Microwave‐assisted polycondensation of 4‐octylaniline with dibromoarylene

The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542     

Measurement of intense microwave field patterns using a neon glow indicator lamp

A novel method using small neon glow lamps with electrodes is developed for measuring intense microwave field patterns. When the lamp axis coincide with the electric field direction, the lamp discharge starts at the feeblest microwave electric field strength. Therefore, the lamp axis shows the field direction and the discharge starting indicates the field strength. The field strength for starting the microwave discharge is less than the strength for AC discharge, because of its low loss discharge mechanism. In the experiments using a microwave oven, it has been demonstrated again comparing with the simulated results that the method is able to use for measuring the intense electric field strength and direction.     

Synthesis of endogenous sperm-activating and attracting factor isolated from ascidian Ciona intestinalis

A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity.     

Time-resolved cavity ringdown spectroscopy on nanoparticle generation in a SiH4–H2 VHF plasma

Time-resolved cavity ringdown (τ-CRD) spectroscopy has been applied to monitor the silyl (SiH₃) radicals and nanoparticles in a pulsed very high frequency (VHF) silane-hydrogen plasma under microcrystalline silicon (μc-Si:H) deposition conditions. The measured cavity loss reveals four time intervals (I up to VI) in the first 4 s of the plasma pulse. By variation of the laser wavelength, it is demonstrated that the small cavity loss at 220 nm reflects the SiH₃ absorption in interval I. In intervals II and III, an additional cavity loss appears. This additional cavity loss corresponds to Rayleigh and Mie scattering by growing nanoparticles. Interval IV reflects the loss of nanoparticles between the electrodes during the afterglow of the plasma pulse. The evolution of the nanoparticle generation determined from the τ-CRD measurements are further confirmed by additional scanning electron microscopy analyses on the nanoparticles created in the plasma pulse.     

The color reactions of sulfonazo-III isomers with lanthanum and alkaline earth metal ions

Six sulfonazo-III isomers were synthesized, and their color reactions with alkaline earth metals and lanthanum investigated. All six reagents had good sensitivities for lanthanum (? = 1.9–5.0·10⁴), but the sensitivities for alkaline earth metals were fairly low except for the barium chelate of sulfonazo-III (? = 2.8 · 10⁴). The position of the sulfo group on the phenyl ring and the symmetry of the reagent are important for the barium reactions, but of little significance for the lanthanum reactions. The effects of water-miscible solvents are also described.     

Magnesium-butadiene addition compounds: Isolation,structural analysis and chemical reactivity

The magnesium-butadiene 1 : 1 (1), 1 : 2 (II) and 1 : 3 addition compounds obtained by the direct metalation of butadiene with metallic magnesium were isolated. These compounds have a polymeric structure. Structural analysis of these compounds by NMR and IR methods was carried out. The process for the formation of II via I and III via II was investigated. The results of protolysis and alkylation of the above magnesium compounds corresponded well to those of crotylmagnesium compounds.     

Self-aggregation of synthetic zinc oxo-bacteriochlorins bearing substituents characteristic of chlorosomal chlorophylls

We prepared novel zinc 8-ethyl-8-methyl-7-oxo- and 7-ethyl-7-methyl-8-oxo-bacteriochlorins 1 and 2 possessing substituents characteristic of chlorosomal chlorophylls, exclusively observed in extramembraneous light-harvesting antennas of photosynthetic green bacteria. The electronic absorption spectra of monomeric 1 and 2 in THF were obviously different: the Q(y) maximum of the former was 724 and that of the latter was 683 nm. This observed spectral difference was clearly explained by theoretical ZINDO/S calculation of their energetically minimized molecules. The optical properties of monomeric 1/2 were controlled by the electronic effect of the 7/8-oxo groups. Specific spectral changes in the electronic, CD, and FT-IR absorption spectra by dilution of the monomeric THF solutions of 1/2 with a 100/200-fold volume of cyclohexane showed the formation of chlorosomal self-aggregation species constructed by 13-C=O...H-O(3(1))...Zn and pi-pi stacking. Especially, the red-shift values in the Q(y) band of 1/2 by self-aggregation were 2450/1970 cm(-1), indicating that exciton interaction among the composite molecules in the self-aggregation of 1 was stronger than in those of 2. Molecular model calculations for dodecamers of 1/2 based on a parallel chain arrangement gave partially different supramolecular structures; the specific hydrogen-bonding distances in 2-dodecamer were larger than those of 1-dodecamer, while both coordinations gave the same Zn-O distance. These modeling results showed that 1 was more tightly packed in the self-aggregates to give a larger red-shift value in the Q(y) band by self-aggregation than 2. The difference in the supramolecular structures is mainly ascribable to the steric effect of 8/7-dialkyl groups in self-aggregates of 1/2.     

Preparation of Polymer Particles Coated with Hydroxyapatite

Polymer particles coated with hydroxyapatite were prepared by treating Pd0 immobilized polystyrene-co-acrylic acid particles in aqueous CaCl2 and NaH2PO2 solutions. Hydroxyapatite coating took place at neutral to alkaline pH conditions, and the homogeneous growth of the hydroxyapatite layer on the surface of polymer particles was observed at relatively low temperature (30-50 degrees C). The thickness of the hydroxyapatite layer increased with reaction time. Copyright 1999 Academic Press.