Correlation of the Solubilizing Abilities of 1-Butyl-1-methyl-pyrrolidinium Tris(pentafluoroethyl)trifluorophosphate, 1-Butyl-1-methylpyrrolidinium Triflate and 1-Methoxyethyl-1-methylmorpholinium Tris(pentafluoroethyl)trifluorophosphate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrolidinium tris(pentafluoroethyl)trifluorophosphate ([BMPyrr]⁺[FAP]^?), 1-butyl-1-methylpyrrolidinium triflate, ([BMPyrr]⁺[Trif]^?), and 1-methoxyethyl-1-methylmorpholinium tris(pentafluoroethyl)trifluorophosphate, ([MeoeMMorp]⁺[FAP]^?), stationary phases at (323, 353 and 383) K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. The three sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.11 and 0.15 log₁₀ units, respectively.     

Intermediate mass fragments emitted in the reaction Ag+14N at 100, 160 and 250 MeV bombarding energy

The fragments produced in the reaction between a ¹⁴N beam of various energies and a natural Ag target have been studied. The atomic numbers of the fragments have been identified up to Z = 17 by means of a E-ΔE counter telescope. The cross sections, the kinetic energy distributions as well as the angular distributions have been measured for each atomic number. The kinetic energy distributions show two components: a high-energy component (quasi-elastic), prevailing at angles close to the grazing angles and for atomic numbers close to Z = 7, and a low-energy component (relaxed), at energies close to the Coulomb repulsion energy, present at all angles and for all the Z. A detailed study of the relaxed components of the kinetic energy seems to account for both them means and the widths of these distributions on a purely statistical basis. The cross sections of the relaxed components appear to be quite large at low Z and to decrease rapidly to a fairly constant value in the region of 10 ≦ Z ≦ 17. A marked even-odd alternation in the cross sections is observed. The angular distributions are strongly forward peaked for Z < 7. For Z > 7 the forward peaking decreases rapidly until, for Z > 13, the limiting form 1/sinθ is attained. Evidence for the existence of a diffusion process along the mass asymmetry coordinate is discussed.     

Macrocyclic paracyclophane synthesis

Macrocyclic stilbene derivatives are prepared using strong base to couple the terminal carbons of 1,12-bis-[4-chloromethylphenyl]-dodecane and its homologs.     

Charge and angular distributions and secondary fission of deep inelastic products from the reaction 197Au + 979 MeV 136Xe 1443 08

Kinetic energy spectra, charge and angular distributions are presented for over 40 elements (Z = 27?68). The kinetic energy spectra show two distinct components: a deep inelastic one and another from secondary fission of the target-like product. The charge distribution widths are comparable to those observed in Kr bombardments, the angular distributions, however, are more extensively side peaked.     

Time-resolved infrared dynamics of C-F bond activation by a tungsten metal-carbonyl

Chemical reactions that break, or activate, C-H and C-F are of tremendous synthetic interest. The intramolecular C-F bond activation of a tungsten carbonyl system has been studied by time-resolved infrared spectroscopy. The formation of solvent complexes and the final product are monitored using time-resolved infrared spectroscopy of the CO stretches. The rate of the reaction is shown to be limited by the formation of an intermolecular complex between the tungsten metal center and a solvent molecule. Comparison with DFT calculations shows that in the absence of solvent molecules the intramolecular complex with the tethered perfluorobenzene ring is energetically favorable, but is not the primary kinetic product because of the initial geometry of the complex.     

Influence of copolymer configuration on the phase behavior of ternary blends

The influence of copolymer configuration on the phase behavior of various ternary polymer blends containing a crystallizable polyester, a noncrystallizable polyether, and an acrylic random copolymer of different chain configuration was investigated. In these ternary blends, the acrylic random copolymer is typically added to control rheological properties at elevated temperatures. In fact, the acrylic random copolymers composed of various compositions of MMA and nBMA were found to have different miscibility with polyester as well as polyether, leading to substantially different phase behavior of ternary blends. Remarkable temperature dependence was also found. The mean-field Flory-Huggins theory for the free energy of mixing, extended to ternary polymer blends, was adopted for predicting phase diagrams where the exact spinodal and binodal boundaries could be calculated. Phase diagrams of ternary blends, predicted by the Flory-Huggins formulations and related calculations, were in good agreement with experimental phase diagrams. The differences observed in the rheological processes of various ternary blends with different acrylic copolymers were directly related to changes in miscibility, associated phase behavior, and chain configuration.     

Specifying attracting cycles for Newton maps of polynomials

We show that for any set of n distinct points in the complex plane, there exists a polynomial p of degree at most n+1 so that the corresponding Newton map, or even the relaxed Newton map, for p has the given points as a super-attracting cycle. This improves the result in Plaza and Romero [6], which shows how to find such a polynomial of degree 2n. Moreover, we show that in general one cannot improve upon degree n+1. Our methods allow us to give a simple, constructive proof of the known result that for each cycle length n ≥ 2 and degree d ≥ 3, there exists a polynomial of degree d whose Newton map has a super-attracting cycle of length n.     

One-pot enol silane formation-Mukaiyama aldol reactions: Crossed aldehyde-aldehyde coupling,thioester substrates,and reactions in ester solvents

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote both in situ enol silane/silyl ketene acetal formation and Mukaiyama aldol addition reactions between a variety of reaction partners in a single reaction flask. Isolation of the required enol silane or silyl ketene acetal is not necessary. For example, crossed aldol reactions between α-disubstituted aldehydes and non-enolizable aldehydes yield β-hydroxy aldehydes in good yield. In a related reaction, the common laboratory solvent ethyl acetate functions as both an enolate precursor and a green reaction solvent. When thioesters are employed as enolate precursors, high yields for additions to non-enolizable aldehydes are routinely observed.