Influence of oleic acid on the structure of a mixture of hydrated model stratum corneum fatty acids and their soaps

The phase behaviour of a hydrated (32% (w/w) water) mixture of saturated and unsaturated fatty acids and their soaps has been examined. By progressively increasing the proportion of oleic acid, it could be shown that this unsaturated component exists partly as a separate phase within the others. The unsaturated fatty acids form an H_II phase at 25°C, whereas the saturated fatty acids form a fatty acid—soap crystal under the conditions employed. The results help to explain the role played by the fatty acids (and also cholesterol) within the lipid fraction of human stratum corneum. A feature of this study is a comparison of the results obtained by X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy.     

Minimum information estimation of allocation models of different sizes

For allocation models consisting of n = 10, 6 and 4 equations, constrained generalized least squares coefficient estimates are compared with those obtained from the minimum information (MI) criterion in the sense of statistical information theory. The MI estimates are more efficient for n = 10. The bootstrap procedure is illustrated for the assessment of the variability of these estimates.     

Messungen zum lateralen Auflösungsvermögen für Röntgenquanten bei der Elektronenstrahl-Mikroanalyse

Zusammenfassung Die experimentelle Bestimmung der lateralen Ausdehnung des Röntgenemissionsvolumens gelingt aus Intensitätsmessungen an Schichten, deren Dicken in der Größenordnung der lateralen Ausdehnung liegen. Die Schichtsysteme werden dabei mit definierter Geschwindigkeit unter dem Elektronenstrahl hinweg bewegt, was einem Wandern des Röntgenemissionsvolumens durch das Schichtsystem gleichkommt. Von einer Schicht, deren Röntgenintensität gerade das Maximum eines Reinelement-Massivstandards erreicht, kann angenommen werden, daß ihre Dicke der lateralen Ausdehnung entspricht. Zur Messung der Schichtdicken wurden in erster Linie Liniendiagramme herangezogen; die Überprüfung erfolgte aus Röntgenrasterbildern der Elementverteilung.Die geeignete Auswahl der Proben, die aus Schichten leichter (Kohlenstoff), mittlerer (Kupfer) und schwerer (Gold) Elemente bestehen, gestattete die Interpolation der Ergebnisse auf Elemente beliebiger Ordnungszahl. Die Messung der Röntgenintensitäten bei verschiedener Anregungsenergie des Elektronenstrahls ergibt die Abhängigkeit der lateralen Ausdehnung von der Beschleunigungs-spannung.

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Measurements of the lateral resolution of X-ray emission by means of electron microprobe analysis

Summary The experimental determination of the diameter of the X-ray emission volume is obtained from intensity measurements on layers whose thickness lie in the range of this emission volume. The vertically orientated sandwich layers were moved with a definite velocity under the electron probe which amounts to a wandering of the X-ray emission volume through this system of layers. From a layer whose X-ray intensity is equivalent to maximum intensity of a bulk standard of the same material as the layer, one can assume that the diameter of the X-ray emission volume corresponds to the thickness of the layer. To measure the layer thickness, mostly linescans were used, followed by X-ray scan pictures of the element distribution to verify the same.A suitable choice of samples representing light (carbon), medium (copper) and heavy (gold) elements enables to interpolate the results on elements of any other mass number. The measurement of the X-ray intensity under varying electron energies shows the dependance of the diameter of the X-ray emission volume on accelerating voltage.

     

A structure-based design approach to advance the allyltyrosine-based series of HIV integrase inhibitors

As of mid-2017, only one structure of the human immunodeficiency virus (HIV) integrase core domain co-crystallised with an active site inhibitor was reported. In this structure (1QS4), integrase is complexed with a diketo-acid based strand-transfer inhibitor (INSTI). This structure has been a preferred platform for the structure-based design of INSTIs despite concerns relating to structural irregularities arising from crystallographic packing effects. A survey of the current pool of 297 reported integrase catalytic core structures indicated that the anatomy of the active site in the complex structure 1QS4 exhibits subtle variations relative to all other structures examined. Consequently, the 1QS4 structure was employed for docking studies. From the docking of twenty-seven allyltyrosine analogues, a 3-point inhibitor binding motif required for activity was established and successfully utilised in the development of a tripeptide displaying an EC₅₀ value of 10 ± 5 μM in HIV infected human T-cells. Additional docking of “in-house” compound libraries unearthed a methyl ester based nitrile derivative displaying an IC₅₀ value of 0.5 μM in a combined 3′-processing and strand-transfer assay.     

Synthesis,structure and characterization of [Mg7(μ3-OCH2CH2OMe)6(μ-OCH2CH2OMe)6][Al(n-Bu)4]2 – A cationic heptanuclear magnesium complex consisting of discrete cations and tetrabutylaluminate anions

Dibutylmagnesium (contaminated with Al(n-Bu)₃; n_Mg:n_Al ca. 1:0.2) was found to react with MeOCH₂CH₂OH followed by the addition of PhSCH(Me)Ph in the presence of 0.2 equiv n-butyllithium yielding [Mg₇(μ₃-OCH₂CH₂OMe)₆(μ-OCH₂CH₂OMe)₆][Al(n-Bu)₄]₂ (1) as the principal product (yield 40–45% referred to MeOCH₂CH₂OH). The single-crystal X-ray diffraction analysis revealed that the centrosymmetric cationic heptamagnesium complex is built up from seven edge-shared MgO₆ octahedra. The [Al(n-Bu)₄]⁻ anions adopt approximately a tetrahedral AlC₄ symmetry. ¹H, ¹³C and ²⁷Al NMR spectroscopic measurements showed that in THF solution the structures both of the heptamagnesium complex and the tetrabutylaluminate anion are preserved and that there are no cation–anion interactions reducing the symmetry. The ²⁷Al resonance (151.6 ppm) was found to be very sharp (w_1/2 = 5 Hz), the coupling constant ¹J(²⁷Al,¹³C) amounts to 72.3 Hz.     

Simultaneous spectrophotometric flow-through measurements of pH, carbon dioxide fugacity, and total inorganic carbon in seawater

An autonomous multi-parameter flow-through CO₂ system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO₂), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO₂ optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO₂ is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO₂. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO₂, and DIC during the CLIVAR/CO₂ A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO₂, and 2.4 μmol kg⁻¹ for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO₂, and 2.2 ± 6.0 μmol kg⁻¹ for DIC. This system integrates spectrophotometric measurements of multiple CO₂ parameters into a single package suitable for observations of both seawater and freshwater.     

Probing molecular shape. 1. Conformational studies of 5-hydroxyhexahydropyrimidine and related compounds

Understanding the factors that determine molecular shape enables scientists to begin to understand and tailor molecular properties and reactivity. Many biomolecules and bioactive compounds contain aliphatic heterocyclic rings whose conformations play a major role in their biological activity. The interplay of a number of factors, both steric and electronic, is examined for 5-hydroxyhexahydropyrimidine (1) and related compounds with use of spectroscopy and molecular modeling.