Applicability of UV laser-induced solid-state fluorescence spectroscopy for characterization of solid dosage forms

High production output of solid pharmaceutical formulations requires fast methods to ensure their quality. Likewise, fast analytical procedures are required in forensic sciences, for example at customs, to substantiate an initial suspicion. We here present the design and the optimization of an instrumental setup for rapid and non-invasive characterization of tablets by laser-induced fluorescence spectroscopy (with a UV-laser (λ _ex?=?266 nm) as excitation source) in reflection geometry. The setup was first validated with regard to repeatability, bleaching phenomena, and sensitivity. The effect on the spectra by the physical and chemical properties of the samples, e.g. their hardness, homogeneity, chemical composition, and granule grain size of the uncompressed material, using a series of tablets, manufactured in accordance with design of experiments, was investigated. Investigation of tablets with regard to homogeneity, especially, is extremely important in pharmaceutical production processes. We demonstrate that multiplicative scatter correction is an appropriate tool for data preprocessing of fluorescence spectra. Tablets with different physical and chemical characteristics can be discriminated well from their fluorescence spectra by subjecting the results to principal component analysis.     

Infrared extinction by homogeneous particle aggregates of SiC, FeO and : Comparison of different theoretical approaches

Particle shape and aggregation have a strong influence on the spectral profiles of infrared phonon bands of solid dust grains. Calculating these effects is difficult due to the often extreme refractive index values in these bands. In this paper, we use the discrete dipole approximation (DDA) and the T-matrix method to compute the absorption band profiles for simple clusters of touching spherical grains. We invest reasonable amounts of computation time in order to reach high dipole grid resolutions and take high multipolar orders into account, respectively. The infrared phonon bands of three different refractory materials of astrophysical relevance are considered—silicon carbide, wustite and silicon dioxide. We demonstrate that even though these materials display a range of material properties and therefore different strengths of the surface resonances, a complete convergence is obtained with none of the approaches. For the DDA, we find a strong dependence of the calculated band profiles on the exact dipole distribution within the aggregates, especially in the vicinity of the contact points between their spherical constituents. By applying a recently developed method to separate the material optical constants from the geometrical parameters in the DDA approach, we are able to demonstrate that the most critical material properties are those where the real part of the refractive index is much smaller than unity.     

Lyapunov Modes of Two-Dimensional Many-Body Systems; Soft Disks, Hard Disks, and Rotors

The dynamical instability of many-body systems can best be characterized through the local Lyapunov spectrum {}, its associated eigenvectors {}, and the time-averaged spectrum {}. Each local Lyapunov exponent describes the degree of instability associated with a well-defined direction—given by the associated unit vector —in the full many-body phase space. For a variety of hard-particle systems it is by now well-established that several of the vectors, all with relatively-small values of the time-averaged exponent , correspond to quite well-defined long-wavelength modes. We investigate soft particles from the same viewpoint here, and find no convincing evidence for corresponding modes. The situation is similar—no firm evidence for modes—in a simple two-dimensional lattice-rotor model. We believe that these differences are related to the form of the time-averaged Lyapunov spectrum near =0.     

Computer Simulation of Irreversible Expansions via Molecular Dynamics, Smooth Particle Applied Mechanics, Eulerian, and Lagrangian Continuum Mechanics

We simulate the far-from-equilibrium irreversible expansion of a compressed ideal gas in two space dimensions. For this problem the particle trajectories from conventional smooth particle applied mechanics are isomorphic to those from a corresponding molecular dynamics simulation. The smooth-particle weight function used to describe the expanding gas is identical to the pair potential governing the molecular dynamics simulation. These many-body particle simulations are compared with those using a modified smooth-particle algorithm invented by Monaghan, as well as with those based on conventional grid-based Eulerian and Lagrangian methods.     

Challenges and applications of isotachophoresis coupled to mass spectrometry: A review

Electrophoretic separations are of growing interest to tackle complex analytical challenges. Nevertheless, capillary electrophoresis, as the most common mode, still suffers from insufficient detection limits due to low capillary loadability. ITP is of growing interest as preconcentration method for capillary electrophoresis and is also interesting to be applied as an independent analytical method. While mass spectrometric detection is common for capillary electrophoresis, the combination of ITP with MS is still a niche technique. In this work, we want to give an overview on isotachophoretic effects in CE-MS and ITP-MS methods, as well as coupling techniques of ITP with CE-MS. The challenges and possibilities associated with mass spectrometric detection in ITP and its coupling to capillary electrophoresis are critically discussed.     

Lyapunov instability, local curvature, and the fluid-solid phase transition in two-dimensional particle systems

We study the relation between the Lyapunov spectrum and the multidimensional geometry of the potential energy surface in terms of the distribution of stable and unstable modes for different models. For this purpose we determined Lyapunov exponents for the so-called correlated cell model and its smooth generalization as a function of the density for various energies. In the smooth case averaged structural quantities, such as the fraction of unstable modes, the Gaussian curvature, and the Riemannian curvature were computed and compared to the mechanical instability of the system in the sense of Lyapunov. A similar analysis was also carried out for 36-disk systems representing various fluid and solid states. In all studied cases the most-positive Lyapunov exponent exhibits a maximum at the phase transition in agreement with results for the fluid-solid transition in many-particle systems.     

Externally perturbed unstable systems

We discuss computer solutions of Newton's equations of motion for unstable systems in a container with time-dependent walls. An expansion leads to the formation of a cluster and a significant increase of the temperature. The question of entropy increase for expansion and compression of the system and the related problem of the feasibility of a perpetum mobile of the second kind are investigated.