Anomalous thermochromic transition of poly(di‐n‐octylsilane)

The thermochromic behavior of poly(di‐n‐octylsilane) {[Si(C₈H₁₇)₂]_n; PDOS} was studied by ultraviolet (UV) absorption, differential scanning calorimetry, and X‐ray diffraction measurements. The structure of PDOS in the low‐temperature phase strongly depended on not only the temperature but also the rate of cooling, that is, the thermal history. Temperature‐dependent UV absorption spectra were highly dependent on thermal hysteresis. Cooled rapidly (10 K/min), PDOS showed two absorption peaks at 3.32 and 3.51 eV in low‐temperature‐ordered phases, whereas a single absorption peak at 3.32 eV became predominant with slow cooling (0.3 K/min). The appearance of the two peaks at low temperatures suggested that a mixture of different conformations was introduced by rapid cooling. A fiber diffraction pattern measured at 240 K after rapid cooling also showed evidence of the existence of novel conformation. A temperature‐dependent powder X‐ray diffraction pattern changed significantly between 270 and 280 K. Rapid cooling reduced the intensity of the X‐ray diffraction peak in this temperature region. This intensity change was explained by the conformational mixture in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1085–1092, 2001     

Functionalized pyrolytic highly oriented graphite polymer film for surface‐assisted laser desorption/ionization mass spectrometry in environmental analysis

The pyrolytic highly oriented graphite polymer film (PGS) was first employed to analyze low‐mass analytes in environmental analysis by surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS). PGS is a synthetic uniform and highly oriented graphite polymer film with high thermal anisotropic conductivity. We have found that negative ion mode SALDI‐MS using oxidized PGS (PGS‐SALDI‐MS) can be used to detect [M–H]^? ions from perfluorooctanoic acid (PFOA) and other perfluoroalkylcarboxylic acids when the PGS surface is modified with the cationic polymer polyethyleneimine (PEI). The signal intensity of PFOA when employing the PEI modification showed a ten‐fold increase over that obtained from desorption/ionization on porous silicon (DIOS). PFOA was quantified using PGS‐SALDI‐MS and the calibration curve showed a wide linear dynamic range of response (20–1000 ppb). The combination of atmospheric pressure ionization and PGS (AP‐PGS‐SALDI) showed greater signal intensity than vacuum PGS‐SALDI for deprotonated PFOA. Several other environmentally important chemicals, including perfluoroalkylsulfonic acid, pentachlorophenol, bisphenol A, 4‐hydroxy‐2‐chlorobiphenyl, and benzo[a]pyrene, were also successfully used to evaluate PGS‐SALDI‐MS. In addition, we found that nonafluoro‐1‐butanesulfonic acid was able to produce protonated peptides in positive ion PGS‐SALDI‐MS, but that perfluoropentanoic acid and trifluoroacetic acid were not. It is suggested that perfluoroalkylsulfonic acids are better protonating agents than perfluoroalkylcarboxylic acids in SALDI‐MS. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

The equilibrium states for semigroups of rational maps

We consider the dynamics of skew product maps associated with finitely generated semigroups of rational maps on the Riemann sphere. We show that under some conditions on the dynamics and the potential function ψ, there exists a unique equilibrium state for ψ and a unique exp(P(ψ) − ψ)-conformal measure, where P(ψ) denotes the topological pressure of ψ. The research of M. Urbański was supported in part by the NSF Grant DMS 0400481. H. Sumi thanks University of North Texas for kind hospitality, during his stay there.     

A new glycosylation method part 3: study of microwave effects at low temperatures to control reaction pathways and reduce byproducts

The efficiency of microwave irradiation at low temperature for glycosylations is described. Although oligosaccharide synthesis usually requires reactive donors for glycosylations, which have leaving groups on the anomer positions, i.e., trichloroacetoimidates, halogenates, thioalkyl glycosides, etc., the suitable donors in our microwave supported synthesis of Lewis X oligosaccharide were very stable acetate derivatives. Regarding glycosylation with a fucosyl acetate donor and a glucosamine acceptor, microwave irradiation with simultaneous cooling improved yields. Moreover, further synthesis to Lewis X derivatives was achieved only with microwave irradiation at low temperatures. Without microwave irradiation, we could only obtain byproducts and none of the designed product at any reaction temperature.     

Preparation and chemical properties of soluble π‐conjugated poly(aryleneethynylene) consisting of azabenzothiadiazole as the electron‐accepting unit

A soluble charge‐transfer type poly(aryleneethynylene), PAE‐AzaBzTdz , consisting of a highly electron‐accepting azabenzothiadiazole unit was prepared in 99% yield by palladium‐catalyzed polycondensation between 4,7‐dibromo‐2,1,3‐azabenzothiadiazole ( Br₂‐AzaBzTdz ) and 1,4‐diethynyl‐2,5‐didodecyloxybenzene. PAE‐AzaBzTdz showed a number‐average molecular weight, M_n, of 6000 in gel‐permeation chromatography analysis and had good thermal stability as measured by TGA. UV–vis spectrum of PAE‐AzaBzTdz exhibited an absorption peak at 529 nm in chloroform, and the absorption peak shifted to a longer wavelength (601 nm) in film. Addition of MeOH to a CHCl₃ solution of PAE‐AzaBzTdz led to aggregation of the polymer to form stable colloidal particles. Results of filtration experiments using 0.2 and 0.02 μm membranes supported aggregation of the polymer. Addition of trifluoroacetic acid (TFA) to a chloroform solution of PAE‐AzaBzTdz led to a red‐shift of the UV–vis peak from 529 to 640 nm. An X‐ray diffraction pattern of powdery PAE‐AzaBzTdz indicated that the polymer assumed a layer‐to‐layer stacked structure with an interlayer distance of 3.4 Å in the solid state. An X‐ray diffraction pattern of cast film of PAE‐AzaBzTdz revealed that the polymer molecules in the cast film were ordered on the surface of Pt plate with the dodecyl side chain oriented toward the surface of the Pt plate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2975–2982, 2008     

Azacalix[4]arene tetramethyl ether with inherent chirality generated by substitution on the nitrogen bridges

The first inherently chiral azacalix[4]arene has been prepared by introducing three benzyl groups onto the nitrogen bridges. The highly enantioenriched compound was easily obtained via a moderately enantioselective cyclization followed by a simple crystallization procedure. NMR and X-ray crystallographic studies revealed that easy access to the enantiomer was permitted by the non-racemizable 1,3-alternate conformation in solution, up to 110 °C, as well as by the preferential crystallization of a racemic compound.     

Preparation and applications of novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite nanocomposites

Novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite (HAp) nanocomposites were prepared by the reaction of calcium nitrate tetrahydrate and phosphoric acid in the presence of the corresponding oligomer. These fluorinated oligomer/HAp composites thus obtained are nanometer size‐controlled fine particles (83–173 nm), and were found to exhibit good dispersibility in methanol, ethanol, and isopropyl alcohol. These fluorinated HAp nanocomposites were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleophobic characteristics imparted by fluorine on their surface. In addition, the surface structural changes of the modified polyethylene terephtalate and PMMA films treated with these fluorinated nanocomposites before and after soaking in a simulated body fluid (SBF) were analyzed by using SEM, XRD, and EDX to observe the formation of spherical HAp deposits on the surface. Copyright © 2009 John Wiley & Sons, Ltd.