Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior

Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was performed at ?78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (M_w/M_n = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at ?78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4‐ for poly(DMPA), whereas 20–30% of the 1,2‐structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010     

In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

We propose detecting a fragment ion (Ph₂As⁺) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH⁺) of DA, DC, DPAH, and BDPAO could produce Ph₂As⁺ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph₂As⁺ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH⁺ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph₂As⁺.

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Ultrafine Metal–Organic Right Square Prism Shaped Nanowires

We report the structural design and control of electronic states of a new series of ultrafine metal–organic right square prism‐shaped nanowires. These nanowires have a very small inner diameter of about 2.0 Å, which is larger than hydrogen and similar to xenon atomic diameters. The electronic states of nanowires can be widely controlled by substitution of structural components. Moreover, the platinum homometallic nanowire shows a 100 times higher proton conductivity than a palladium/platinum heterometallic one depending on the electronic states.     

New chemosensor for larger guests based on modified cyclodextrin bearing seven hydrophobic chains each with a hydrophilic end group

A new chemosensor for larger guests was prepared. The new chemosensor bears hydrophobic units at the primary hydroxy side and a dansyl unit at the secondary hydroxy side of β-cyclodextrin. Due to the hydrophobic units, the new chemosensor is sensitive to large or slender guests such as SDS and insensitive to 1-adamantanol, which is a good guest for the natural β-CD.     

A new high‐pressure strontium germanate,SrGe2O5

The Sr–Ge–O system has an earth‐scientific importance as a potentially good low‐pressure analog of the Ca–Si–O system, one of the major components in the constituent minerals of the Earth's crust and mantle. However, it is one of the germanate systems that has not yet been fully examined in the phase relations and structural properties. The recent findings that the SrGeO₃ high‐pressure perovskite phase is the first Ge‐based transparent electronic conductor make the Sr–Ge–O system interesting in the field of materials science. In the present study, we have revealed the existence of a new high‐pressure strontium germanate, SrGe₂O₅. Single crystals of this compound crystallized as a co‐existent phase with SrGeO₃ perovskite single crystals in the sample recovered in the compression experiment of SrGeO₃ pseudowollastonite conducted at 6 GPa and 1223 K. The crystal structure consists of germanium–oxygen framework layers stacked along [001], with Sr atoms located at the 12‐coordinated cuboctahedral site; the layers are formed by the corner linkages between GeO₆ octahedra and between GeO₆ octahedra and GeO₄ tetrahedra. The present SrGe₂O₅ is thus isostructural with the high‐pressure phases of SrSi₂O₅ and BaGe₂O₅. Comparison of these three compounds leads to the conclusion that the structural responses of the GeO₆ and GeO₄ polyhedra to cation substitution at the Sr site are much less than that of the SrO₁₂ cuboctahedron to cation substitution at the Ge sites. Such a difference in the structural response is closely related to the bonding nature.     

Protonation-induced structural change of lyotropic liquid crystals in oley- and alkyldimethylamine oxides/water systems

Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain.