Fluorescence from the second excited singlet state of [18] annulenes

The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S₂ → S₀ emission. In addition, fluorescence from the S₁ state can be observed in monofluoro [13] annulene by exciting into the S₂ or directly into the S₁ absorption.     

Die Bildungsenthalpien einiger Siliciumtetrahalogenid—Pyridin-Addukte

The enthalpies of formation of the addition compounds F₄Si(py)₂, Cl₄Si(py)₂, Br₄Si(py)₂ and I₄Si(py)₄ have been measured calorimetrically by two different ways (see table 1). It was not possible to confirm enthalpy data published in^{7, 8}. The sequence SiF₄4～SiBr₄>SiI₄(?) is proposed for the acceptor power of the silicon tetrahalides towards pyridine.     

Application of a new standardization method in activation analysis with registration of soft gamma radiation

An application of a new standardization method for rapid activation mass analysis with registration of the strongly absorbed low-energy gamma radiation is described. This method makes it possible to avoid the use of the time-consuming and laborious method of Internal Standard.     

Dynamics of end-grafted polystyrene brushes in theta solvents

The dynamics of the concentration fluctuations in end-grafted polystyrene brushes in a theta solvent (cyclohexane) are probed by evanescent wave dynamic light scattering at different wavevectors q and temperatures. When the solvent quality changes from marginal to poor, the relaxation function C(q, t) exhibits strong effects as compared with the smooth variation of the brush density profile. From a single exponential above 50 °C, C(q, t) becomes a two-step decay function. The fast decay is still assigned to the cooperative diffusion albeit slower than in the good solvent regime whereas the slow nonexponential and nondiffusive process might relate to microsegragated and/or chain dynamics in the present polydisperse brush. The relaxation function of the present three brushes with different grafting density reveals similarities and disparities between wet brushes and semidilute polymer solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3590–3597, 2006     

Electron spin resonance studies of the radiolysis of bi-π-cyclopentadienylalkyls of molybdenum and tungsten

Exposure of (C₅H₅)₂MO(CH₃)₂ and (C₅H₅)₂W(CH₃)₂, prepared from the corresponding dichlorides, to ²⁰Co γ-rays at 77 K gave H₂C.CML₃ carbene species characterised by their ESR spectra, together with a central feature possibly due to the parent cations. Dilute solutions in CD₃OD gave features assigned to the parent anions which were converted on bleaching with visible light into methyl radicals, and H₂C.ML₃ radicals. From the magnitude of the ¹H and ¹⁸³W hyperfine coupling constants, it is deduced that the SOMO for H₂C.WL₃ radicals is strongly localised on carbon.Dilute solutions in aqueous sulphuric acid also gave species with A(2H) = 20 G, identified as the carbene derivatives, H₂C.Ml₃. These were formed on annealing, as signals assigned to HSO₄ · radicals were lost.     

Cellulosic value-added products from sugarcane bagasse

Cellulose - Sugarcane bagasse (SCB) is a major by-product of the sugarcane industry and one of the most common renewable and sustainable cellulosic materials for various industrial...     

Crystal structure of cis-[Ru(bpy)2{PMe(o-tol)2}Cl+][ClO−4]: Steric effects in some PMen(o-tol)3−n (n = 1-3) derivatives of ruthenium(II)

The complex cis-[Ru(bpy)₂{PMe(o-tol)₂}Cl⁺][ClO^– ₄] crystallizes in space group P2₁/c witha = 9.375(2) Å, b = 22.019(7) Å, c = 16.153(4) Å, = 90.83(2)°, V = 3333.9(16) ų and D(calc'd) = 1.547 g/cm³ for Z = 4. The Ru-PMe(o-tol)₂ bond length of 2.357(3) Å is significantly longer than distances of Ru-PMe₂(o-tol) = 2.324(2) Å and Ru-PMe₃ = 2.310(2) Å in analogous complexes. The corresponding Ru-P(o-tol)₃ complex has eluded synthesis, probably due to steric hindrance.     

Separation of dansylated 17β-estradiol, 17α-estradiol, and estrone on a single HPLC column for simultaneous quantitation by LC–MS/MS

We show here that baseline separation of dansylated estrone, 17β-estradiol, and 17α-estradiol can be done, contrary to previous reports, within a short run time on a single RP-LC analytical column packed with particles bonded with phenyl-hexyl stationary phase. The chromatographic method coupled with isotope dilution tandem MS offers a simple assay enabling the simultaneous analysis of these analytes. The method employs ¹³C-labeled estrogens as internal standards to eliminate potential matrix effects arising from the use of deuterated estrogens. The assay also offers adequate accuracy and sensitivity to be useful for biological samples. The practical applicability of the validated method is demonstrated by the quantitative analyses of in vivo samples obtained from rats treated with Premarin®.