Effect of Substrates on the Addition Polymerization of 1,4-Benzenedithiol to 1,4-Diethynylbenzene in the Solid State and the Electronic Properties of the Resulting Polymer

The effect of substrates on the addition polymerization of 1,4-benzenedithiol (BDT) to 1,4-diethynylbenzene (DEB) in the solid state and the electronic properties of the polymers obtained were studied. As the substrate polymer sheets, for instance, PET (poly (ethylene terephthalate)) sheet, ON-6 (oriented nylon-6) sheet and so on having surface free energies Γ_s from 27.4 to 55.0 erg/cm² were used. At the monomer sublimation temperature of 60°C, the S wt% (sulfur content) and the cis content of the polymers were not affected by the kind of polymer sheets. However, the molecular weights, M¯_n of the polymers polymerized on the polymer sheets were 13,000–30,000, and the values were several times higher than the molecular weight of the polymers polymerized on glass plate. On the other hand, at the sublimation temperature of 82°C, the cis content of the polymers apparently increased with decreasing d-value of the polymer sheets. On X-ray diffraction patterns of monomer mixtures sublimed onto polymer sheets, the diffraction intensities and the diffraction peak positions were concerned with the d-value of the polymer sheets. Using polymer sheets, the diffraction peak intensities of the monomer mixture at 7.73 and 7.58 Å decreased compared with those on glass plate. In contrast, the peak at 3.65 Å, which is a negligibly small peak on glass plate, obviously increased. However, as the d-value of the polymer sheets (PET 3.45 Å; OPP (oriented polypropylene) 5.2 Å) increased, the diffraction peak intensities at 7.73 Å and 7.58 Å gradually increased and the diffraction peak intensity at 3.65 Å gradually decreased. The parallel electrical conductivities (σ_||) toward the layered structural polymer on PET, ON-6 and glass plate under air atmosphere were 10⁻⁷, 10⁻⁹ and 10⁻¹¹ S/cm, respectively. Under a reduced pressure of 10⁻³ mmHg, the σ_|| values of each polymer lowered by one or two orders of magnitude. On the other hand, the σ_|| values of the nonlayered structural polymers under air atmosphere were about 10⁻¹¹–10⁻¹² S/cm and were independent of the substrates. Even under a reduced pressure of 10⁻³ mmHg, the σ_|| values hardly changed and remained at 10⁻¹¹–10⁻¹² S/cm. The vertical electrical conductivities (σ_⟂) of the layered structural polymers on conductive PET sheet coated by indium tin oxide or NESA glass plates were independent of the substrates and were 10⁻¹⁴ S/cm under air atmosphere. The σ_⟂ values of the nonlayered structural polymers also exhibited the same values. The reversible change of the amount of the layered structural polymer on PET sheet was also caused by irradiation of the photo-light which is the effective wavelength for the phase transition of the polymers mounted on glass plate. The σ_|| value of the layered structural polymer on ON-6 sheet reversibly changed with the amount of the layer structure controlled by the photo-light, that is, the σ_|| increased up to about one order of magnitude by the photo-light at 545.6 nm. On the other hand, the _|| decreased to about one order of magnitude by the photo-light at 539.6 nm. Anisotropic conductivity with respect to σ_|| and σ_⟂, and oxygen doping mechanisms were discussed in relation to the layer structure of polymers. © 1997 John Wiley & Sons, Ltd.     

Synthesis of a star-shaped polymer via coordination of ester-linked pyridyl-terminated poly(oxyethylene) with ru(II)

The star-shaped polymer with trans-tetrapyridyl complex of Ru(II) as a core was prepared by complexation of ester-linked pyridyl-terminated poly(oxyethylene) (M̄_n = 2000) with a Ru₅Cl₁₂²⁻ cluster. The unimodal peak of the star-shaped polymer in the gel-permeation chromatogram was shifted to a higher molecular weight region than that of the starting prepolymer. The electron-withdrawing ester substituent in para position of the pyridine ring shifted the metal-to-ligand charge transfer (MLCT) band into the visible region.     

Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal. The introduction of simple M⁺X⁻ salts such as Na⁺PF₆⁻ and K⁺I⁻ into the ionic channel of 1 enhanced the ionic conductivity of the Col_h phase of the M⁺·(1)·X⁻ salts, with the highest ionic conductivity reaching ∼10⁻⁶ S cm⁻¹ for K⁺·(1)·I⁻ and Na⁺·(1)·PF₆⁻ at 460 K, which was approximately 5 orders of magnitude higher than that of 1. The introduction of non-ferroelectric 1 into the ferroelectric N,N′,N′′-tri(tetradecyl)-1,3,5-benzenetricarboxamide (3BC) elicited a ferroelectric response from the mixed Col_h phase of (3BC)_x(1)_1−x with x = 0.9 and 0.8. The further doping of M⁺X⁻ into the ferroelectric Col_h phase of (3BC)_0.9(1)_0.1 enhanced the ferroelectric polarisation assisted by ion displacement in the half-filled ionic channel for the vacant dibenzo[18]crown-6 of (3BC)_0.9[(M⁺)_0.5·(1)·(X⁻)_0.5]_0.1.

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal.     

Studies on the constituents of Gardenia species. III. New iridoid glycosides from the leaves of Gardenia jasminoides cv. fortuneana Hara

Two new iridoid glycosides, 7 beta,8 beta-epoxy-8 alpha-dihydrogeniposide (1) and 8-epiapodantheroside (2), were isolated, together with six known (3-8) and three artifact (9-11) iridoids, from the leaves of Gardenia jasminoides cv. fortuneana Hara. Their structures were established based on chemical and spectral data.     

Ambident reactivity of the thiocyanate anion revisited: can the product ratio be explained by the hard soft acid base principle?

Laser flash photolysis and stopped-flow methods have been employed to determine the kinetics of the reactions of benzhydrylium ions with both termini of the thiocyanate ion. In contrast to previous investigations which reported sulfur/nitrogen ratios of k(S)/k(N) = 2-10 for the reactions of carbocations with SCN(-), values of k(S)/k(N) = 10(3)-10(4) are now derived from absolute rate constants. This discrepancy is explained by the fact that the data determined in this investigation are the first which refer to activation-controlled attack of carbocations at both termini of the thiocyanate ion, while previous reactivity ratios included diffusion-controlled reactions. It is concluded that the selectivities of the reactions of carbocations with the thiocyanate ion cannot be explained by the hard soft acid base principle.     

Identification of Shiga toxins in Shiga toxin-producing Escherichia coli using immunoprecipitation and high-performance liquid chromatography-electrospray ionization mass spectrometry

We developed a rapid and reliable identification method for Shiga toxins in Shiga toxin-producing Escherichia coli (STEC) using immunoprecipitation and high-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS). Polyclonal antisera specific for Shiga toxin 1 (Stx1) and Shiga toxin 2 (Stx2) were raised in rabbits so as to be used for the immunoprecipitation. The immunoprecipitaion was carried out by mixing sample solutions with 50 microl each of the antisera to Stx1 and Stx2 followed by allowing the mixed solutions to stand for 30 min. The quantity required to obtain the immunoprecipitate was more than 0.5 microg of Shiga toxins. HPLC-ESI-MS analysis of the resulting immunoprecipitates provided accurate molecular weight information on Shiga toxins, leading to direct evidence for the presence of these toxins. It requires at most two days to perform our procedure from toxin extraction to measurement of HPLC-ESI-MS whereas the previous method using isolation procedures required about two weeks to complete. The usefulness of the present method has been demonstrated by identifying Stx1, Stx2 and a variant of Stx2 (Stx2e) in the immunoprecipitates prepared from STEC strains.     

Reversible control of enzymatic transglycosylations in supercritical fluoroform using a lipid-coated beta-D-galactosidase

The transgalactosylation rate catalyzed by the lipid-coated beta-d-galactosidase in supercritical fluoroform (scCHF3) can be reversibly controlled by changing temperature or pressure (reflecting polarity changes) without damaging enzymes.     

Convenient synthesis of 3,3,3-trifluoropropenyl compounds from aromatic aldehydes by means of the TBAF-mediated Horner reaction

A simple synthesis of 3,3,3-trifluoropropenyl compounds by means of the TBAF-mediated Horner reaction is described. The reagent, 2,2,2-trifluoroethyldiphenylphosphine oxide, was readily prepared either by Arbuzov reaction of ethyl diphenylphosphinite with 2,2,2-trifluoroethyl iodide or by treating chlorodiphenylphosphine with trifluoroacetic acid and water. Treatment of the phosphine oxide with aromatic aldehydes in the presence of TBAF at room temperature afforded the corresponding 3,3,3-trifluoropropenyl compounds in good yields. The present method is very convenient for preparing 3,3,3-trifluoropropenyl compounds from aromatic aldehydes in terms of availability of the reagent, operational simplicity, and good yields of the products.     

An indication of magnetic-field-induced superconductivity in a bifunctional layered organic conductor,kappa-(BETS)(2)FeBr(4)

Hybrid systems consisting of the conducting layers of organic donor molecules and the magnetic layers of inorganic anions have been focused on as possible bifunctional materials, whose conducting properties can be tuned by controlling the magnetic state of the anion layers on an application of magnetic field. Here we report the magnetoresistance of the antiferromagnetic organic superconductor, kappa-(BETS)2FeBr4 [BETS = bis(ethylenedithio)tetraselenafulvalene], consisting of the two-dimensional superconducting layers of the BETS semications and the insulating layers of the FeBr4- anions. Due to the metamagnetic nature of the Fe3+ spin system, characteristic resistivity decrease was observed just below the antiferromagnetic superconductor-to-ferromagnetic metal transition at 1.6 T. Furthermore, an indication of the onsets of the magnetic-field-induced superconductivity was discovered around 12.5 T.     

A conducting crystal based on a single-component paramagnetic molecule, [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate)

A single-component conducting molecular crystal composed of paramagnetic copper complexes, [Cu(dmdt)2]0+, was prepared. The crystal has an unprecedented three-dimensionally packed molecular arrangement and exhibits a fairly high conductivity (1 S cm-1 at room temperature). The magnetic susceptibility measurements revealed that [Cu(dmdt)2]0+ molecule keeps most of S = 1/2 spin moments. The difference of the bond lengths between [Cu(dmdt)2]0+ and [Cu(dmdt)2]2- is consistent with the result of the molecular orbital calculation.