Low-melting, low-viscous, hydrophobic ionic liquids: 1-alkyl(alkyl ether)-3-methylimidazolium perfluoroalkyltrifluoroborate

A series of twenty two hydrophobic ionic liquids, 1-alkyl(alkyl ether)-3-methylimidazolium ([C(m)mim]+ or [C(m)O(n)mim]+; where Cm is 1-alkyl, Cm = nCmH(2m+1), m = 1-4 and 6; C(m)O(n) is 1-alkyl ether, C2O1 = CH3OCH2, C3O1 = CH3OCH2CH2, and C5O2 = CH3(OCH2CH2)2) perfluoroalkyltrifluoroborate ([RFBF3]-, RF = CF3, C2F5, nC3F7, nC4F9), have been prepared and characterized. Some of the important physicochemical properties of these salts including melting point, glass transition, viscosity, density, ionic conductivity, thermal and electrochemical stability, have been determined and were compared with those of the reported [BF4](-)-based ones. The influence of the structure variation in the imidazolium cation and the perfluoroalkyltrifluoroborate ([RFBF3]-) anion on the above physicochemical properties was discussed. The key features of these new salts are their low melting points (-42 to 35 degrees C) or extremely low glass transition (between -87 and -117 degrees C) without melting, and considerably low viscosities (26-77 cP at 25 degrees C).     

Identification of novel substituted fused aromatic compounds, meshimakobnol A and B, from natural Phellinus linteus fruit body

Novel 1H,6H-pyranyl[4,3-c][2]benzopyrane-1,6-diones, meshimakobnol A and B, were isolated from natural Phellinus linteus fruit body. The structure elucidation of these fused aromatic compounds was achieved by a spectroscopic method including the measurement of FG-HMBC with various delay times.     

A layered tungstic acid H2W2O7 x nH2O with a double-octahedral sheet structure: conversion process from an aurivillius phase Bi2W2O9 and structural characterization

The conversion process of an Aurivillius phase, Bi(2)W(2)O(9), into a layered tungstic acid by hydrochloric acid treatment has been investigated, and resultant H(2)W(2)O(7) x nH(2)O has been fully characterized. The c parameter of Bi(2)W(2)O(9) [2.37063(5) nm] decreases to 2.21(1) nm in an acid-treated product dried at ambient temperature. The a and b parameters of Bi(2)W(2)O(9) [a = 0.54377(1) nm and b = 0.54166(1) nm] also decrease slightly to a = 0.524(1) nm and b = 0.513(1) nm in the acid-treated product dried at ambient temperature, indicating structural changes in the ReO(3)-like slabs in Bi(2)W(2)O(9) upon acid treatment. Drying at 120 degrees C leads to a further decrease in the c parameter [1.86(1) nm] with no notable change in the a and b parameters [a = 0.5249(2) nm and b = 0.513(2) nm]. The formation of an expandable layered structure is demonstrated by the successful intercalation of n-octylamine [interlayer distance 2.597(9) nm] and n-dodecylamine [interlayer distance 3.56(2) nm]. The compositions of the acid-treated products are determined to be H(2)W(2)O(7) x nH(2)O typically with n = 0.58 for the air-dried product and n = 0 for the product dried at 120 degrees C. As a consequence, the composition of the layer is H(2)W(2)O(7), and the decrease in the c parameter upon drying is ascribable to the loss of interlayer water. Scanning electron microscopy reveals no morphological change during acid treatment, which strongly suggests a selective leaching of the bismuth oxide sheets as a reaction mechanism. High-resolution transmission electron microscopy (HREM) observation of the acid-treated product shows consistency with a structural model for H(2)W(2)O(7), derived from Bi(2)W(2)O(9) through removal of the bismuth oxide sheets and contraction along the c axis. HREM observation also reveals that the WO(6) octahedra arrangement changes slightly with acid treatment. A one-dimensional electron density map projected on the c axis for the product dried at 120 degrees C, H(2)W(2)O(7), shows good consistency with that calculated for the structural model.     

Doppler-free two-photon excitation spectroscopy and the Zeeman effects of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) band of naphthalene-d8

Doppler-free two-photon excitation spectrum and the Zeeman effect of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) transition of naphthalene-d8 have been measured. 908 lines of Q(Ka)Q(J)KaKc transition of J=0-41, Ka=0-20 were assigned, and the molecular constants of the S1 1B1u(v21=1) state were determined. Perturbations were observed, and those were identified as originating from Coriolis interaction. No perturbation originating from an interaction with triplet state was observed. The Zeeman splittings from lines of a given J were observed to increase with Kc, and those of the Kc=J levels increased linearly with J. The Zeeman effects are shown to be originating from the magnetic moment of the S1 1B1u state, which is along the c axis and is induced by mixing of the S2 1B3u state to the S1 1B1u state by J-L coupling. Rotationally resolved levels were found not to be mixed with a triplet state from the Zeeman spectra. Accordingly, it is concluded that nonradiative decay of an isolated naphthalene excited to low rovibronic levels in the S1 1B1u state does not occur through the intersystem mixing. This is at variance with generally accepted understanding of the pathways of the nonradiative decay.     

Doppler-free two-photon excitation spectroscopy and the Zeeman effects. Perturbations in the 14(0)1 and 1(0)(1)14(0)1 bands of the S1 <-- S0 transition of C6D6

Doppler-free two-photon excitation spectra and the Zeeman effects for the 1 band of the S1 1B2u <-- S0 1A1g transition in gaseous benzene-d6 were measured. Although the spectral lines were strongly perturbed, almost all of the lines near the band origin could be assigned. From a deperturbation analysis, the perturbation near the band origin was identified as originating from an anharmonic resonance interaction. Perturbation centered at K = 28-29 in the 14(0)1 band was analyzed, and it was identified as originating from a perpendicular Coriolis interaction. The symmetry and the assignment of the perturbing state proposed by Schubert et al. (Schubert, U.; Riedle, E.; Neusser, H. J. J. Chem. Phys. 1989, 90, 5994.) were confirmed. No perturbation originating from an interaction with a triplet state was observed in both bands. From the Zeeman spectra and the analysis, it is demonstrated that rotationally resolved levels are not mixed with a triplet state. The intersystem mixing is not likely to occur at levels of low excess energy in the S1 state of an isolated benzene. Nonradiative decay of an isolated benzene in the low vibronic levels of the S1 state will occur through the internal mixing followed by the rotational and vibrational relaxation in the S0 state.     

Homopolymerizations and random copolymerizations of olefins with amino‐substituted cyclopentadienylchromium complexes

1‐(2‐N,N‐Dimethylaminoethyl)‐2,3,4,5‐tetramethylcyclopentadienyl‐chromium dichloride ( 1 ), (2‐N,N‐dimethylaminoethyl)cyclopentadienylchromium dichloride ( 6 ), and (2‐N,N‐dimethylaminoethyl)indenylchromium dichloride ( 7 ) in the presence of modified methylaluminoxane exhibit high catalytic activities for the polymerization of ethylene with random copolymerizations of ethylene with propylene, ethylene with 1‐hexene, and propylene with 1‐hexene. These initiators conduct polymerizations to give high molecular weight polymers with low polydispersities. However, the stereoregularities are very poor in these reactions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2759–2771, 2002     

Structure and chemical behavior of an organoaluminum compound [Rb2AlOCR′NPh]2, a stereospecific catalyst for polymerization of acetaldehyde

A series of organoaluminum compounds [R₂AlOCR′NPh]₂, which are the reaction products between trialkylaluminum compounds and secondary acid amides and are excellent catalysts for stereospecific polymerizations of aldehydes, were isolated in the crystalline state. Chemical behavior of such compounds toward Lewis acids and bases were interpreted in terms of the structures of [Me₂AlOCPhNPh]₂ and its trimethylamine oxide complex Me₃NO·AlMe₂OCPhNPh which were determined by X-ray structure analyses. Reaction products of primary and tertiary acid amides with trialkylaluminum compounds were also studied.     

New Combinatorial Bounds for Authentication Codes and Key Predistribution Schemes

This paper provides new combinatorial bounds and characterizations of authentication codes (A-codes) and key predistribution schemes (KPS). We first prove a new lower bound on the number of keys in an A-code without secrecy, which can be thought of as a generalization of the classical Rao bound for orthogonal arrays. We also prove a new lower bound on the number of keys in a general A-code, which is based on the Petrenjuk, Ray-Chaudhuri and Wilson bound for t-designs. We also present new lower bounds on the size of keys and the amount of users' secret information in KPS, the latter of which is accomplished by showing that a certain A-code is hiding inside any KPS.     

Strong continuity implies uniform sequential continuity

Uniform sequential continuity, a property classically equivalent to sequential continuity on compact sets, is shown, constructively, to be a consequence of strong continuity on a metric space. It is then shown that in the case of a separable metric space, uniform sequential continuity implies strong continuity if and only if one adopts a certain boundedness principle that, although valid in the classical, recursive and intuitionistic setting, is independent of Heyting arithmetic.