Determination of pharmaceuticals in environmental and biological matrices using pressurised liquid extraction—Are we developing sound extraction methods?

Pressurised liquid extraction (PLE) is now a well established and extensively applied extraction technique in environmental analysis for pollutants such as persistent organic pollutants (POPs). During the past decade, an emerging group of environmentally interesting analytes are pharmaceuticals that are continuingly released into the environment. This class is comprised with compounds of various properties. As the field of the analysis of these compounds grows, an increasing number of PLE methods for pharmaceuticals of varying quality are developed and published. This review summarises the critical PLE parameters during PLE method development and highlight them with examples from recently published papers utilising pressurised liquid extraction for the determination of pharmaceuticals in environmental and biological matrices. These recent methods are summarised and critically discussed with the aim to provide important reflections to alleviate in future PLE development for pharmaceuticals in environmental matrices.     

Evolution of Porosity by Freeze Casting and Sintering of Sol-Gel Derived Ceramics

Freeze cast of aqueous ceramic powder slurries is described as a versatile process to fabricate complex-shaped ceramic parts. Since freezing of aqueous sols or powder suspensions include the nucleation and growth of ice crystals the evolving microstructure in particular the pore characteristics which are left behind after elimination of the solvent can be controlled by the freezing process. The freezing kinetics have then to be used to manifest the conditions for the formation of the intended porosity. The temperature profile in the freezing slurry was measured and calculated, in particular the movement of the freezing front through the slurry was determined. The results show that a homogeneous microstructure is reached in the surface region of the consolidated part. Individual ice crystals are detected within a distance of some hundred micrometers from the surface. The final pores are dendritic in shape with an elliptical cross section. The pores can grow up to several millimeters in length under the process conditions used in this study. The limits of freeze-sensitive slurry compositions should be investigated in further studies and the approach should be followed to increase the porosity by additional foaming steps.     

Properties and characterization of hydrophobized microfibrillated cellulose

Microfibrillated cellulose (MFC) obtained by disintegration of bleached softwood sulphite pulp in a homogenizer, was hydrophobically modified by surface silylation with chlorodimethyl isopropylsilane (CDMIPS). The silylated MFC was characterized by Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), transmission electron spectroscopy (TEM), X-ray photoelectron spectroscopy (XPS) and white light interferometry (WLI). The degree of surface substitution (DSS) was determined using Si concentrations from XPS survey scans, as well as deconvoluted peaks in high-resolution C1s XPS spectra. The DSS values obtained by the two methods were found to be in good agreement. MFC with DSS between 0.6 and 1 could be dispersed in a non-flocculating manner into non-polar solvents, TEM observations showing that the material had kept its initial morphological integrity. However, when CDMIPS in excess of 5 mol CDMIPS/glucose unit in the MFC was used, partial solubilization of the MFC occurred, resulting in a drop in the observed DSS and a loss of the microfibrillar character of the material. The wetting properties of films cast from suspension of the silylated MFC were also investigated. The contact angles of water on the films increased with increasing DSS of the MFC, approaching the contact angles observed on super hydrophobic surfaces for the MFC with the highest degree of substitution. This is believed to originate from a combination of low surface energy and surface microstructure in the films.     

Atomic beam preparation for hydrogen maser operation with unpolarized atoms

The conventional atomic beam preparation technique for hydrogen maser operation consists of a six pole magnetic field focussing in combination with adiabatically changing magnetic fields in the transition region between focusser and maser cavity, which results in a state selected, polarized ensemble of hydrogen atoms. Hydrogen maser operation with state selected, but unpolarized atoms has the advantage to reduce considerably the sensitivity of hydrogen maser frequency on coherently excited, low frequency,Δm _F =±1 Zeeman transitions. The influence of the magnetic field pattern in the transition region on the energy level population probabilities for the focussed hydrogen beam has been analysed. Atomic beam preparation techniques using non-adiabatically changing magnetic field configurations in the transition region are described. The dependence of hydrogen maser oscillation on the energy level population within the atomic beam is theoretically investigated and the results are used for the analysis of the experimentally achieved atomic beam populations. It has been shown that a pulsed magnetic spin guidance field in the transition region, which switches between adiabatically changing magnetic field configurations and a sudden magnetic field reversal, results in an ensemble of hydrogen atoms with vanishing time averaged polarization, which does not deteriorate the conventionally achieved maser oscillation amplitude.     

Aromatic reactivity : LVIII. Base-cleavage of bonds between trimethylsilyl groups and polynuclear aromatic rings

The relative rates of cleavage of aryl-SiMe₃ compounds in a mixture of 1.0 M potassium hydroxide (1 vol) and DMSO (6 vol) at 70° have been found to be as follows: (aryl = ) Ph, 1.0; 1-naphthyl, 12.5; 2-naphthyl, 4.7; 9-phenanthryl, 51; 1-pyrenyl, 71. The order of reactivity is the same as that observed for hydrogen-exchange of the corresponding hydrocarbons in cyclohexylamine containing lithium cyclohexylamide, and it seems that the stability of the aryl carbanion is the dominant influence in both cases.     

The numerical radius of exterior powers

Let λ₁ and α₁ be respectively the eigenvalue of largest modulus and largest singular value of a linear operator A. Then A is called radial if |λ₁| = α₁. This paper is concerned with an examination of radial compound matrices. It turns out that the radial property for compound matrices is equivalent to an investigation of the case of equality in the classical inequalities of H. Weyl relating products of eigenvalues and singular values.     

Angewandte Physik

Ohne Zusammenfassung     

Conditions for the indistinguishability of thermal equilibrium and single atomic collision relative level populations

Single atomic collision and thermodynamic equilibrium level populations are compared. The population distributions for relatively cascade free levels with similar lifetimes are shown to be easily described by a Boltzmann relation even if the excitation mechanism is non-thermal.