Transient charge carrier dynamics in organic solar cell devices studied by simultaneous optical and electric detection.

For the clarification of dynamics of photogenerated carriers in practical organic solar cell devices, we have developed a methodology to simultaneously acquire reflection-mode transient optical absorption (ΔA) and transient electric current (Δi) signals. For a typical polythiophene:fullerene bulk heterojunction solar cell device, both the ΔA and Δi signals due to the photogenerated carriers are characterized by the power-law decays of ∝t-α, which are interpreted by detrapping-limited recombination at earlier times than ∼1 μs and trap-free diffusion/drift at later times. Furthermore, we have succeeded in observing switching of the power index α for ΔA signals as well as for Δi signals; the time at which switching occurs indicates the extraction of carriers by electrodes (transit times).

Rapid expansion of the invasive-like red macroalga, Chondria tumulosa (Rhodophyta), on the coral reefs of the Papahānaumokuākea Marine National Monument.

A cryptogenic, invasive-like red macroalga, Chondria tumulosa, was first observed in 2016 forming thick mats on the forereef of Manawai Atoll within Papahānaumokuākea Marine National Monument. Subsequent expeditions revealed an increased abundance of this alga. In 2021, unattached C.

Triarylamine-Substituted Benzimidazoliums as Electron Donor-Acceptor Dyad-Type Photocatalysts for Reductive Organic Transformations.

Triarylamine-substituted benzimidazoliums (BI-PhNAr), new electron donor-acceptor dyad molecules, were synthesized. Their photocatalytic properties for reductive organic transformations were explored using absorption and fluorescence spectroscopy, redox potential determinations, density functional theory calculations, transient absorption spectroscopy, and reduction reactions of selected substrates. The results show that irradiation of BI-PhNAr promotes photoinduced intramolecular electron transfer to form a long-lived (∼300 μs) charge shifted state (BI-PhNAr).

Transient photocurrent and optical absorption of disordered thin-film semiconductors: In-depth injection and nonlinear response.

The time-of-flight method is a fundamental approach for characterizing the transport properties of semiconductors. Recently, the transient photocurrent and optical absorption kinetics have been simultaneously measured for thin films; pulsed-light excitation of thin films should give rise to non-negligible in-depth carrier injection. Yet, the effects of in-depth carrier injection on the transient currents and optical absorption have not yet been elucidated theoretically.

An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence.

1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Hückel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative.

Photogenerated Radical Pair between Flavin and a Tryptophan-Containing Transmembrane-Type Peptide in a Large Unilamellar Vesicle.

Electron-transfer (ET) reactions in biological systems, such as those with magnetic sensors based on flavoproteins and electron transport at biomembrane interfaces, are interesting and important issues that require understanding. As a model system of flavoproteins in biomimetic environments, we report the dynamics of the radical pair generated by photoinduced ET between riboflavin tetrabutylate (RFTB) and tryptophan (Trp) residues in a transmembrane-type polypeptide, both of which are distributed in a large unilamellar vesicle of 1,2-dimyristoyl--glycero-3-phosphocholine. The Trp residues locate near the hydrophilic membrane interface, as confirmed by a dual-fluorescence quenching assay.

Peak autumn leaf colouring along latitudinal and elevational gradients in Japan evaluated with online phenological data.

We evaluated the spatial characteristics of the first day of peak leaf colouring (PLC) and their relationships with air temperature along latitudinal and elevational gradients in Japan from 2015 to 2017. Leaf colouring information collected from more than 740 sites via citizen science was analysed, representing elevations from 0 to 2800 m and latitudes from 32°N to 44°N. We found that locations with earlier PLC dates (day of year 265-294) displayed steeper slopes in elevation per degree of latitude than locations with later PLC dates (day of year 295-314).

Cultivation potential projections of breadfruit (Artocarpus altilis) under climate change scenarios using an empirically validated suitability model calibrated in Hawai'i.

Humanity faces significant challenges to agriculture and human nutrition, and changes in climate are predicted to make such challenges greater in the future. Neglected and underutilized crops may play a role in mitigating and addressing such challenges. Breadfruit is a long-lived tree crop that is a nutritious, carbohydrate-rich staple, which is a priority crop in this regard.

Effects of the Peripheral Substituents, Central Metal, and Solvent on the Photochemical and Photophysical Properties of 5,15-Diazaporphyrins.

Metal complexes of 3,7,13,17-tetrakis(di(4-carboxyphenyl)amino)-5,15-diazaporphyrin (MDAP-COOH; M=Pd, Cu) and their ethyl ester precursors (MDAP-COOEt; M=Pd, Cu) have been synthesized for use as near-infrared (NIR)-light-responsive photosensitizers. Under irradiation with visible or NIR light, PdDAP-COOEt in toluene generated singlet oxygen ( O ) with an excellent quantum yield (Φ =0.99), whereas CuDAP-COOEt exhibited a lower efficiency (Φ =0.

Spin-dependent electron transfer dynamics in a platinum-complex-donor-acceptor triad studied by transient-absorption detected magnetic field effect.

For realization of efficient organic light-energy conversion systems, controlling the lifetime of photogenerated charge separated states in donor (D)-acceptor (A) molecules is of much importance; the spin dynamics is one of the important controlling factors. We previously reported that the covalently-linked 1,3-bis(2-pyridylimino)-isoindolate platinum (BPIPt)-dimethoxytriphenylamine (D)-naphthaldiimide (A) triad molecule (BPIPt-DA) exhibits a triplet-born long-lived charge separated state (BPIPt-DA), the lifetime of which is significantly increased from 4 µs to 10 µs by an applied magnetic field of 270 mT in room temperature tetrahydrofuran (THF). The purpose of the present study is to clarify detailed dynamics of spin-dependent generation and the decay of BPIPt-DA.

Mania induced by isoniazid preventive therapy during steroid treatment for rheumatoid arthritis and organising pneumonia.

Isoniazid preventative therapy is widely used for latent tuberculosis infection. Isoniazid is highly effective but has many adverse effects, including neuropsychiatric. We describe the case of an 80-year-old woman with mania.

Improved Characterisation of Vegetation and Land Surface Seasonal Dynamics in Central Japan with Himawari-8 Hypertemporal Data.

Spectral vegetation index time series data, such as the normalized difference vegetation index (NDVI), from moderate resolution, polar-orbiting satellite sensors have widely been used for analysis of vegetation seasonal dynamics from regional to global scales. The utility of these datasets is often limited as frequent/persistent cloud occurrences reduce their effective temporal resolution. In this study, we evaluated improvements in capturing vegetation seasonal changes with 10-min resolution NDVI data derived from Advanced Himawari Imager (AHI), one of new-generation geostationary satellite sensors.

Magnetoconductance Study on Nongeminate Recombination in Solar Cell Using Poly(3-hexylthiophene) and [6,6]-Phenyl-C-butyric Acid Methyl Ester.

The magnetoconductance (MC) effect was investigated for two types of organic solar cells with single junction (SJ) and bulk junction (BJ) of poly(3-hexylthiophene) (P3HT) as donor (D) and [6,6]-phenyl-C-butyric acid methyl ester (PCBM) as acceptor (A). Three components with different half-field-at-half-maximums ( ) of 4 ± 1, 20 ± 15 and >400 mT, hereafter referred to MC in a sequence, were observed in the magnetic field dependence of the MC effects measured under dark and light conditions. The magnitude of the MC components is sensitive to not only the junction structure of the cell but also the presence or absence of incident light.

Gigantic Magnetic Field Effect on the Long-Lived Intermolecular Charge-Separated State Created at the Nonionic Bilayer Membrane.

For realization of low-cost organic photon-energy conversion, the supramolecular approach has been a focus of attention as a counter approach to precise synthesis of covalently linked donor (D)-acceptor (A) molecules. Here we report photogeneration of a long-lived (∼3 μs) intermolecular charge-separated (CS) state of metal porphyrins (D) and an alkyl viologen (A) at an interface of a vesicle membrane formed by self-assembly of nonionic surfactant and cholesterol molecules. The yield of escaped free radicals is negligibly low as in the case of CS states in covalently linked D-A systems.

Visible Light and Hydroxynaphthylbenzimidazoline Promoted Transition-Metal-Catalyst-Free Desulfonylation of N-Sulfonylamides and N-Sulfonylamines.

A visible light promoted process for desulfonylation of N-sulfonylamides and -amines has been developed, in which 1,3-dimethyl-2-hydroxynaphthylbenzimidazoline (HONap-BIH) serves as a light absorbing, electron and hydrogen atom donor, and a household white light-emitting diode serves as a light source. The process transforms various N-sulfonylamide and -amine substrates to desulfonylated products in moderate to excellent yields. The observation that the fluorescence of 1-methyl-2-naphthoxy anion is efficiently quenched by the substrates suggests that the mechanism for the photoinduced desulfonylation reaction begins with photoexcitation of the naphthoxide chromophore in HONap-BIH, which generates an excited species via intramolecular proton transfer between the HONap and BIH moieties.

Quantifying urban growth patterns in Hanoi using landscape expansion modes and time series spatial metrics.

Urbanization has been driven by various social, economic, and political factors around the world for centuries. Because urbanization continues unabated in many places, it is crucial to understand patterns of urbanization and their potential ecological and environmental impacts. Given this need, the objectives of our study were to quantify urban growth rates, growth modes, and resultant changes in the landscape pattern of urbanization in Hanoi, Vietnam from 1993 to 2010 and to evaluate the extent to which the process of urban growth in Hanoi conformed to the diffusion-coalescence theory.

Benzimidazolium Naphthoxide Betaine Is a Visible Light Promoted Organic Photoredox Catalyst.

Benzimidazolium naphthoxide (ONap-BI) was first synthesized and utilized as an unprecedented betaine photoredox catalyst. Photoexcited state of ONap-BI generated by visible light irradiation catalyzes the reductive deiodination as well as desulfonylation reactions in which 1,3-dimethyl-2-phenylbenzimidazoline (Ph-BIH) cooperates with as an electron and hydrogen atom donor. Significant solvent effects on the reaction progress were discovered, and specific solvation toward imidazolium and naphthoxide moieties of ONap-BI was proposed.

Computational study on formation of 15-membered azalactone by double reductive amination using molecular mechanics and density functional theory calculations.

Formation of 15-membered azalactone by double reductive amination was analyzed using molecular mechanics and density functional theory calculations for simplified model compounds. As a result, the following aspects were clarified. When methylamine attacks a linear bis-aldehyde in the first step, there are possibilities that two regioisomers are formed.

Biological processes dominate seasonality of remotely sensed canopy greenness in an Amazon evergreen forest.

Satellite observations of Amazon forests show seasonal and interannual variations, but the underlying biological processes remain debated. Here we combined radiative transfer models (RTMs) with field observations of Amazon forest leaf and canopy characteristics to test three hypotheses for satellite-observed canopy reflectance seasonality: seasonal changes in leaf area index, in canopy-surface leafless crown fraction and/or in leaf demography. Canopy RTMs (PROSAIL and FLiES), driven by these three factors combined, simulated satellite-observed seasonal patterns well, explaining c.

Solvent Viscosity Effect on Triplet-Triplet Pair in Triplet Fusion.

The effect of the solvent viscosity dependence of time-resolved magnetoluminescence (ML) on the delayed fluorescence of 9,10-diphenylanthracene (DPA) sensitized by platinum octaethylporphyrin has clarified the structure and dynamics of the triplet-triplet pair (TT), i.e., the transition state of triplet fusion.