Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

The copper‐catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn‐chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5 . The potential of this approach was illustrated by the preparation of two consecutive all‐carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from ?35 to ?20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ‐nonconjugated unsaturated esters 4 . Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu] . Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti‐selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn‐ 3 and anti‐ 3 can be obtained, at will, from the same precursor cyclopropenyl esters 1 .     

DC-Pulsed Plasma for Dry Reforming of Methane to Synthesis Gas

The carbon dioxide reforming of methane to synthesis gas under DC-pulsed plasma was investigated. The effects of specific input energy and feed ratio on the product distribution and also feed conversion was studied. At the input energy of about 11 eV/molecule per methane and/or carbon dioxide the feed conversion of 38% for CH₄ and 28% for CO₂ and product selectivity of 74% has been attained for H₂ and CO at feed flow rate of 90 ml/min. The energy consumption in this work displays potential to further study and optimization of the process. The importance of the electron impact reactions in the process was discussed. The results show that by prudent tuning of system variables, the process be able to run in the way of synthesis gas, instead of hydrocarbon production.     

Competitive Self and Induced Aggregation of Calix[4]arene Ethers and Their Interaction with Pinacyanol Chloride and Methylene Blue in Nonaqueous Media

Long chain calix[4]arene ethers have been examined for aggregation in nonaqueous solvents by using UV-vis molecular absorbance spectroscopy. It has been observed that tetraalkylated (alkyl = hexadecyl and octadecyl, respectively) calix[4]arene ethers tend to aggregate in chloroform and tetrahydrofuran, possibly via π–π stacking interactions of the phenyl moieties, and the aggregation process appears to be facilitated by the alkyl chains. The analogous dialkylated compounds do not show any self-aggregation, plausibly due to strong hydrogen bonding between the –OH and the –O– of calix aryl ether which seems to disrupt the aggregation process. Addition of the anionic surfactant sodium dodecylsulfate (SDS) appears to hinder the aggregation process in nonpolar chloroform but the same surfactant facilitates aggregation in the polar tetrahydrofuran. The cationic surfactant (cetyltrimethyl ammonium bromide) and the nonionic surfactant (Brij-35) have no effect on this aggregation process. Unexpectedly, SDS induces aggregation of dialkylated calix[4]arene ethers in chloroform. It has been observed that the aggregated form of the tetraalkylated calix[4]arene ethers tend to increase the dimerization efficiency of cationic dyes (pinacyanol chloride and methylene blue) in chloroform.     

The lowest singlet-triplet excitation energy of BN: A converged coupled cluster perspective

The notoriously small X 3Pi-a 1Sigma+ excitation energy of the BN diatomic has been calculated using high-order coupled cluster methods. Convergence has been established in both the one-particle basis set and the coupled cluster expansion. Explicit inclusion of connected quadruple excitations T4 is required for even semiquantitative agreement with the limit value, while connected quintuple excitations T5 still have an effect of about 60 cm(-1). Still higher excitations only account for about 10 cm(-1). Inclusion of inner-shell correlation further reduces Te by about 60 cm(-1) at the CCSDT, and 85 cm(-1) at the CCSDTQ level. Our best estimate, Te = 183+/-40 cm(-1), is in excellent agreement with earlier calculations and experiment, albeit with a smaller (and conservative) uncertainty. The dissociation energy of BN(X 3Pi) is De = 105.74+/-0.16 kcal/mol and D0 = 103.57+/-0.16 kcal/mol.     

Reference Electrode for Ionic Liquids

Reference electrodes for room temperature ionic liquid (RTIL) applications were constructed that have a known and reproducible potential versus the ferrocene/ferrocenium couple. They are based on reference electrodes of the first kind, Ag/Ag⁺ couple type, or of the second kind, based on Ag/AgCl in M⁺Cl^?. The former uses AgNO₃ salt and the latter tetrabutylammonium chloride, Bu₄NCl, dissolved in acetonitrile which are then introduced to the ionic liquid of choice for a final concentration of 0.1 M. The reference electrodes can be easily and reproducibly constructed. An ionic contact of these reference systems with the test electrolyte was made using an asbestos fiber liquid junction. The internal compartment of the reference system was filled with the same ionic liquid as used for the electrochemical experiment. The performance of these reference electrodes was tested in selected ionic liquids using the ferrocene/ferrocenium redox couple. The stability, reproducibility, and temperature behavior of the two reference systems have been characterized in the following ionic liquids: 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIBF₄), 1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI(CF₃SO₂)₂N), and 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIPF₆). It has been found that the formal potentials of the examined reference systems are stable over several days. There is a linear relationship for the temperature studied in the range from 25 to 60 °C.     

Solubility of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N]

The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF₆]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF₄]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf₂N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky–Kasarnovsky equation and Henry’s constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained show that the solubility of H₂S in these three ionic liquids was in the sequence: [hmim][BF₄] > [hmim][PF₆] ≈ [hmim][Tf₂N].     

Measuring persistence in a stationary time series using the complex network theory

A growing interest exists currently in the analysis of time series by the complex network theory. Here we present a simple and quick way for mapping time series to complex networks. Using a simple rule allows us to transform time series into a textual sequence then we divide it into words with fixed size. Distinct words are nodes of the network, and we have complete control on the network scale by adjusting the word size. Two nodes are linked if their associated words co-occur in sequence. We show that the network topological measures quantify the persistence and the long range correlations in fractional Brownian processes. For a particular word size we assume some relations between the topological measures and the Hurst exponent which characterised the persistence in fractional Brownian processes.