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.     

Metal components analysis of metallothionein-III in the brain sections of metallothionein-I and metallothionein-II null mice exposed to mercury vapor with HPLC/ICP-MS

Mercury vapor is effectively absorbed via inhalation and easily passes through the blood–brain barrier; therefore, mercury poisoning with primarily central nervous system symptoms occurs. Metallothionein (MT) is a cysteine-rich metal-binding protein and plays a protective role in heavy-metal poisoning and it is associated with the metabolism of trace elements. Two MT isoforms, MT-I and MT-II, are expressed coordinately in all mammalian tissues, whereas MT-III is a brain-specific member of the MT family. MT-III binds zinc and copper physiologically and is seemed to have important neurophysiological and neuromodulatory functions. The MT functions and metal components of MTs in the brain after mercury vapor exposure are of much interest; however, until now they have not been fully examined. In this study, the influences of the lack of MT-I and MT-II on mercury accumulation in the brain and the changes of zinc and copper concentrations and metal components of MTs were examined after mercury vapor exposure by using MT-I, II null mice and 129/Sv (wild-type) mice as experimental animals. MT-I, II null mice and wild-type mice were exposed to mercury vapor or an air stream for 2 h and were killed 24 h later. The brain was dissected into the cerebral cortex, the cerebellum, and the hippocampus. The concentrations of mercury in each brain section were determined by cold vapor atomic absorption spectrometry. The concentrations of mercury, copper, and zinc in each brain section were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mercury accumulated in brains after mercury vapor exposure for MT-I, II null mice and wild-type mice. The mercury levels of MT-I, II null mice in each brain section were significantly higher than those of wild-type mice after mercury vapor exposure. A significant change of zinc concentrations with the following mercury vapor exposure for MT-I, II null mice was observed only in the cerebellum analyzed by two-way analysis of variance. As for zinc, the copper concentrations only changed significantly in the cerebellum. Metal components of metal-binding proteins of soluble fractions in the brain sections were analyzed by size-exclusion high-performance liquid chromatography (HPLC) connected with ICP-MS. From the results of HPLC/ICP-MS analyses, it was concluded that the mercury components of MT-III and high molecular weight metal-binding proteins in the cerebellum of MT-I, II null mice were much higher than those of wild-type mice. It was suggested that MT-III is associated with the storage of mercury in conditions lacking MT-I, and MT-II. It was also suggested that the physiological role of MT-III and some kind of high molecular weight proteins might be impaired by exposure to mercury vapor and lack of MT-I and MT-II.     

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.     

Synthesis of poly(vinylene-arsine)s: alternating radical copolymerization of arsenic atomic biradical equivalent and phenylacetylene

Novel organoarsenic polymers, poly(vinylene-arsine)s, were synthesized by a free-radical alternating copolymerization of phenylacetylene with cyclooligoarsines as an atomic biradical equivalent. The polymerization between pentamethylpentacycloarsine (1a) or hexaphenylhexacycloarsine (1b) with phenylacetylene (2) in the presence of a catalytic amount of AIBN (in benzene; refluxing; for 12 h) gave the corresponding poly(vinylene-arsine)s. The obtained polymers were soluble in common organic solvents such as THF, chloroform, and benzene. From gel permeation chromatographic analysis (chloroform, PSt standards), the number-average molecular weights of the polymers from 1a and 1b were found to be 11500 and 3900, respectively. The structures of the polymers were supported by 1H and 13C NMR spectroscopies. The corresponding polymer was also obtained by irradiation of a benzene solution of 1a and 2 with xenon lamp at room temperature. After the polymer from 1a was stirred vigorously with 30% H2O2, the 1H NMR spectrum of the polymer showed the methyl proton that was assigned to As(III)-Me, suggesting the insensitivity of the trivalent state arsenic in the main chain to the oxidation. The structures and the molecular weights of the polymers were insensitive to the feed ratio of the monomers. This result indicates that the addition of the arsenic radical to phenylacetylene was a rate-determining step in the copolymerization.     

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.     

Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics

Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics.     

Effects of various thiol molecules added on morphology of dendrimer-gold nanocomposites

Interactions between poly(amidoamine) dendrimer (PAMAM)-gold nanocomposites and alkanethiols and between the former nanocomposites and thiol-modified poly(amidoamine) dendrons in ethyl acetate were investigated by adding alkanethiols, such as 1-propanethiol and 1,3-propanedithiol, and thiol-modified poly(amidoamine) dendrons, generations 0.5 and 2.5 (G0.5-SH and G2.5-SH). The PAMAM dendrimers with surface methyl ester groups used were generations 1.5 and 5.5 (G1.5 and G5.5). The mean particle sizes of PAMAM-gold nanocomposites were about 2.1 for G1.5 and 2.4 nm for G5.5. In both nanocomposite systems where 1-propanethiol and 1,3-propanedithiol were added, the mean particle size was about 4 nm, twice that of the systems where these thiols were not added. Increasing the addition of 1,3-propanedithiol made the average particle size smaller for both nanocomposites systems. To compare with alkanethiol, thiol-modified poly(amidoamine) dendron with a highly branched structure on one side was synthesized. Using G2.5-SH as a protective agent, dendron-gold nanocomposites with mean diameters of 3 to 4 nm were obtained. The difference in particle size was seen only when the combination of PAMAM-gold nanocomposites and thiol-modified dendron was less sterically dense, modified dendron (G0.5-SH). The mechanisms for morphology changes in the dendrimer-gold nanocomposites by the addition of these thiols are discussed.     

Distribution of polymer deposition in plasma polymerization. III. Effect of discharge power

Distribution of polymer deposition in an inductively coupled rf discharge system is studied as a function of level of discharge power with acetylene and styrene as monomers. When a fixed flow rate is used, the discharge power has a relatively small effect on the pattern of distribution of polymer deposition as long as values of W/FM, where W is discharge wattage, F is flow rate, and M is molecular weight of monomer, are maintained above a critical level to maintain full glow in the reaction tube. It has been shown that plasma polymerization of two monomers which have different molecular weights can be compared in a fair manner by selecting conditions to yield similar value of W/FM.