The analysis of some heterocyclic compounds

The mass spectra of some relatively simple sulphur compounds have been obtained. Comments upon the McLafferty rearrangement are reported.     

On the symmetry of iron(III) tris-acetylacetonate crystals

The crystal structure of iron tris-acetylacetonate is re-determined. Crystal data at 293 K are: a = 15.4524(5) Å, b = 13.5876(4) Å, c = 16.5729(7) Å, Z = 8; at 150 K: a = 15.2541(4) Å, b = 13.4451(3) Å, c = 16.4256(5) Å, Z = 8. The structure is molecular and comprises isolated molecules. The coordination polyhderon of iron is an almost regular octahedron, Fe-O bond lengths are 1.977–2.003 Å (293 K) and 1.982–2.006 Å (150 K). In the crystalline state, the molecules are arranged in layers, and iron atoms are located on a plane yielding an almost regular trigonal net with the Fe...Fe separations of 7.558–8.103 Å (293 K) and 7.472–8.017 Å (150 K). The adjacent layer is positioned exactly over the first one with a Fe...Fe distance of 8.303 Å (293 K) and 8.236 Å (150 K).     

Effect of the specific activity of the tracer on rat luteinizing hormone radioimmunoassay

Rat luteinizing hormone /LH/ was labelled with¹²⁵I by the Chloramine T method.¹²⁵I-LH, used as tracer in radioimmunoassay, was separated from the labelling reaction mixture by gel filtration. By using the proper protein/radioiodine ratio in the labelling reaction mixture the specific activity of¹²⁵I-LH was adjusted to 2.5–20.5 MBq g^–1. The influence of the specific activity on the assay parameters as well as on the tracer stability was investigated.     

New catalytic method for the synthesis of vitamins K

A new catalytic method for the synthesis of vitamins of the K family is suggested. In this method 2-methyl-1-naphthol is oxidized by dioxygen in the presence of Mo-V-P heteropoly acids or their salts in a two-phase system (organic solvent + water) to 2-methyl-1,4-naphthoquinone or vitamin K3, which is the precursor of all K family vitamins.     

Membrane filtration studies of aquatic humic substances and their metal species: a concise overview. Part 2. Evaluation of conditional stability constants by using ultrafiltration

The assessment of conditional stability constants of aquatic humic substance (HS) metal complexes is overviewed with special emphasis on the application of ultrafiltration methods. Fundamentals and limitations of stability functions in the case of macromolecular and polydisperse metal-HS species in aquatic environments are critically discussed. The review summarizes the advantages and application of ultrafiltration for metal-HS complexation studies, discusses the comparibility and reliability of stability constants. The potential of ultrafiltration procedures for characterizing the lability of metal-HS species is also stressed.     

Fermi resonances in the Raman spectra of alkali halide/BH4−

Raman spectra of a series of alkali-halide/BH^?₄ (and BD^?₄ crystals have been obtained. These spectra show some interesting examples of Fermi resonance type interactions between the stretching mode levels and overtone and combination band levels of the bending modes. Two resonances will be considered: (i) that between ν₁ and 2ν₄(A₁), and (ii) that between ν₃, 2ν₄ (F₂) and (ν₂+ν₄) (F₂).The F₂ resonance between ν₃, 2ν₄ and ν₂+ν₄ appears in the infrared spectrum and it has been studied on several occasions. However the equivalent Raman spectrum is of interest because the relative intensities of the bands are significantly different to those shown by the infrared spectrum.In the A₁ (and E) Raman spectrum of the stretching mode region there are two strong bands for each for the ¹⁰B and ¹¹B isotopes. The ν₁ would not be expected to show any ¹⁰B and ¹¹B splitting, but the observed bands are both closely resonating mixtures of ν₁ and 2ν₄(A₁). In fact the analysis shows that the stronger band has the higher proportion of 2ν₄ character, and the larger isotopic shift of the more intense band can then be seen to be reasonable.     

Role of ionic defects in photolysis of lithium hydride

Kinetic parameters of photoconductivity and dark conductivity of lithium hydride under uv irradiation have been investigated. A kinetic scheme of lithium hydride photolysis is suggested. Kinetic features of hydrogen evolution under uv irradiation of lithium hydride are explained. The contributions of radiation induced defects and equilibrium cation vacancies to processes leading to gas evolution under photolysis are determined.     

The molecular and electronic structure of the Mo12S24 macromolecule as a model of the active component of a hydrodesulfurization catalyst

The density functional theory (DFT) with the B3P86 hybrid exchange-correlation functional was used to calculate the molecular and electronic structure of the Mo₁₂S₂₄ macromolecule as a single MoS₂ layered structure slab. Calculations with geometry optimization are indicative of insignificant relaxation of the coordinatively unsaturated Mo and S atoms, which corresponds with the literature DFT data on the MoS₂ single slab obtained with periodic boundary conditions. The calculated forbidden band width (0.85–0.98 eV) is comparable with its experimental value (1.30 eV) and the results of DFT calculations of MoS₂ with periodic boundary conditions (0.89 eV). An analysis of the electronic state of the surface Mo centers in the Mo₁₂S₂₄ macromolecule showed that these centers were reduced to a greater degree than the Mo(IV) atoms in the bulk. The adsorption complex between the Mo₁₂S₂₄ macromolecule and six H₂S molecules was calculated to characterize the adsorption ability of the coordinatively unsaturated Mo centers. The structure and energy characteristics of the adsorption complex corresponded to weak donor-acceptor interaction between the π lone pair of H₂S and the surface (reduced) Mo centers. The suggestion was made that the active center of the catalytic cycle of thiophene hydrodesulfurization should induce the oxidative addition of H₂ followed by the occlusion of hydrogen into the MoS₂ matrix.     

Rapid analysis of dosage forms of some pharmaceuticals by nonaqueous thermometric titrimetry

The use of the technique of solution thermochemistry is proposed for the rapid assay for quality control and quality assurance of dosage amounts of some ethical formulations of some antimalarial drugs. The active ingredients are chloroquine, hydroxychloroquine, dapsone, proguanil hydrochloride, and pyrimethamine.Assay is done without the separation of the excipients and without isolation or derivatisation of the analytes. The titrations are done in glacial acetic acid and utilise the catalysed hydrolysis of acetic anhydride by perchloric acid to indicate the endpoint of the reactions.The time taken for a typical assay, of a typical dosage amount is about 3–5 minutes. The reproducibility is of the order of 1% for the milligramme amounts of analyte present in the dosage amounts of the drugs.

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Zusammenfassung Es wird die Anwendung eines lösungsthermochemischen Verfahrens zu Schnellbestimmungen bei der Qualitätskontrolle und — sicherung von Wirkstoffeinsatzmengen einiger rezeptpflichtiger Präparate von einigen antimalarischen Arzneimitteln empfohlen. Die aktiven Bestandteile sind Chloroquin, Hydroxychloroquin, Dapson, Proguanilhydrochlorid und Pyrimethamin.Die Bestimmungen werden ohne jegliche Abtrennung der Bindestoffe und ohne Isolierung oder Derivatisierung der zu bestimmenden Substanzen durchgeführt. Die Titrierungen werden in Eisessig durchgeführt und bedienen sich der katalytischen Hydrolyse von Essigsäureanhydrid durch Perchlorsäure als Endpunktindikation der Reaktion.Die Dauer für eine typische Probe bei einer typischen Wirkstoffmenge beträgt etwa 3–5 Minuten. Die Reproduzierbarkeit liegt in der Größenordnung von 1% für Milligrammengen der zu analysierenden Stoffe im Arzneimittel.

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We acknowledge the Nigerian Government for the provision of a grant to one of us (S.I.A.). We acknowledge the following for the gifts of samples of the authentic drugs and the tablets assayed in this work: Imperial Chemical Industries plc; May and Baker plc; Winthrop Laboratories plc; Wellcome Foundation (Medical Division).