Biochemical Characterization of a Book RedoxRegulated Metacaspase in a Underwater Diatom

We report an anomalous photoinduced reconstructing and dark self-healing process on Bi2O2S nanoplates by monitoring the time profile of open-circuit potential (OCP). When the light was switched on and off on the nanoplates, we observed pronounced and repeatable decrement-recovery cycles of the OCP signal, which are inexplicable by a rapid electron-hole separation-recombination process only as in a conventional semiconductor. It is proposed that upon irradiation, accumulation of photogenerated holes at the electrode surface caused oxidation of the S layers of Bi2O2S nanoplates into certain intermediates, which, when the light was turned off, were then reduced back to the original state by the electron back flow. Raman scattering spectroscopy provided te S-S vibrational signature of the intermediate, evidencing the hole oxidative dimerization of the S2- species and the inverse reductive S-S dissociation process. The photophysics and photochemistry of semiconductor nanoplates reported here may inspire the development of energy devices, switches, and memristors.A monolith bonding system has a high reliability for dissimilar material bonding. The epoxy monolith layer fabricated on a substrate guarantees bond strength by the anchor effect, regardless of the compatibility of the used materials. Designing a high-performance monolith bonding system requires the suppression of an interfacial failure between the monolith and the substrate. In this study, silane and phosphine coupling agents containing amino and epoxy groups were used to construct a robust interfacial structure between the monolith and the substrates such as glass and metals. The internal and interfacial monolith structures were characterized by three-dimensional X-ray imaging as a nondestructive observation method in addition to the scanning electron microscopy of the sample cross sections. The modification of the substrate-monolith interface using the coupling agents improved the strength of dissimilar material bonding of the glass and metal substrates in combination with thermoplastic resins such as poly(ethylene terephthalate) and polycarbonate bisphenol-A.Polluted water is a worldwide problem; therefore, effective separation of oil/water and removal of dyes, organic micropollutants, and heavy metals in wastewater are the need of the hour. Herein, hydrophilic β-cyclodextrin-grafted carboxymethyl cellulose, biodegradable polyvinyl alcohol, and chitosan were used as main raw materials to construct a multifunctional aerogel framework by simple sol-gel and directional freeze-drying methods. Featuring intrinsic superamphiphilic wettability in air, robust superoleophobic wettability underwater, and excellent shape-recovery characteristics, the biomass-derived aerogel presents durable oil/water separation even after 10 cycles. The aerogels possess prominent adsorption capacity for methyl blue, 1-naphthylamine, and Cu2+, which was as high as 121.55 mg/g, 33.96 mg/g, and 122.6 mg/g, respectively. MK-1775 concentration In addition, various pollutant mixtures could be effectively adsorbed by the aerogel at the same time with the adsorption capacity of 121.75 mg/g for methyl blue, 0.97 mg/g for bisphenol A, and 20.11 mg/g for Cu2+.The new alkaloids marinacarbolines E-Q (1-10, 12-14), caerulomycin N (15), and actinoallonaphthyridine A (16), together with the known marinacarboline C (11) and cyanogramide (17), were isolated from the actinomycete Actinoalloteichus sp. ZZ1866. The structures of the isolated compounds were elucidated based on their HRESIMS data, extensive NMR spectroscopic analyses, Mosher's method, ECD calculations, single-crystal X-ray diffraction analysis, and chemical degradation studies. Marinacarbolines E-L (1-8) share an indole-pyridone-imidazole tetracyclic skeleton, which is the first example of this kind of skeleton. Caerulomycin N (15) and cyanogramide (17) exhibited cytotoxic activity against both human glioma U251 and U87MG cells with IC50 values of 2.0-7.2 μM. Marinacarbolines E (1), G (3), I (5), and M (9) showed cytotoxic activity against U87MG cells with IC50 values of 2.3-8.9 μM.Quantifying vibronic couplings in molecular excited states is crucial for the elucidation of a broad range of photophysical phenomena. In this study, we compare different theoretical approaches for the calculation of reorganization energy, a measure of vibronic coupling strength, and provide a rigorous derivation to show that molecular transition density characterizing electron-hole excitation could be used to quantify the magnitude of reorganization energy. The theory enables a descriptor based on molecular-orbital coefficients and atomic transition densities to quantify the magnitude of reorganization energies in molecular excited states. Applying the approach to low-lying excited states of polyacenes, we demonstrate that transition density distribution explains the difference in the magnitude of the reorganization energy of different excited states. Furthermore, to clarify the applicability of the transition density descriptor in molecular design for small-reorganization energy molecules, we investigate a broad range of molecular chromophores to show the effectiveness of the proposed theory. With this perspective on the relationship between reorganization energy and transition density, we successfully provide a quantitative rule to identify π-conjugated systems with small reorganization energy in the excited state, which should be useful for the development of novel optoelectronic materials.Intermolecular crowding of densely tethered polymers promotes chain extension and anisotropy that induces many unique properties. In this study, we used conformation-sensitive infrared spectroscopy to determine that chain extension in a polymer brush is associated with local conformation rearrangements, i.e., contraction of side groups and increased proportion of gauche twists in the backbone, which served to increase molecular disorder at or below the segmental scale. This conformational transition points to a particular molecular mechanism for chain extension in densely tethered polymers, wherein increased local disorder facilitates global chain ordering (i.e., chain extension) and therefore supplements our current understanding of chain orientation at a molecular level.