Geometries, Electronic Couplings, and Hole Dissociation Dynamics of Photoinduced Electron-Hole Pairs in Polyhexylthiophene-Fullerene Dyads Rigidly Linked by Oligophenylenes.

To shed a light on fundamental molecular functions of photoinduced charge conductions by organic photovoltaic materials, it is important to directly observe molecular geometries of the intermediate charges just after the photoinduced electron-transfer reactions. However, highly inhomogeneous molecular environments at the bulk heteojunction interfaces in the photoactive layers have prevented us from understanding the mechanism of the charge conductions. We have herein investigated orbital geometries, electronic couplings, and hole-dissociation dynamics of photoinduced charge-separated (CS) states in a series of poly(3-hexylthiophene)-fullerene linked dyads bridged by rigid oligo-p-phenylene spacers by using time-resolved EPR spectroscopy. It has been revealed that one-dimensional intramolecular hole-dissociations exothermically take place from localized holes in initial CS states, following bridge-mediated, photoinduced charge-separations via triplet exciton diffusions in the conjugated polymer-backbones. This molecular wire property of the photoinduced charges in solution at room temperature demonstrates the potential utility of the covalently bridged polymer molecules applied for the molecular devices.

Remarkable Dependence of the Final Charge Separation Efficiency on the Donor-Acceptor Interaction in Photoinduced Electron Transfer.

The unprecedented dependence of final charge separation efficiency as a function of donor-acceptor interaction in covalently-linked molecules with a rectilinear rigid oligo-p-xylene bridge has been observed. Optimization of the donor-acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100% efficiency. This finding is extremely useful for the rational design of artificial photosynthesis and organic photovoltaic cells toward efficient solar energy conversion.

Overcoming Coulombic Traps: Geometry and Electronic Characterizations of Light-Induced Separated Spins at the Bulk Heterojunction Interface.

Recent progress is overviewed on experimental elucidations of fundamental molecular functions of the light-energy conversions by the photoactive layers of the organic photovoltalic (OPV) cells by means of the time-resolved electron paramagnetic resonance spectroscopy. Positions and orientations of the unpaired electrons and electronic coupling matrix elements are clarified in photoinduced, primary charge-separated (CS) states. Connections between the molecular geometries and the electronic couplings have been characterized for the initial CS states to elucidate how the structure, orbital delocalization, and molecular libration play roles on exothermic carrier dissociation via a vibrationally relaxed charge-transfer complex with prevention of the energy-wasting charge recombination. Superior functions to biological molecules are presented for the efficient photocurrent generations induced by orbital delocalization and by shallow trap depths at polymer-stacking domains. The above structural and electronic characteristics of the primary electron-hole pairs are essential to evaluations, designs, and developments of the efficient solar cells using organic molecules.

Time-Resolved EPR Study of Electron-Hole Dissociations Influenced by Alkyl Side Chains at the Photovoltaic Polyalkylthiophene:PCBM Interface.

Nanosecond time-resolved electron paramagnetic resonance (TREPR) spectroscopy has been utilized at T = 77 K to characterize alkyl side-chain effects on geometries and on the electronic couplings (VCR) of transient charge-separated (CS) states in the photoactive layers fabricated by the spin-coating of mixed solutions of regioregular polyalkylthiophenes (RR-P3AT) and [6,6]-C61-butyric acid methyl ester (PCBM). By increasing the alkyl side-chain number from 6 to 12 in P3AT, a highly distant and long-lived CS state has been obtained. This result is explained by a coupling of the hole dissociation to the polymer librations by the side-chains. From an exponential decay of VCR with respect to the CS distance, the attenuation factor (ße) has been determined to be ße = 0.2 Å(-1). Such a long-range tunneling feature is explained by the generations of the shallowly trapped, delocalized electron-hole pairs by the dissociation of the hole toward π-stacking directions at the organic photovoltaic interface.

How to identify water from thickener aqueous solutions by touch.

Water detection is one of the most crucial psychological processes for many animals. However, nobody knows the perception mechanism of water through our tactile sense. In the present study, we found that a characteristic frictional stimulus with large acceleration is one of the cues to differentiate water from water contaminated with thickener. When subjects applied small amounts of water to a glass plate, strong stick-slip phenomena with a friction force of 0.46 ± 0.30 N and a vertical force of 0.57 ± 0.36 N were observed at the skin surface, as shown in previous studies. Surprisingly, periodic shears with acceleration seven times greater than gravitational acceleration occurred during the application process. Finite-element analyses predicted that these strong stimuli could activate tactile receptors: Meissner's corpuscle and Pacinians. When such stimuli were applied to the fingertips by an ultrasonic vibrator, a water-like tactile texture was perceived by some subjects, even though no liquid was present between the fingertip and the vibrator surface. These findings could potentially be applied in the following areas: materials science, information technology, medical treatment and entertainment.

Tactile impression and friction of water on human skin.

Water has a unique touch as well as characteristic physical properties. However, nobody knows the real identity of its touch. Here, we show that water creates a stick-slip feel when a small amount is rubbed using fingertip on an artificial skin that mimics the structure of human skin. The results of frictional analyses predict that this stick-slip feel is caused by a drastic change in frictional resistance. The present result is valuable for biologists and robot engineers as well as cognitive scientists and tribologists, because it is a new example of stick-slip phenomena on biological surfaces. The tactile texture of this most familiar material could also be applied to consumer products or virtual reality systems.

Ecophysiology of seed germination in Erythronium japonicum (Liliaceae) with underdeveloped embryos.

Erythronium japonicum (Liliaceae) (Japanese name, katakuri) is indigenous to Japan and adjacent Far East regions. We examined their embryo elongation, germination, and seedling emergence in relationship to the temperature. In incubators, seeds did not germinate at 20°/10° (light 12 h/dark 12 h alternating temperature), 20°, 15°, 5°, or 0°C with a 12-h light photoperiod for 200 d. They germinated at 15°/5° or 10°C, starting on day 135. If seeds were kept at 20° or at 25°/15°C before being exposed to 5°C, the seeds germinated, but if kept at 25° or 30°C they did not. Embryos at 25°/15°C grew to half the seed length without germinating; at 0° or 5°C, embryos elongated little. Embryos grew and seeds germinated when kept at 25°/15°C for 90 d and then at 5°C. In the field, seeds are dispersed in mid-June in Hokkaido and in Honshu, mid-May to mid-June. Seeds do not germinate immediately after dispersal because the embryo is underdeveloped. Embryos elongated at medium temperatures in autumn after summer heat, and germination ends in November at 8°/0°C. After germination, seedling emergence was delayed, and most seedlings were observed in early April around the snowmelt when soil cover was 2-3 mm.