Mass spectrometry of transition-metal π-complexes. III—a study of an iron-coordinated tautomer of phenol

A study of the fragmentation of the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{\left({{\rm C}_{\rm 6} {\rm H}_{\rm 6} {\rm O}} \right){\rm Fe}} \right]_{}^{_.^ + } $\end{document} ion formed from two different precursors suggests that the ions adopt different structures over that part of the energy distribution giving rise to decomposition in the ion source.     

Electrolytically generated silver(II) as a coulometric titrant

The use of electrolytically generated silver(II) as a coulometric titrant has been studied. Difficulties arising from the current efficiency for generation of silver (II) at a platinum or gold electrode and from the reduction of silver(II) by water, have been overcome. The precautions necessary for accurate titrations of oxalic acid, cerium(III), arsenic(III) and vanadium(IV) by amperometric or potentiometric methods are detailed. Manganese and chromium could not be determined directly. Substances which reduce nitric acid could be determined if care was taken.     

Electron solvation dynamics in I-(NH3)n clusters

Femtosecond photoelectron spectroscopy (FPES) is used to monitor the dynamics associated with the excitation of the charge-transfer-to-solvent (CTTS) precursor states in I-(NH3)n = 4-15 clusters. The FPE spectra imply that the weakly bound excess electron in the excited state undergoes partial solvation via solvent rearrangement on a time scale of 0.5-2 ps, and this partially solvated state decays by electron emission on a 10-50 ps time scale. Both the extent of solvation and the lifetimes increase gradually with cluster size, in contrast to the more abrupt size-dependent effects previously observed in I-(H2O)n clusters.     

Analysis and interpretation of excess molar properties of amphiphile + water systems : Part 3. Excess molar volumes of isopropoxyethanol + water and isobutoxyethanol + water

Excess molar volumes at 25°C, are reported for the systems isoPrOEtOH + water and isoBuOEtOH + water across their entire composition ranges. These data have been compared to those for their normal alkyl analogs in order to assess the effects of both - and β-chain branching.

The results are discussed in terms of the relative abilities of the amphiphiles to form structured aggregates.     

A molecular-dynamics study of a model S(N)1 dissociation reaction at the water liquid/vapor interface

The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation.     

A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate

A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.

     

Some non-existence results on divisible difference sets

In this paper, we shall prove several non-existence results for divisible difference sets, using three approaches:

1. character sum arguments similar to the work of Turyn [25] for ordinary difference sets,
2. involution arguments and
3. multipliers in conjunction with results on ordinary difference sets.

Among other results, we show that an abelian affine difference set of odd orders (s not a perfect square) inG can exist only if the Sylow 2-subgroup ofG is cyclic. We also obtain a non-existence result for non-cyclic (n, n, n, 1) relative difference sets of odd ordern.     

Dopant-induced excimer laser ablation of poly(tetrafluoroethylene)

Clean ablation of poly(tetrafluoroethylene) (PTFE) at etch rates in excess of 7µm/pulse has been achieved with an excimer laser using 308nm radiation and a 25 ns pulse width. This was accomplished by doping the ultraviolet-transparent PTFE polymer with polyimide. Ablation rates were investigated as a function of fluence in the range from 1 to 12J/cm² and dopant levels up to 15% (wt/wt). Results show that at a given fluence there exists an optimum absorption coefficient _max, for which maximum ablation rates are achieved. The value of _max was found to decrease with increasing fluence. The relationship between _max and fluence was determined from existing ablation rate models and found to compare favorably with empirical results.