Thermodynamics of polyether solutions

Measurements are reported of the vapor pressures and the heats and volumes of mixing of solutions of poly(ethylene glycol dimethyl ether) in chloroform and in carbon tetrachloride. The measurements have been used to calculate the thermodynamic mixing functions for mixing with zero volume change. These values have been compared with the predictions of the lattice theory of mixtures at three different levels of approximation, viz., the generalized “first approximation” theory of Barker, the “zeroth approximation” theory, and the Flory theory. In the hydrogen-bonding chloroform solutions the Barker theory is more successful than the other forms of the lattice theory. The results have also been used, in conjunction with those for solutions of poly(propylene glycol dimethyl ether) in the same two solvents, to test the ability of the Barker theory to correlate the properties of related systems. Good correlation is found between the two carbon tetrachloride solutions but not between the chloroform solutions. It is probable that the side-chain methyl groups in the propylene oxide repeating unit cause the hydrogen-bonding interaction to be weaker in this polymer than it is in the polymer with the ethylene oxide repeating unit.     

Radiation chemistry of linear low-density polyethylene. II. Kinetics of alkyl and allyl free-radical decay reactions

Quenched and annealed samples of linear low-density polyethylene (LLDPE) were γ irradiated in vacuo at 77 K; the kinetics of the alkyl free-radical decay reactions were studied at room temperature, and of the allyl free-radical reactions at 60, 70, and 80°C. The ESR signals saturate at a slightly higher microwave power in the LLDPE than in high-density polyethylene (HDPE), and the alkyl radicals start decaying at a lower temperature in the LLDPE than in the HDPE. As in the HDPE the decay of the alkyl free radicals at room temperature in the LLDPE follows the kinetic equation for two simultaneous first-order reactions with the fraction of the faster-decaying component being slightly greater in the quenched than in the annealed samples. In the case of the allyl free radicals the decay at 60°C follows the equation based on one fraction of the radicals decaying according to second-order kinetics in the presence of other nondecaying radicals. At higher temperatures the data are best understood in terms of a second-order rate equation with a continuously variable time-dependent rate constant as suggested by Hamill and Funabashi.     

Radiation chemistry of linear low-density polyethylene. I. Gel formation and unsaturation effects

Quenched and annealed samples of linear low-density polyethylene (LLDPE) were irradiated with ⁶⁰Co γ rays in vacuo at room temperature. The data follow rather accurately Charlesby's equation s = k/r, where s is the soluble fraction, r the dose, and k a constant from which G(X), the G-value for crosslinks, was calculated. Crosslinking in the LLDPE is about twice as extensive at equal doses as in LHDPE. Production of vinylene unsaturation was approximately the same in the two types of polyethylene.     

Determination of pharmaceutical compounds in skin by imaging matrix-assisted laser desorption/ionisation mass spectrometry

Matrix-assisted laser desorption/ionisation (MALDI) quadrupole time-of-flight mass spectrometry (Q-TOFMS) has been used to detect and image the distribution of a xenobiotic substance in skin. Porcine epidermal tissue was treated with 'Nizoral', a medicated shampoo containing ketoconazole (+/-)-1-acetyl-4-[p-[[(2R,4S)-2-(2,4-dichlorophenyl)-2-(imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]piperazine) as active ingredient. Following incubation for 1 h at 37 degrees C all excess formulation was washed from the surface. A cross-section of the drug-treated tissue was then blotted onto a cellulose membrane, precoated in matrix (alpha-cyano-4-hydroxycinnamic acid (CHCA)), by airspray deposition. In separate experiments the tissue surface was treated with Nizoral within a triangular former, and subsequently blotted onto a matrix-coated membrane. Sample membranes were then mounted into the recess of specialised MALDI targets with adhesive tape. All samples were analysed by MALDI-TOFMS using an Applied Biosystem 'Q-star Pulsar i' hybrid Q-TOF mass spectrometer fitted with an orthagonal MALDI ion source and imaging software. Detection of the protonated molecule was readily achievable by this technique. Treatment of the tissue within a template gave rise to images depicting the expected distribution of the drug, demonstrating that this technique is capable of producing spatially useful data. Ion images demonstrating the permeation of the applied compound into the skin were achieved by imaging a cross-sectional imprint of treated tissue. A calibration graph for the determination of ketoconazole was prepared using the sodium adduct of the matrix ion as an internal standard. This enabled construction of a quantitative profile of drug in skin. Conventional haematoxylin and eosin staining and microscopy methods were employed to obtain a histological image of the porcine epidermal tissue. Superimposing the mass spectrometric and histological images appeared to indicate drug permeation into the dermal tissue layer.     

Long-lived nuclear spin states in high-field solution NMR

Nuclear spin order may be stored in a liquid for a much longer time than the longitudinal relaxation time T1, by using rf fields to isolate states of different symmetry. The method is demonstrated on a sample containing AX spin systems.     

Some conjectures for cogwheel phase cycling

Cogwheel phase cycles are often significantly shorter than traditional nested phase cycles. However, optimal solutions for cogwheel cycles are often difficult to find. This paper presents techniques and conjectures which the authors have found useful for generating cogwheel phase cycles either without the need for computer searches or with significantly smaller searches than would otherwise be necessary. The conjectures presently lack proofs but have been tested successfully for a large number of cases.     

Heteronuclear polarization transfer by symmetry-based recoupling sequences in solid-state NMR

We demonstrate a new set of methods for transferring spin polarization between different nuclear isotopes in magic-angle-spinning solid-state NMR. The technique employs symmetry-based recoupling sequences on one irradiation channel and a simple sequence of between one and three strong radiofrequency pulses on the second channel. A phase shift of the recoupling sequences is applied at the same time as a pi/2 pulse on the second channel. The trajectory of the transferred polarization may be used to estimate heteronuclear distances. The method is particularly attractive for nuclei with low gyromagnetic ratios or for those experiencing strong anisotropic spin interactions, where conventional Hartmann-Hahn cross-polarization is difficult to apply. We demonstrate the method on 1H-13C, 1H-15N and 19F-109Ag systems.     

Quantum Hall Quantized Cyclotron Entrance Channels

Quantum Hall plateaus are entered via quantized cyclotron (QC) cloud-chamber orbits that have Landau-level (LL) energies and uniquely-defined angular momenta. The conservation of angular momentum in the quantum Hall system requires both canonical and magnetic angular momentum components, which add together to form the invariant kinematic angular momentum. The only LL radial eigenfunctions that satisfy the conservation-law requirements of the QC to LL transition are the u _n,l eigenstates u _n,2n+1, where n = 0, 1, 2, .... These same eigenstates uniquely have the correct scaled sizes to tile the observed families of = 1/(2n + 1) Hall plateaus. Quantum Hall plateau formation is a direct consequence of this tiling.     

Bis­[μ‐3{5}‐(2‐pyridyl)­pyrazolido]­bis­[(aceto­nitrile)copper(II)] diperchlorate

The title compound, [Cu₂(C₈H₆N₃)₂(C₂H₃N)₂](ClO₄)₂, con­tains a centrosymmetric dinuclear dication, with square‐pyrami­dal Cu^II centres linked by two 1,2‐pyrazolide bridging groups. There is a weak apical interaction between each Cu ion and a perchlorate O atom.