Protein inactivation by reactive oxygen species (ROS) such as singlet oxygen ((1)O2) and superoxide radical (O2(•-)) is considered to trigger cell death pathways associated with protein dysfunction; however, the detailed mechanisms and direct involvement in photodynamic therapy (PDT) have not been revealed. Herein, we report Ir(III) complexes designed for ROS generation through a rational strategy to investigate protein modifications by ROS. The Ir(III) complexes are effective as PDT agents at low concentrations with low-energy irradiation (≤ 1 J cm(-2)) because of the relatively high (1)O2 quantum yield (> 0.78), even with two-photon activation. Furthermore, two types of protein modifications (protein oxidation and photo-cross-linking) involved in PDT were characterized by mass spectrometry. These modifications were generated primarily in the endoplasmic reticulum and mitochondria, producing a significant effect for cancer cell death. Consequently, we present a plausible biologically applicable PDT modality that utilizes rationally designed photoactivatable Ir(III) complexes.

The temperature dependence of the Mott metal-insulator transition (MIT) is studied with a VO2-based two-terminal device. When a constant voltage is applied to the device, an abrupt current jump is observed with temperature. With increasing applied voltages, the transition temperature of the MIT current jump decreases. We find a monoclinic and electronically correlated metal (MCM) phase between the abrupt current jump and the structural phase transition (SPT). After the transition from insulator to metal, a linear increase in current (or conductivity) is shown with temperature until the current becomes a constant maximum value above TSP T ≈68• C. The SPT is confirmed by micro-Raman spectroscopy measurements. Optical microscopy analysis reveals the absence of the local current path in micro scale in the VO2 device. The current uniformly flows throughout the surface of the VO2 film when the MIT occurs. This device can be used as a programmable critical temperature sensor.PACS numbers: 71.27. +a, 71.30.+hThe first-order Mott discontinuous metal-insulator transition (MIT) has been studied as a function of temperature in numerous materials such as Ti 2 O 3 , V 2 O 3 , and VO 2 etc [1]. Almost all have a transition temperature, T MIT , below room temperature except VO 2 which has T MIT ≈68• C. In particular, VO 2 thin films were used for fabrication of two-and three-terminal devices controlled by an electric field [2]. A high-speed Mott switching device using an abrupt current jump as observed in I-V measurements was predicted for manufacturing in the nano-level transistor regime [3,4].Moreover, Raman experiments [5] for a VO 2 film have showed monoclinic-insulator peaks after the film had undergone an electric-field-induced transition from an insulator to a metal. Furthermore, tetragonal-metal peaks have been associated with the structural phase transition (SPT) above 68• C. Also no evidence of phonon softening near the transition temperature has been found by the temperature dependence of Raman spectra measured with a VO 2 single crystal and a thin film [6]. These results support the electron correlation model of the MIT. However, some reports argue that the electric field-induced MIT is due to Joule heating by current and is accompanied by SPT, and that, furthermore, the local current path or current filament formed by the dielectric breakdown [7] can also cause the jump (MIT). The dielectric breakdown was described by depinning and the collective transport of charge carriers above a threshold voltage. Here, we try to elucidate this ambiguity through the analysis of our present research.Another interesting aspect in VO 2 is that the T MIT can be modified by doping [8,9] and stress [10]. VO 2 thin films deposited on (001) and (110) TiO 2 substrates showed a modified T MIT of 27 and 96• C, respectively, where the c-axis length was stressed by a lattice mismatch between the film and the substrate [10]. The modification of the T MIT by doping and stress is restricted to within a fixed temperature, whereas the T MIT indu...

We have systematically studied a variety of vanadium dioxide (VO 2 ) crystalline forms, including bulk single crystals and oriented thin films, using infrared (IR) near-field spectroscopic imaging techniques. By measuring the IR spectroscopic responses of electrons and phonons in VO 2 with sub-grain-size spatial resolution (~20 nm), we show that epitaxial strain in VO 2 thin films not only triggers spontaneous local phase separations but also leads to intermediate electronic and lattice states that are intrinsically different from those found in bulk. Generalized rules of strain and symmetry dependent mesoscopic phase inhomogeneity are also discussed. These results set the stage for a comprehensive understanding of complex energy landscapes that may not be readily determined by macroscopic approaches.

We demonstrate ultrafast all-optical control of terahertz (THz) radiation through nanoresonators, slot antennas with a hundred micron length but submicron width in thin gold layers, fabricated on vanadium dioxide (VO2) thin films. Our THz nanoresonators show almost perfect transmission at resonance. By virtue of phase transition of VO2 from insulating to metallic state, induced in subpicosecond time scale by moderate optical pump, ultrafast control of THz transmission is enabled. This is compared to bare VO2 films where no switching dynamics are observed under similar conditions.