Oligo-Quinolylene–Vinylene Foldamers

Quinoline based aromatic amide foldamers are known to adopt stable folded conformations. We have developed a synthetic approach to produce similar oligomers where all amide bonds, or part of them, have been replaced by an isosteric vinylene group. The results of solution and solid state structural studies show that oligomers exclusively containing vinylene linkages are not well folded, and adopt predominantly flat conformations. In contrast, a vinylene segment flanked by helical oligoamides also folds in a helix, albeit with a slightly lower curvature. The presence of vinylene functions also result in an extension of π-conjugation across the oligomer that may change charge transport properties. Altogether, these results pave the way to foldamers in which both structural control and specific electronic properties may be engineered.     

Formation of two isomeric closo-[(eta5-C5H5)FePC2B8H10] phosphadicarbaborane analogues of ferrocene via isolable eta1-bonded complexes of the [7-[(eta5-C5H5)Fe(CO)2]-(eta1-nido-PC2B8H10)] type

The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.     

Analysis of correlation between percolation concentration and elongation at break in filled electroconductive epoxy-based adhesives

Electrical conductivity and elongation at break of epoxy filled with electroconductive carbon black, graphite or with silver-coated basalt particles or fibres were investigated in this paper. Percolation concentrations were determined to be 14 vol% for epoxy/carbon black composites, 22 vol% for epoxy/graphite composites, 28-29 vol% for both epoxy/silver-coated basalt particles and fibres. The steepest increase in electrical conductivity and the most pronounced decrease in elongation at break occurs at similar filler concentration range for all investigated systems. A good correlation between phenomenological model, introduced in [J. Mater. Sci. Lett. 18 (1998) 1457] and experimental data for all investigated systems was observed.     

Polymerization of ethylene oxide with potassium-graphite inclusion compounds

The polymerization of ethylene oxide (EO) in tetrahydrofuran (THF) initiated by inclusion compounds of potassium in graphite (C₂₄K) at 50°C was studied. During the initial slow stage of the polymerization the catalyst efficiency increases, while during the second rapid stage the reaction proceeds at a constant concentration of the active centers. The influence of the catalyst and monomer concentrations on the concentration of the active centers and on the catalyst efficiency was studied. The existence of the slow stage is explained by diffusion of ethylene oxide between the graphite planes, where both initiation and initial chain growth take place. The diffusion of the growing chains from the catalyst into the solution brings about the formation of a necessary concentration of active centers in the solution, which ensures the rapid growth of the polymer chains under homogeneous conditions. An x-ray study of the catalyst after polymerization shows a strongly disturbed crystal structure of the graphite. Poly-(ethylene oxide) obtained at a higher degree of conversion, does not contain low molecular weight fractions.     

Signature of the conformational preferences of small peptides: a theoretical investigation

An extensive computational study of the conformational preferences of N-acetylphenylalaninylamide (NAPA) is reported, including conformational and anharmonic frequency analyses, as well as calculations of excitation energies of the four NAPA conformers lowest in energy. Particular attention is paid to the influence of hydrogen-bonding interactions on the relative stability of the conformers, which was found to be very sensitive to both the level of quantum chemical computations and the anharmonic treatment of molecular vibrations. The assignments of the UV spectral peaks are well supported by the multireference CASSCF/MS-CASPT2 calculations. Upon consideration of the second-order M?ller-Plesset (MP2) and density functional theory (DFT) structures, overall energetics, and harmonic and anharmonic corrections, we found no conclusive theoretical evidence for the assumed conformational propensity of small model peptides toward extended beta-strand structures.     

Synthesis of novel ferrocene-containing 1,3-thiazinan-2-imines: One-pot reaction promoted by ultrasound irradiation

A simple one-pot synthesis of new ferrocene-containing 1,3-thiazinan-2-imines from 3-arylamino-1-ferrocenylpropan-1-ols and phenyl isothiocyanate has been developed. The key intermediate β-hydroxy thioureas were generated in situ using ultrasound irradiation and subsequent cyclization was achieved by the addition of acetic acid. The scope of the reaction towards various 3-arylamino-1-ferrocenylpropan-1-ols has been explored and the corresponding 3-aryl-6-ferrocenyl-N-phenyl-1,3-thiazinan-2-imines were obtained in moderate to high yields (52–90%).     

Heteropoly acid as a novel efficient catalyst for Fries rearrangement

Heteropoly acid H3PW12O40 is a very efficient and environmentally benign catalyst for the Fries rearrangement of phenyl acetate in homogeneous or heterogeneous liquid-phase systems at 100-150 degrees C.