Physicochemical Principles of Extraction with Supercritical Gases

The present review considers some physicochemical properties of fluid mixtures that are of importance for fluid extraction and supercitical fluid chromatography (SFC). Firstly, the important types of phase diagrams are treated, the occurrence of solid phases also being considered in some simple cases. Specific examples are given of mixtures of a highly volatile component I (e.g. CO₂, C₂H₆) with a relatively involatile component II (e.g. squalane) of very different molecular size, shape, structure, and/or polarity, and it is shown how the rather complicated types of phase diagrams can be calculated and correlated. The importance of fluid mixtures extends far beyond the fields of science and technology reviewed.     

87Rb NMR study of the temperature and electric field dependence of the soliton density near the lock-in transition of incommensurate Rb2ZnCl4

The frequency distribution of the⁸⁷Rb NMR 1/2–1/2 central transition is measured in a detailed manner as a function of the temperature and the crystal orientation in the normal (N), incommensurate (IC), and commensurate (C) phases of high quality single crystals of Rb₂ZnCl₄ (RZC). Special emphasis is laid upon the region around the lock-in transition atT _c . While in the N and C phases discrete lines are observed, in the IC phase a continuous distribution of frequencies is detected. In a temperature interval not exceeding 15 K aboveT _c some centers of intensity termed C lines can be observed in the frequency distribution. They reflect the fact that in the IC phase close toT _c several nuclei feel a local surrounding very similar to that of the low temperature C phase. For the first time in the region aroundT _c the influence could be studied which an electric field favouring the ferroelectric C phase has on the NMR spectra. The experimental results are related to the temperature and electric field dependence of the soliton density near the lock-in transition. A general definition of the soliton density is developed whose validity is not limited to the very narrow soliton limit. The meaning of this definition is also discussed in terms of well known phenomenological theories of the three phases of RZC. The experimental NMR data can be well described by this general definition.Dedicated to Prof. Dr. H.E. Müser on the occasion of his 60th birthday     

PHOTOCHEMICAL RING-OPENING IN meso-CHLORINATED CHLOROPHYLLS

Abstract— Irradiation of 20-chloro-chlorophylls of the a-type with visible light produces long-wavelength shifted photoproducts, which transform in the dark to linear tetrapyrroles (bile pigments). The possible significance for chlorophyll degradation is discussed.     

Clathrate formation and phase transitions in β-hydroquinone

Clathrate thermodynamic stability conditions and the phase transitions associated with either the orientational ordering of the guest molecules or with the condensation of the guest molecules in the host lattice are investigated by means of the common microscopic model. The theory proposed describes the thermodynamic properties of -hydroquinone (Q ) clathrates. The dielectric constant (T) was measured experimentally inQ ·CH₃OH andQ ·SO₂ in the temperature range from 4.2 to 300 K and the phase transitions were found. It is shown that the theory qualitatively explains the experimental data obtained.Dedicated to Professor H. M. Powell.     

High-pressure phase studies on fluid mixtures of low-volatile organic substances with supercritical carbon dioxide

Two high-pressure phase equilibrium cells working according to the analytical method in the temperature range 300 to 450 K and up to 200 MPa have been developed. In the first cell p,T,x,y equilibrium data can be determined by sampling and GC analysis. With this cell the gas-liquid phase behaviour of the ternary systems carbon dioxide + tridecane + hexadecane and carbon dioxide + tridecane + 1-hexadecanol were determined at 423.4 K and between 8 and 35 MPa. For the second apparatus a spectroscopic high-pressure cell fitted with two pairs of sapphire windows was developed. Molar absorptivities are obtained from calibration runs in the homogeneous region. Gasliquid phase equilibria in the system decane + CO₂ were investigated from 342.8 to 400.2 K and between 10 and 20 MPa; here absorption data were measured in the NIR region.     

Determining consanguinity by oligonucleotide fingerprinting with (GTG)5/(CAC)5

Simple tandemly organized (GTG)n/(CAC)n sequences are spread throughout the human chromosomes. The most informative DNA fingerprints for the testing of pedigrees and/or paternity were obtained with the simple triplet repeat probe (GTG)5 or its complement (CAC)5. These hypervariable simple-repeat fragments are stably inherited in a Mendelian fashion. Using these highly discriminating probes, all human individuals could, theoretically, be differentiated, except for genetically identical monozygotic twins. Examples from actual case work are reported and pertinent advantages of this methodology are discussed.     

Quantitative analysis by high-performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry: The determination of the renin inhibitor CP-80,794 in human serum

A specific method was developed for the quantitative determination of the renin inhibitor CP-BO,794. Serum extracts containing the drug and an internal standard were injected into a standard reverse-phase high-performance liquid chromatography (HPLC) column. The mobile phase, methanol/water (8/2), flowed at 1 ml/min through the column and then via a heated nebulizer interface into a corona discharge atmospheric pressure chemical ionization source. The assay minimum limit of quantification was 50 pg/mL. It exhibits satisfactory accuracy and precision over the range 50 pg/ml, to 10 ng/mL. A minor modification of the HPLC mobile phase was necessary to attain extremely low detection limits. The addition of a structural analogue contributed to enhancing the precision of the assay.