Investigation of Degradation Mechanism of Y6-Based Inverted Organic Solar Cells and Their Utilization in Durable Near-Infrared Photodetection.

The device durability of inverted organic solar cells (OSCs) is investigated based on Y6, which is an effective nonfullerene acceptor for high-performance OSCs. The durability of Y6-based inverted OSCs is poor and it can be caused by aggregation of Y6 in the bulk-heterojunction layer due to heating by continuous photo-irradiation (≈65 °C, 100 mW cm-2 , and 72 h). It is found that the aggregation of Y6 is suppressed at a low temperature (≈50 °C), and that the Y6-based devices can be useful as a photodurable near-infrared detector upon continuous laser irradiation.

A Structurally Robust Chiral Borate Ion: Molecular Design, Synthesis, and Asymmetric Catalysis.

Catalysis by chiral weakly-coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non-nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O-tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins-type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.

Catalyst-Enabled Site-Divergent Stereoselective Michael Reactions: Overriding Intrinsic Reactivity of Enynyl Carbonyl Acceptors.

A site-divergent stereoselective Michael reaction system is developed based on the identification of two distinct catalysts. Cinchonidine-derived thiourea catalyzes the 1,4-addition of prochiral azlactone enolates to enynyl N-acyl pyrazoles in a highly diastereo- and enantioselective manner to give stereochemically defined alkynes, while P-spiro chiral triaminoiminophosphorane catalytically controls the stereoselective 1,6-addition and the consecutive γ-protonation of the vinylogous enolate intermediate to afford Z,E-configured conjugated dienes. This 1,6-adduct serves as a valuable precursor for the synthesis of a 2-amino-2-deoxy sugar.

Magnetic and conducting properties of new halide-bridged mixed-valence Cu(I)-Cu(II) 1D coordination polymers including a hexamethylene dithiocarbamate ligand.

New mixed-valence Cu(I)-Cu(II) coordination polymers with one-dimensional, infinite-chain structures, [Cu(I)(2)Cu(II)X(2)(Hm-dtc)(2)(CH(3)CN)(2)](n) [Hm-dtc(-) = hexamethylene dithiocarbamate; X = Br(-) (1), I(-) (2)], have been prepared and structurally characterized by X-ray diffraction. These complexes consist of a mononuclear copper(II) unit Cu(II)(Hm-dtc)(2) and dinuclear copper(I) units Cu(I)(2)(CH(3)CN)(2)X(2). Magnetic studies have revealed that these complexes have a relatively strong antiferromagnetic interaction [J = -26.9 cm(-1) (1) and J = -22.2 cm(-1) (2)] between the unpaired electrons of the Cu(II) ions through the dinuclear copper(I) halide unit of Cu(I)(2)X(2) in the chain. The electrical properties of 1 and 2 are investigated using an impedance spectroscopy technique, and it is revealed that these complexes exhibit intriguing semiconducting properties with small activation energies [E(a) = 0.562 eV (1) and E(a) = 0.479 eV (2)].

[Development and evaluation of communication skills learning suitable for community pharmacy].

It is a prerequisite for community pharmacists to maintain appropriate communication with patients, but a pharmacist licensee usually must learn communication-skills after starting work as a pharmacist. However, an education system and its evaluation methods are expected to be established, since the extent of self-training and rapidity of skill acquisition may vary largely among pharmacists. Therefore in this study we developed a communication-skills education program suitable for community pharmacies, developed objective-structured clinical examination (OSCE) appraisal charts, and carried out that education and its evaluation for a period of 8 months. The appraisal charts created by us were based on items of the "patient-communication station" categorized as one of the six stations in the five areas of pharmacy OSCE. Our questionnaire for pharmacist trainees after receiving communication-skills education/evaluation resulted in responses including such comments as: the education helped to improve their communication-skills; was useful in actual patient consultations; and increased self-confidence in their work. The OSCE scores gradually increased as the trainees completed more courses in the education program. These results show that the education program, which employs an OSCE appraisal chart, leads to specific outcomes in communication skills learning.

N-Sulfonyl α-imino ester-derived chiral oxaziridines: catalytic asymmetric synthesis and application as a modular chiral organic oxidant.

A novel class of chiral N-sulfonyl oxaziridines is introduced for use as structurally modifiable chiral oxidants. These oxaziridines are readily prepared from N-sulfonyl α-imino esters in a highly enantioenriched form by oxidation with hydrogen peroxide using l-isoleucine-derived triaminoiminophosphorane as a catalyst. The distinct advantage of their structural modularity is demonstrated through the identification of an optimal oxaziridine that exhibits high reactivity and enantiospecificity in the asymmetric oxidation of a silyl enol ether and N-sulfonyl allylic and homoallylic amines.

Enantioselective reductive multicomponent coupling reactions between isatins and aldehydes.

A metal-free stereoselective reductive coupling reaction between isatins and aldehydes is reported. The reaction relies on commercial diethyl phosphite (∼€70 kg-1) as the stoichiometric reductant. Base-catalyzed Pudovik addition and phosphonate/phosphate rearrangement achieved polarity inversion on the isatin, and the derived carbanions were trapped by aldehydes with subsequent dialkoxyphosphinyl migration. Chiral iminophosphoranes were used as basic catalysts to achieve high diastereo- and enantioselectivities with excellent yields.

Crystal structure and carrier transport properties of a new semiconducting 2D coordination polymer with a 3,5-dimethylpiperidine dithiocarbamate ligand.

A novel mixed-valence Cu(I)-Cu(II) coordination polymer with an infinite two-dimensional structure, [Cu3(I)Cu(II)Br3(3,5-Dmpip-dtc)2]n (3,5-Dmpip-dtc(-) = 3,5-dimethylpiperidine dithiocarbamate), was prepared, and its structure was characterized by X-ray diffraction. It shows semiconducting behavior with a relatively small activation energy and high carrier mobility, which were investigated using impedance spectroscopy and flash photolysis time-resolved microwave conductivity measurements, respectively.

Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(I)-Cu(II) coordination polymer including pyrrolidine dithiocarbamate ligand.

A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σµâˆ¼ 0.4 cm(2) V(-1) s(-1).

The eta isoform of protein kinase C inhibits UV-induced activation of caspase-3 in normal human keratinocytes.

Protein kinase C (PKC) fulfills a central role in the decision of cell fate in keratinocytes. Both PKC delta and PKC eta induce growth inhibition and differentiation of normal human keratinocytes (NHK). Here we show that PKC delta and PKC eta play opposite roles in UVB-induced apoptosis in NHK. PKC delta enhanced UVB-induced caspase-3 activity, while overexpression of PKC eta reduced it. In keeping with these observations, the dominant negative mutant of PKC delta significantly inhibited the activation of caspase-3, whereas dominant negative PKC eta increased it in a dose (MOI)-dependent manner. Unlike PKC delta, cleavage and translocation to mitochondria of PKC eta were not observed, resulting in no detection of cytochorome c release. Furthermore, UV-induced activation of p38 MAP kinase, which suppressed the caspase-3 activity in NHK, was blocked by dominant negative PKC eta. These findings suggest that PKC eta negatively regulates UV-induced apoptosis through its localization, resistance to cleavage, and the p38 MAPK pathway.