Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Results from GRACE/SUSY at one-loop

We report the recent development on the SUSY calculations with the help of GRACE system. GRACE/SUSY/1LOOP is the computer code which can generate Feynman diagrams in the MSSM automatically and compute one-loop amplitudes in the numerical way. We present new results of various two-body decay widths and chargino pair production at ILC (international linear collider) at one-loop level.      

Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007     

An enrichment method of molybdenum on a cellulose nitrate resin for the determination by electrothermal atomic absorption spectrometry coupled with the resin suspension injection.

Cellulose derivative resin (CDR) suspensions containing resin particles of cellulose nitrate (CDR(CN)), cellulose acetate (CDR(CA)), or cellulose triacetate (CDR(CTA)) were prepared as the sorbent for resin suspension injection (RSI) electrothermal atomic absorption spectrometry (ETAAS), in which fine resin particles holding a desired trace element were directly injected into the graphite tube as the suspension. To compare the sorption ability, the distribution ratios of the Mo(VI)-phenylfluorone complex were measured between the aqueous phase and the sorbents, including the CDRs mentioned above and the finely divided anion exchange resin (AR). The results showed that the sorption ability decreases in the following order: CDR(CN) > or = AR > CDR(CA) > or = CDR(CTA). It was concluded that CDR(CN) was able to extract more than 98% of Mo(VI), and was suitable for RSI-ETAAS as well as AR. CDR(CN) was used for the determination of Mo in NIES certified reference materials, No. 10 Rice flour-unpolished; the results showed fairly good agreements between the analytical values and the certified values.     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.     

Phase rotation scheme of laser-produced ions for reduction of the energy spread

In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented.