Development and evaluation of a nano-electrospray ionisation source for atmospheric pressure ion mobility spectrometry

A nano-electrospray ionisation source has been designed and constructed for a high temperature ion mobility spectrometer. The drift cell was modified by replacement of the 63Ni atmospheric pressure chemical ionisation source with a tube lens/desolvation region and operated using commercial nano-electrospray capillaries. Ions were introduced into the drift region via a Bradbury-Nielson gate (pulse width 50 micros, repetition period 20 ms). A unidirectional flow of nitrogen was used as the drift gas at temperatures in the range 100-150 degrees C to aid desolvation. The performance of the nano-electrospray ion source has been demonstrated for analytes including crown ethers, amino acids and peptides. Reduced mobilities determined by nano-ESI were consistent with those reported using a 63Ni ion source.     

Structure and synthesis of a newly discovered terpenoid isolated from Lavandin oil: Trans-5-hydroxy-2-isopropenyl-5-methylhex-3-enyl acetate

A newly discovered component of the oil of Lavandin abrialis has been shown by spectroscopic data to be trans-5-hydroxy-2-isopropenyl-5-methylhex-3-enyl acetate (I). A synthesis of this material is described.     

Isostructural or not? Adducts of some aryl­tin halides with (E)‐1,2‐bis(4‐pyridyl)­ethene

The title complexes [μ‐(E)‐4,4′‐(ethene‐1,2‐diyl)­di­pyridine‐κ²N:N′]­bis­[halotris(4‐methyl­phenyl)­tin(IV)], [Sn₂(C₇H₇)₆X₂(C₁₂H₁₀N₂)], where halo is chloro (X = Cl) and bromo (X = Br) are isostructural. In both crystals, the mol­ecules lie on inversion centers, and there are voids of ca 80 ų that could, but apparently do not, accommodate water mol­ecules. The corresponding iodo structure (X = I) is almost, but not quite, isostructural with the other two compounds; when Br is changed to I, the length of the c axis decreases by more than 1 Å and the voids are no longer large enough to accomodate any solvent mol­ecule. The related complex [μ‐(E)‐4,4′‐(ethene‐1,2‐diyl)­di­pyridine‐κ²N:N′]­bis­[chloro­tri­phenyl­tin(IV)], [Sn₂(C₆H₅)₆Cl₂(C₁₂H₁₀N₂)], crystallizes in a related structure, but the mol­ecules lie on general rather than on special positions. The molecular structures of the four complexes are similar, but the conformation of the phenyl derivative is approximately eclipsed rather than staggered.     

Comparison of FM dye lasers in standing-wave and ring configuration

We have compared the operation of a frequency-modulated dye laser (FML) in a standing-wave and ring configuration. As expected, for a given frequency detuning (difference between the drive frequency for the phase modulator and the cavity mode spacing) the enhanced modulation index is twice as large for the standing-wave configuration as for the ring configuration. In addition, we have demonstrated that application of small amounts of phase modulation in the ring configuration leads to improved mode stability. The fine structure of the rf beats for both FM lasers, have been studied and the results suggest that spatial hole burning complicates the detailed structure.     

The nuclear magnetic resonance spectra of pyrazines—II : The influence of side-chain alkyl substitution on the benzylic coupling constants

The benzylic coupling constants ⁵J_m and ⁶J_p for a series of 2-alkyl-3-methoxypyrazines, in which the size of the 2-alkyl group is progressively increased, are reported and discussed. ⁵J_m remains virtually constant, while ⁶J_p falls steadily with increasing alkyl group size. These effects are largely attributed to variations in the time-averaged orientation of the benzylic protons and are consistent with the generally accepted mechanisms for meta and para benzylic coupling. The results illustrate the importance of taking conformational aspects into account when attempting to use benzylic coupling constants derived from substituted side-chains in making structural assignments.     

Frequency offset locking of a synchronously pumped mode-locked dye laser

We have developed a scheme of frequency offset locking for transferring the frequency stability of a commercial dye laser to a synchronously pumped mode-locked dye laser. By observing the beat frequency between the two dye lasers, mode stability of less than 2 MHz has been observed for the mode-locked dye laser mode. The use of the mode-locked system as a spectroscopic tool has been demonstrated by observing Doppler-free multiple pulse two photon spectra of the sodium 3S-4D transition.     

A locking-free hp DPG method for linear elasticity with symmetric stresses

We present two new methods for linear elasticity that simultaneously yield stress and displacement approximations of optimal accuracy in both the mesh size $h$ and polynomial degree $p$ . This is achieved within the recently developed discontinuous Petrov–Galerkin (DPG) framework. In this framework, both the stress and the displacement approximations are discontinuous across element interfaces. We study locking-free convergence properties and the interrelationships between the two DPG methods.     

Dy2Ti2O7 spin ice: a test case for emergent clusters in a frustrated magnet

Dy2Ti2O7 is a geometrically frustrated magnetic material with a strongly correlated spin ice regime that extends from 1 K down to as low as 60 mK. The diffuse elastic neutron scattering intensities in the spin ice regime can be remarkably well described by a phenomenological model of weakly interacting hexagonal spin clusters, as invoked in other geometrically frustrated magnets. We present a highly refined microscopic theory of Dy2Ti2O7 that includes long-range dipolar and exchange interactions to third nearest neighbors and which demonstrates that the clusters are purely fictitious in this material. The seeming emergence of composite spin clusters and their associated scattering pattern is instead an indicator of fine-tuning of ancillary correlations within a strongly correlated state.