Application of matrix-assisted laser desorption/ionization to on-line aerosol time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization (MALDI) mass spectra were obtained from single biological aerosol particles using an aerosol time-of-flight mass spectrometer (ATOFMS). The inlet to the ATOFMS was coupled with an evaporation/condensation flow cell that allowed the aerosol to be coated with matrix material as the sampled stream entered the spectrometer. Mass spectra were generated from aerosol composed either of gramicidin-S or erythromycin, two small biological molecules, or from aerosolised spores of Bacillus subtilis var niger. Three different matrices were used: 3-nitrobenzyl alcohol, picolinic acid and sinapinic acid. A spectrum of gramicidin-S was generated from approximately 250 attomoles of material using a molar ratio of 3-nitrobenzyl alcohol to analyte of approximately 20:1. A single peak, located at 1224 Da, was obtained from the bacterial spores. The washing liquid and extract solution from the spores were analyzed using electrospray mass spectrometry and subsequent MS/MS product ion experiments. This independent analysis suggests that the measured species represents part of the B. subtilis peptidoglycan. The on-line addition of matrix allows quasi-real-time chemical analysis of individual, aerodynamically sized particles, with an overall system residence time of less than 5 seconds. These results suggest that a MALDI-ATOFMS can provide nearly real-time identification of biological aerosols. Copyright 2000 John Wiley & Sons, Ltd.     

Application of the Floquet theory to multiple quantum NMR of dipolar-coupled multi-spin systems under magic angle spinning

A new analytical Liouville-space representation of the time-propagator under magic angle spinning (MAS) is introduced using the formalized quantum Floquet theory. This approach has the advantage that it is applicable to the analysis of any type of NMR experiment where MAS is combined with multiple-pulse excitation. General relationships describing the spectral parameters in multiple-quantum (MQ) MAS spectra are derived in this representation. Their use is illustrated with an application to double-quantum (DQ) NMR spectra of dipolar-coupled multi-spin systems. Corresponding to the separation of the MAS time-propagator into a rotor modulated and a dephasing component, two distinct mechanisms for DQ excitation are identified. One of them exploits the rotor-modulated component to excite DQ coherences through dipolar-recoupling techniques, which are familiar for spin pairs. Analytical expressions of the integral intensities and linewidths in the resulting DQ sideband pattern are derived in the form of power series expansions of the inverse rotor frequency, of which coefficients depend on structural parameters. In a multi-spin system they can most reliably be extracted in the fast spinning regime. The other mechanism exploits the dephasing component, which is characteristic to multi-spin systems only. This is shown to give rise to DQ coherences by free evolution at full rotor periods. The possibility to exploit it for selective excitation of higher order MQ coherences is discussed. In either case, the dephasing component also leads to residual broadening. The main results of the theoretical developments are demonstrated experimentally on adamantane.     

A mathematical model of aging-related and cortisol induced hippocampal dysfunction

Background  

The hippocampus is essential for declarative memory synthesis and is a core pathological substrate for Alzheimer's disease (AD), the most common aging-related dementing disease. Acute increases in plasma cortisol are associated with transient hippocampal inhibition and retrograde amnesia, while chronic cortisol elevation is associated with hippocampal atrophy. Thus, cortisol levels could be monitored and managed in older people, to decrease their risk of AD type hippocampal dysfunction. We generated an in silicomodel of the chronic effects of elevated plasma cortisol on hippocampal activity and atrophy, using the systems biology mark-up language (SBML). We further challenged the model with biologically based interventions to ascertain if cortisol associated hippocampal dysfunction could be abrogated.     

Gram-Schmidt orthogonalization of the Zernike polynomials on apertures of arbitrary shape

An orthonormal hexagonal Zernike basis set is generated from circular Zernike polynomials apodized by a hexagonal mask by use of the Gram-Schmidt orthogonalization technique. Results for the first 15 hexagonal Zernike polynomials are shown. The Gram-Schmidt orthogonalization technique presented can be extended to both apertures of arbitrary shape and other basis functions.     

Diagnosing unknown aberrations in an adaptive optics system by use of phase diversity

We outline a novel method for estimating a fixed aberration that is in the image path but not in the wave-front-sensor (WFS) path of an adaptive optics (AO) imaging system. We accomplish this through a nontraditional application of the Gonsalves [Proc. SPIE 207, 32 (1997)] least-squares phase-diversity technique, using an ensemble of images and WFS data. The diversity phases required for this technique are provided by the temporal differences in WFS residual phase measurements for different members of the ensemble. We demonstrate the technique by using actual observations from an operational AO system exhibiting such an aberration. An estimate of this aberration was obtained by the proposed algorithm that agrees reasonably well with the observed point-spread function.     

Constrained matched filtering for extended dynamic range and improved noise rejection for Shack-Hartmann wavefront sensing

We recently introduced matched filtering in the context of astronomical Shack-Hartmann wavefront sensing with elongated sodium laser beacons [Appl. Opt. 45, 6568 (2006)]. Detailed wave optics Monte Carlo simulations implementing this technique for the Thirty Meter Telescope dual conjugate adaptive optics system have, however, revealed frequent bursts of degraded closed loop residual wavefront error [Proc. SPIE 6272, 627236 (2006)]. The origin of this problem is shown to be related to laser guide star jitter on the sky that kicks the filter out of its linear dynamic range, which leads to bursts of nonlinearities that are reconstructed into higher-order wavefront aberrations, particularly coma and trifoil for radially elongated subaperture spots. An elegant reformulation of the algorithm is proposed to extend its dynamic range using a set of linear constraints while preserving its improved noise rejection and Monte Carlo performance results are reported that confirm the benefits of the method.