Nanostructure control in polymer solar cells by self‐organization

Recently, polymer solar cells (PSCs) based on “bulk heterojunctions” using a simple mixture of electron donor and acceptor materials in thin films have been extensively studied. Although relatively high power conversion efficiencies have been achieved by using this approach, further improvement is necessary to precisely construct stable, reproducible nanostructures that are suitable for both efficient charge separation and transport inside such films. For this purpose, it is highly desirable to utilize a bottom‐up approach, such as the self‐organized formation of inorganic and organic nanostructures. In this review, an overview of our recent studies on the control of nanostructures in PSCs is presented. DOI 10.1002/tcr.201000015     

Multinuclear Pd/Zn complex-catalyzed asymmetric alkylative ring-opening reaction of oxabicyclic alkenes

A multinuclear palladium catalyst can be used to realize the efficient catalytic asymmetric alkylative ring-opening reaction of oxabicyclic alkenes using dimethylzinc. The use of (R)-BINOL-PHOS bearing bisphosphine and diol moieties is essential for achieving excellent catalytic performance; the corresponding monophosphine and hydroxy-protected derivatives showed lower catalytic activities and/or enantioselectivities. The generation of Pd/Zn-multinuclear complexes is a key feature of the present catalysis.     

Quantitative analysis of specific target DNA oligomers using a DNA-immobilized packed-column system

Although a DNA-immobilized packed-column (DNA-packed column), which relies on sequence-dependent interactions of target DNA or mRNA (in the mobile phase) with DNA probes (on the silica particle) in a continuous flow process, could be considered as an alternative platform for quantitative analysis of specific DNA to DNA chip methodology, the performance in practice has not been satisfactory. In this study, we set up a more efficient quantitative analysis system based on a DNA-packed column by employing a temperature-gradient strategy and DMSO-containing mobile phase. Using a temperature-gradient strategy based on T _m values of probe/target DNA hybridizations and DMSO (5%)-containing mobile phase, we succeeded in the quantitative analysis of a specific complementary target distinguishable from non-complementary DNA oligomers or other similar DNA samples. In addition, two different target DNA oligomers even with similar T _m values were separated and detected quantitatively by using a packed column carrying two different DNA probes.     

HPLC determination of methylphenidate and its metabolite,ritalinic acid,by high-performance liquid chromatography with peroxyoxalate chemiluminescence detection

An HPLC–peroxyoxalate chemiluminescence (PO-CL) method for simultaneous determination of methylphenidate (MPH) and ritalinic acid (RA) was developed. The method was used to monitor MPH and RA after administration of MPH to rats. Deproteinized plasma spiked with 1-(3-trifluoromethylphenyl)piperazine (IS) was dried and labeled with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F). The labeled sample was cleaned with two kinds of solid-phase extraction cartridge, and the DBD-labels were separated on an ODS column with gradient elution using a mixture of CH₃CN and imidazole–HNO₃ buffer. Separation of MPH and RA can be achieved within 33 min. The LODs of MPH and RA at a signal-to-noise ratio of 3 were 2.2 and 0.4 ng mL⁻¹, respectively. Moreover, monitoring of MPH and RA after MPH administration (10 mg kg⁻¹) to rat could be performed. The concentration of RA 480 min after administration was eight times higher than that of MPH. The proposed HPLC–PO-CL method was useful for determination of MPH and RA in rat plasma and was successfully used to monitor these substances after MPH administration.     

A new diterpenoid glucoside and two new diterpenoids from the fruit of Vitex agnus-castus

A new labdane-type diterpenoid glucoside and two new labdane-type diterpenoids were isolated from the fruit (chasteberry) of Vitex agnus-castus L. (Verbenaceae) along with 14 known compounds comprising seven labdane-type diterpenoids, one halimane-type diterpenoid, two oleanane-type triterpenoids, two ursane-type triterpenoids, one aromadendrane-type sesquiterpenoid, and one flavonoid. Their structures were characterized on the basis of spectroscopic data as well as chemical evidence. Furthermore, the antioxidative activities of the flavonoid were evaluated using five different analyses.     

Macromolecular crowding effects on reactions of TePixD (Tll0078)

To reveal macromolecular crowding effects on a chemical reaction of a BLUF (sensors of blue light using FAD) protein (PixD from a thermophilic cyanobacterium Thermosynechococcus elongatus BP-1 [TePixD, Tll0078]), the photoreaction was studied at various concentrations of the macromolecule Ficoll-70 by UV/Vis absorption spectroscopy and the pulsed laser-induced transient grating (TG) method. The absorption spectrum did not change with varying concentration of Ficoll-70. The crowding did not affect the quantum yield of the spectral red shift reaction, recovery rate of the product, rate constant of the volume change reaction and the magnitude of the volume change. However, the magnitude of the TG signal representing the diffusion-sensitive conformation change significantly increased on addition of Ficoll-70. This dependence was attributed to the crowding effect on the TePixD decamer-pentamer equilibrium in the solution. This result indicates that the TePixD reaction is more efficient in cellular than in in vitro conditions.     

Flow injection analysis combined with a hydrothermal flow reactor: application to kinetic determination of trace amounts of iridium using a water-soluble porphyrin

A new type of flow injection analysis (FIA) system combined with an extremely high temperature reactor, namely hydrothermal flow injection analysis (HT-FIA), has been successfully constructed for the first time. Fundamental characteristics of HT-FIA system, such as limit temperature, pressure, and flow rate, were examined as an analytical tool. To demonstrate the potential of HT-FIA, the catalytic activity of Ir(IV) for the degradation of a water-soluble porphyrin, 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (TPPS), was applied for the determination of trace amounts of Ir(IV). Although the indicator reaction is very slow at room temperature, HT-FIA system enables to accelerate the reaction. A linear calibration curve was acquired at 10⁻⁸ M level of Ir(IV) and the interferences of platinum group metal ions were examined. The detection limit of Ir(IV) was 5.8 × 10⁻⁹ M and a fairly high-throughput analysis, of which more than 30 samples can be analyzed within 80 min, was achieved.     

Effects of methylation at position 2 of cation ring on rotational dynamics of imidazolium-based ionic liquids investigated by NMR spectroscopy: [C4mim]Br vs [C4C1mim]Br

We investigated the rotational dynamics of two imidazolium-based ionic liquids, 1-butyl-3-methylimidazolium bromide ([C(4)mim]Br) and 1-butyl-2,3-dimethylimidazolium bromide ([C(4)C(1)mim]Br), to reveal the effects of methylation at position 2 of the imidazolium ring (C(2) methylation). The rotational correlation time (τ(local)) for each carbon in the cations is derived from the spin-lattice relaxation time of (13)C nuclear magnetic resonance. The τ(local) results obtained here provide three principle insights into the rotational dynamics of ionic liquids. First, all τ(local) values for [C(4)C(1)mim]Br are greater than those for [C(4)mim]Br owing to a viscosity increase due to C(2) methylation. Second, the rate of change in τ(local) on C(2) methylation differs among the carbons in the cation, which indicates that each carbon has a different microviscosity. Third, the τ(local) increase in the (13)C at the root of the butyl group on C(2) methylation is very small compared to both intuitive prediction and the results from quantum chemical calculations. This indicates that the motion of the butyl group root in [C(4)C(1)mim]Br is not significantly inhibited by the methyl group at the position 2 of the imidazolium ring. The finding provides conclusive information on the origin of the increases in the melting point on C(2) methylation. Hunt previously found through calculation that decreases in entropy are caused by two factors, namely, reductions in the rotational mobility of the butyl group and in the number of stable anion interaction sites with C(2) methylation, resulting in an increase in melting point and viscosity. Our finding experimentally illustrates that the origin of the increases in melting point is not the inhibition of butyl group motion and that the reduction in stable anion interaction sites plays a major role in the increases. Additionally, it is suggested that the viscosity increase on C(2) methylation can be interpreted in the same manner.     

Fabrication of mesoporous polymer monolith: a template-free approach

Mesoporous polyacrylonitrile (PAN) monolith has been fabricated by a template-free approach using the unique affinity of PAN towards a water/dimethyl sulfoxide (DMSO) mixture. A newly developed Thermally Induced Phase Separation Technique (TIPS) has been used to obtain the polymer monoliths and their microstructures have been controlled by optimizing the concentration and cooling temperature.     

Analysis of the unbinding force between telomestatin derivatives and human telomeric G-quadruplex by atomic force microscopy

The force analysis between a macrocyclic hexazole (6OTD) monomer/dimer and telomeric DNA using atomic force microscopy revealed the difference in their binding modes. The 6OTD dimer bound to the G-quadruplex more strongly than the monomer by sandwiching the G-quadruplex.