorporating a newly-developed Mie scattering integration method, has clarified the observed absorption profiles as consisting of three peaks of anisotropic plasmon and polaron exitations. The behavior of the deconvoluted components indicates that VO and Cs+ provide localized and delocalized electrons, respectively, both contributing to the collective plasmon resonance against external electromagnetic waves.