Validation of a novel LC-MS/MS method for the quantitation of colistin A and B in human plasma

A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method, characterized by complete automation and high-throughput, was developed for the determination of colistin A and B in human plasma. All sample preparation procedures were performed by using 2.2 mL 96-deep-well plates, whereas robotic liquid-handling workstations were utilized for all liquid transfer steps, including solid-phase extraction (SPE). The whole preparation procedure was very rapid, whereas the method had a very short chromatographic run time of just 2 min. Sample analysis was performed by reversed phase LC-MS/MS, with positive electrospray ionization, using multiple reaction monitoring. The absence of available purified colistin A and B standards led to the development of a novel LC method with evaporative light-scattering detector for the determination of their stoichiometries in the standard mixture, along with its purity. The proposed bioanalytical method was fully validated and it was proven to be selective, accurate, precise, reproducible and suitable for the determination of colistin A and B in human plasma. It was applied successfully to a pharmacokinetic study for the determination of both analytes in samples of patients.     

The influence of temperature on rheological properties of blood mixtures with different volume expanders—implications in numerical arterial hemodynamics simulations

During the complicated cardiac surgery on a non-beating heart with cardiopulmonary bypass, protection of the heart is accomplished by injecting cold cardioplegic solutions. In most forms of circulatory shock, it is necessary to immediately restore the circulating volume. Intravenous solutions of volume expanders, such as hydroxyethyl starch and dextrans, are used to increase the volume of fluid in the circulating blood. In this work, blood samples of six donors were obtained and used to prepare mixtures with different volume expanders in concentrations ranging from 10 to 50 vol./vol.%. The flow curves of all mixtures in the temperature range from 4°C to 37°C were constructed and fitted to the Herschel–Bulkley model, in order to extract the shear thinning and yield stress parameters. To assess the influence of the observed changes in the rheological properties of blood on the hemodynamics in arterial vasculature, a realistic three-dimensional rigid-wall computational model was constructed from MRI images of the right carotid bifurcation obtained in vivo from a healthy male volunteer. The time-varying flow field was numerically computed using the Newtonian model as well as the Herschel–Bulkley model with the Papanastasiou regularization. The numerical simulations indicate only moderate changes in the time-averaged flow field that become accentuated when the instantaneous flow field is considered. We also found that although the influence of temperature, hematocrit, and volume expanders on hemodynamics is significant, this can primarily be attributed to the changes in the nominal viscosity of the flow medium.     

Estimation of the droplet size spread with the laser induced fluorescence/Mie technique

The laser measurement technique based on the ratio between the laser induced fluorescence (LIF) and the scattered light (Mie) intensities of droplets is presently limited to the evaluation of the Sauter mean diameter of the droplets. The important measurement of the droplet size spread is currently missing. An extension of the LIF/Mie technique for the measurement of droplet size spread is proposed here and is evaluated numerically. The method is based on the imperfect relationships between the scattered light intensity and the droplet surface area or the fluorescent light intensity and the droplet volume, which convey additional information that can be used to evaluate the droplet size spread.     

Multiaxial ratcheting with advanced kinematic and directional distortional hardening rules

Ratcheting is defined as the accumulation of plastic strains during cyclic plastic loading. Modeling this behavior is extremely difficult because any small error in plastic strain during a single cycle will add to become a large error after many cycles. As is typical with metals, most constitutive models use the associative flow rule which states that the plastic strain increment is in the direction normal to the yield surface. When the associative flow rule is used, it is important to have the shape of the yield surface modeled accurately because small deviations in shape may result in large deviations in the normal to the yield surface and thus the plastic strain increment in multi-axial loading. During cyclic plastic loading these deviations will accumulate and may result in large errors to predicted strains.This paper compares the bi-axial ratcheting simulations of two classes of plasticity models. The first class of models consists of the classical von Mises model with various kinematic hardening (KH) rules. The second class of models introduce directional distortional hardening (DDH) in addition to these various kinematic hardening rules. Directional distortion describes the formation of a region of high curvature on the yield surface approximately in the direction of loading and a region of flattened curvature approximately in the opposite direction. Results indicate that the addition of directional distortional hardening improves ratcheting predictions, particularly under biaxial stress controlled loading, over kinematic hardening alone.     

Resonance method of electric-dipole-moment measurements in storage rings

A "resonance method" of measuring the electric dipole moment (EDM) of nuclei in storage rings is described, based on two new ideas: (1) Oscillating particles' velocities in resonance with spin precession, and (2) alternately producing two sub-beams with different betatron tunes--one sub-beam to amplify and thus make it easier to correct ring imperfections that produce false signals imitating EDM signals, and the other to make the EDM measurement.     

A Study of Parameters that Influence the Accuracy of the Planar Droplet Sizing (PDS) Technique

A combined theoretical and experimental study of the parameters affecting the accuracy of Planar Droplet Sizing (PDS) measurements is presented. The principle of the PDS technique relies on the assumption that the intensity emitted by a fluorescent dye added to a liquid is proportional to the volume of a resulting droplet during atomisation and that the scattered light intensity is proportional to its surface area, allowing measurement of Sauter Mean Diameter (SMD) by taking the ratio of these intensities. A geometrical optics light scattering approach was extended to calculate the fluorescence intensity emitted by a droplet, in addition to providing the scattered light intensity integrated over the collection aperture. The theoretical approach quantified the influences of scattering angle, refractive index, droplet size and dye concentration on the PDS technique. Experiments with monodisperse droplet streams confirmed the calculations in terms of dependence of the scattered and fluorescence intensities. The limitations of the technique have been established together with an appropriate calibration procedure for application in dense sprays.     

CO2 laser excitation of triethylsilane: Time resolved luminescence of diethylsilyl radical

The infrared multiphoton excitation of triethylsilane in the gas phase, with a pulsed CO₂ laser at high intensities (I > 700 MW/cm²), produced an intense luminescence. The spectrum and time profile of this luminescence was studied as a function of pressure, and laser frequency. The radiative lifetime of this emission was 357 ± 10 ns, and the quenching rates by Cl₂ and NO were determined from lifetime measurements. A reasonable mechanism for the interpretation of this luminescence involves the initial infrared multiphoton decomposition of triethylsilane, followed by the secondary infrared multiphoton excitation of the primary photofragment diethylsilyl radical, which subsequently undergoes relaxation to an excited electronic state. The addition of O₂ resulted in a new chemiluminescence at shorter wavelengths, which corresponds to the SiO* chromophore group. © 1994 John Wiley & Sons, Inc.     

Vibrational relaxation of highly excited molecules: VV transfer from SF6 to N2O

Vibrational energy transfer from SF₆ to N₂O was studied as a function of SF₆ vibrational energy. The intensity, rise time and decay time of N₂O fluorescence increased monotonically with the level of donor excitation. The observations are consistent with a mechanism that is not mode specific, with donor VT relaxation faster than intermolecular VV transfer.