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.

Metal–organic framework (MOF) nanoparticles with high porosity and greater tunability have emerged as new drug delivery vehicles. However, premature drug release still remains a challenge in the MOF delivery system. Here, we report an enzyme-responsive, polymer-coated MOF gatekeeper system using hyaluronic acid (HA) and PCN-224 nanoMOF. The external surface of nanoMOF can be stably covered by HA through multivalent coordination bonding between the Zr cluster and carboxylic acid of HA, which acts as a gatekeeper. HA allows selective accumulation of drug carriers in CD44 overexpressed cancer cells and enzyme-responsive drug release in the cancer cell environment. In particular, inherent characteristics of PCN-224, which is used as a drug carrier, facilitates the transfer of the drug to cancer cells more stably and allows photodynamic therapy. This HA-PCN system enables a dual chemo and photodynamic therapy to enhance the cancer therapy effect.

Aggregates of amyloidogenic peptides are involved in the pathogenesis of several degenerative disorders. Herein, an iridium(III) complex, Ir-1, is reported as a chemical tool for oxidizing amyloidogenic peptides upon photoactivation and subsequently modulating their aggregation pathways. Ir-1 was rationally designed based on multiple characteristics, including 1) photoproperties leading to excitation by low-energy radiation; 2) generation of reactive oxygen species responsible for peptide oxidation upon photoactivation under mild conditions; and 3) relatively easy incorporation of a ligand on the IrIII center for specific interactions with amyloidogenic peptides. Biochemical and biophysical investigations illuminate that the oxidation of representative amyloidogenic peptides (i.e., amyloid-β, α-synuclein, and human islet amyloid polypeptide) is promoted by light-activated Ir-1, which alters the conformations and aggregation pathways of the peptides. Additionally, their potential oxidation sites are identified as methionine, histidine, or tyrosine residues. Overall, our studies on Ir-1 demonstrate the feasibility of devising metal complexes as chemical tools suitable for elucidating the nature of amyloidogenic peptides at the molecular level, as well as controlling their aggregation.

Dye-sensitized photo-rechargeable battery (DSPB) harvests and stores dim light efficiently, realizing indoor-light-harvesting battery to operate IoT devices successfully without sun light.

A vacancy‐ordered double perovskite, Cs2SnI6, has emerged as a promising lead‐free perovskite in the optoelectronic field. However, the charge transfer kinetics mediated by its surface state remains unclear. Here, the charge transfer mechanism of Cs2SnI6 is reported and the role of its surface state in the presence of a redox mediator is clarified. Specifically, charge transfer through the surface state of Cs2SnI6 and its subsequent surface state charging are demonstrated by cyclic voltammetry and Mott–Schottky measurements, respectively. Because it is expected that the surface state of Cs2SnI6 is capable of regenerating oxidized organic dyes, a Cs2SnI6‐based regenerator is developed for a dye‐sensitized solar cell composed of fluorine‐doped tin oxide (FTO)/dyed mesoporous TiO2/regenerator/poly(3,4‐ethylenedioxythiophene)/FTO. As expected, the performance of the Cs2SnI6‐based regenerator is strongly dependent on the highest occupied molecular orbital of the dyes. Consequently, Cs2SnI6 shows efficient charge transfer with a thermodynamically favorable charge acceptor level, achieving a 79% enhancement in the photocurrent density (14.1 mA cm−2) compared with that of a conventional liquid electrolyte (7.9 mA cm−2). The results suggest that the surface state of Cs2SnI6 is the main charge transfer pathway in the presence of a redox mediator and should be considered in future designs of Cs2SnI6‐based devices.