Die Anwendung des Derivatographen zur Gleichzeitigen Dilatometrischen und Differential-Thermischen Analyse von Gläsern

Simultaneous DTA and dilatometric measurements were made and the derivatives of the dilatometric curves were taken for three glasses by means of a derivatograph. Glass blocks were used as test pieces with a boring for the thermoelement. A maximum was observed in the rate of length change, which can be explained by overheating phenomena. A comparison with DTA curves of glass powders published by Yamamoto showed that the break points in the DTA curves of glass blocks do not coincide with the Tg points, but under identical conditions they can serve for the rapid characterization of the transformation range.     

Two-step photoionization of Na2: dependence on alignment

Laser light is used for two-step photoionization of Na₂. the first step depends on the moleculer orientation, the second step doesnot. This yields a method for the analysis of molecular alignment.     

Analytical and radioanalytical quality control of purity and stability of radiopharmaceutical compound [186gRe]Re-HEDP for bone metastases pain palliation

Summary The nuclear properties of ^186gRe make it a useful agent for radionuclide therapy and imaging. The coordination compound [^186gRe]Re-HEDP has proved to be a successful bone seeking agent for palliation of metastatic bone pain. Chemical, radiochemical and radionuclidic purity of commercial radiopharmaceutical [^186gRe]Re-HEDP have been checked by means by γ- and β-spectrometries, INAA and paper radio-chromatography. The results indicate a good radionuclidic purity, with levels of contamination from the short-lived ¹⁸⁸Re well below the required specifications. After injection of the radiopharmaceutical, the radiochemical measurements conducted in vivo, on biological matrices, blood, plasma and urine, have shown that, entering the systemic circulation, ^186gRe dissociates from the bis-phosphonate complex as hydrosoluble [^186gRe]ReO₄-, and the two chemical species follow different biokinetics.     

Application of capillary zone electrophoresis and reversed-phase high-performance liquid chromatography in the biopharmaceutical industry for the quantitative analysis of the monosaccharides released from a highly glycosylated therapeutic protein

Two assays for the quantitative determination of the neutral and amino-monosaccharides attached to a therapeutic glycoprotein were developed using capillary zone electrophoresis (CZE) and RP-HPLC. These assays meet the strict batch release requirements of the quality control in biopharmaceutical industry. The monosaccharides were released from the glycoprotein by hydrolysis with 2N trifluoroacetic acid. In the CZE assay the monosaccharides were reacetylated prior to derivatization with 8-aminopyrenesulfonic acid (APTS), reacetylation in the glycoprotein matrix was investigated in detail. The RP-HPLC method used pre-column derivatization with anthranilic acid in methanol-acetate-borate reaction medium; reacetylation was not necessary. However, epimerization of the different monosaccharides was observed and studied in detail. For the quantitative assay, separation of the amino-monosaccharide epimers had to be developed. The HPLC assay was validated.     

Electromagnetic interactions with rough metal surfaces

When surfaces are structured on the scale of the wavelength, we can expect incident light to be strongly modified by the surface. This is especially the case when the surface is metallic. We have developed a formalism for computing these modifications, closely analogous to electron scattering theory, which we briefly review and present some results for optical properties of, and electron energy loss in, colloids. Our main theme is another effect associate with rough or structured metallic surfaces: Surface Enhanced Raman Scattering, or SERS. We model the rough surface by a periodic array of spheres and obtain the correct magnitude for the enhancement and for the frequency shifts observed.     

Fluorine absorption spectra and some fluorides in condensed state

The absorption spectra of liquid F₂, NF₃, N₂F₄, CF₄, BF₃, NF₃, SF₆ have been obtained at diminished temperatures in the near ultra-violet region of the spectrum. It is shown that the absorption spectrum does not differ from the spectra in the gaseous phase, therefore the elementary absorption act is characterized by the cross section of photon absorption by an individual molecule. The absorption cross sections of the above mentioned molecules are represented in the liquid phase, which do not differ strongly from absorption cross sections of these molecules in the gaseous phase. The dependence of the absorption cross sections of liquid fluorine on its concentrations in solutions with N₂, Ar, NF₃, O₂ at - 196°C has been studied. The cross sections of photon absorption by the fluoride molecule in different liquid media with small fluorine concentrations have been obtained.     

A rapid non-acidolytic method for deprotection and removal of peptides from solid phase resins - applications of ammonium formate catalytic transfer hydrogenation

Ammonium formate aided catalytic transfer hydrogenation has been employed in the cleavage, and concommitant deprotection, of the pentapeptide leucine enkephalin from the Merrifield peptide resin under ambient conditions of temperature and pressure in a neutral medium.     

Structural studies on layered alkylpyridinium iodopalladate networks

The reaction of alkylpyridinium (CnH2n + 1NC5H5, hereafter Cn-Py) iodide salts in aqueous acetonitrile with a preformed palladium iodide precursor afforded two different types of organic-inorganic phases depending on the molar ratio. A 2:1 ratio yielded the phase [Cn-Py]2[PdI4] (3, n = 14, 16), which crystallized in the triclinic crystal system. The X-ray crystal structure of 3, (n = 14), refined in the space group P1 (a = 8.918(3) A, b = 9.894(3) A, c = 29.062(12) A, alpha = 93.51(3) degrees, beta = 94.17(3) degrees, gamma = 115.60(3) degrees, and Z = 2), consists of interdigitated bilayers with a basal spacing of 29.0 A. The aliphatic chains of the cations, which run almost parallel to the stacking direction, are fully stretched between polar planes built on isolated [PdI4]2- anions and cation headgroups. Changing the organic cation to palladium ratio to 1:1 led to a new phase [Cn-Py]2[Pd2I6] (4, n = 14, 16), which crystallizes in the triclinic P1 space group (a = 9.399(4) A, b = 14.264(6) A, c = 29.415(13) A, alpha = 92.11(4) degrees, beta = 90.07(4) degrees, gamma = 104.53(3) degrees, Z = 3 for 4(n = 14); a = 9.417(2) A, b = 14.215(3) A, c = 31.552(6) A, alpha = 87.96(3) degrees, beta = 87.63(3) degrees, gamma = 75.67(3) degrees, Z = 3 for 4(n = 16)). The layered structure is basically of a continuously interdigitated single-layer type, with a bilayer sublattice superimposed. Isolated [Pd2I6]2- anions contribute to the inorganic planes. A high degree of interdigitation and tilting of the aliphatic chains lead to basal spacings of 29.4 and 31.5 A for 4(n = 14) and 4(n = 16), respectively. The [Cn-Py]2[PdI4] and [Cn-Py]2[Pd2I6] phases were characterized by thermal analysis. Mesomorphic behavior was observed only for 3(n = 16), which was confirmed by variable-temperature powder XRD and optical microscopy.     

Cubic phases as structures of disclinations

We look for possible ordered geometrical configurations with bicontinuous or cellular topologies, optimizing the frustration of a periodic system of frustrated fluid films. The solutions found have the same symmetries as those observed for cubic phases of amphiphilic molecules. This agreement leads to consider cubic structures as structures of defects of rotation, or disclinations.This paper was presented at the workshop Ringing gels and Cubic phases, University of Bayreuth, October 25–26th, 1988.     

The synthesis of cis- and trans-1,2-dibromocyclopropane

A preparative route to cis- and trans-1,2-dibromocyclopropane ($\text{1}$) was developed via the Hunsdiecker reaction of silver cyclopropane-1,2-dicarboxylate ($\text{2}$). Cis- and trans-$\text{2}$ gave the same ratio of cis- and trans-$\text{1}$ (1:3.2). The mechanism of this reaction is briefly discussed.