A study of the headgroup motion of sphingomyelin using 31P NMR and an analytically soluble model

A 31P NMR investigation has been carried out of the headgroup dynamics of sphingomyelin molecules in bilayers for the L alpha and L beta' phases. The resulting line shapes have been analysed in terms of a reduced-parameter model, using van Faassen's method for obtaining an analytic solution to first-order stochastic differential equations to simulate the line shapes of oriented and non-oriented samples. Our treatment results in good fits to measured data but using fewer parameters than traditional methods. Angles and correlation times (tau parallel and tau perpendicular) describing the geometry and dynamics of the headgroup are obtained by optimising the agreement between simulated and experimental data. The results are contrasted with those obtained for the lecithins DMPC and DPPC using a similar analysis. Not only are tau parallel and tau perpendicular now equal in value for the L alpha phase, but this value is also found to be nearly four times larger than the longest correlation time for the lecithins. We interpret this as evidence of inter- and intramolecular hydrogen bonding in the L(alpha) phase of sphingomyelin. In the L beta' phase of sphingomyelin, however, although tau(parallel) and tau(perpendicular) remain equal their value is now 32% smaller than that of the lecithins in the same phase. This indicates less difference between the fluidities in the headgroup region of the two phases of sphingomyelin as compared to that of the lecithins. Another significant difference between the L beta' phases is that the tilt angle for sphingomyelin is found to be nearly twice as large as for the lecithins. We argue that these combined observations point to the existence of hydrogen bonding in this phase also. Again in contrast to our previous work on lecithins, our results provide evidence of a negative diamagnetic anisotropy in sphingomyelin molecules, even in the L beta' phase. This is provided for in our model by the assumption that our unoriented samples consist of prolate ellipsoidal liposomes whose major axes are oriented parallel to the static magnetic field. The apparently different diamagnetic behaviour of sphingomyelin in the present work is due to the higher static field used rather than any intrinsic difference in this respect between sphingomyelin and the lecithins DMPC and DPPC.     

Heteronuclear decoupling interference during symmetry-based homonuclear recoupling in solid-state NMR

We examine the influence of continuous-wave heteronuclear decoupling on symmetry-based double-quantum homonuclear dipolar recoupling, using experimental measurements, numerical simulations, and average Hamiltonian theory. There are two distinct regimes in which the heteronuclear interference effects are minimized. The first regime utilizes a moderate homonuclear recoupling field and a strong heteronuclear decoupling field; the second regime utilizes a strong homonuclear recoupling field and a weak or absent heteronuclear decoupling field. The second regime is experimentally accessible at moderate or high magic-angle-spinning frequencies and is particularly relevant for many realistic applications of solid-state NMR recoupling experiments to organic or biological materials.     

Raman scattering studies of the high-pressure stability of pentaerythritol tetranitrate, C(CH2ONO2)4

High-pressure Raman scattering studies have been performed on a crystalline energetic material, pentaerythritol tetranitrate C(CH2ONO2)4 (PETN), an important secondary explosive. In situ, ambient-temperature investigations employed diamond anvil cell techniques and nitrogen as a quasi-hydrostatic-pressure-transmitting medium. The pressure-induced alterations in the profiles of the Raman lines, including positions, bandwidths, and intensities, were studied in a compression sequence up to about 31.3 GPa and in a subsequent decompression to ambient conditions. The observed changes of the Raman spectra implied that PETN gradually densified and compressed smoothly up to the highest investigated pressures. Compression below 12 GPa gradually shifted all Raman peaks to higher frequencies without significantly changing their relative intensities or bandwidths. At higher pressures, the peak intensities of the Raman spectra decreased considerably and the bands broadened significantly. The Raman spectrum of the material quenched from 31.3 GPa to ambient conditions indicated that no pressure-driven permanent reconstructive modification or decomposition of the PETN structure occurred. That is, the spectral changes were completely reversible upon compression and subsequent decompression to ambient conditions.     

Pump-probe differencing technique for cavity-enhanced, noise-canceling saturation laser spectroscopy

We present an experimental technique that permits mechanical-noise-free, cavity-enhanced frequency measurements of an atomic transition and its hyperfine structure. We employ the 532-nm frequency-doubled output from a Nd:YAG laser and an iodine vapor cell. The cell is placed in a folded ring cavity (FRC) with counterpropagating pump and probe beams. The FRC is locked with the Pound-Drever-Hall technique. Mechanical noise is rejected by differencing the pump and probe signals. In addition, this differenced error signal provides a sensitive measure of differential nonlinearity within the FRC.     

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.     

3,6-dioxypyridazine bridged tungsten-tungsten quadruple bonds. Comparisons of electron delocalisation with oxalate bridged compounds

The preparation and characterisation of the tungsten-tungsten quadruply bonded, 3,6-dioxypyridazine bridged complex [((t)BuCO(2))(3)W(2)](2)([micro sign]-H(2)C(4)N(2)O(2)) and its single electron oxidised radical cation are reported and, when compared with related bridged dimolybdenum complexes, reveal a different mechanism of electronic coupling from that seen in related oxalate bridged systems.     

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.