Sulfanilamide-containing coordination compounds of Cu(II) with isatin and N-methylisatin thiosemicarbazones

Isatin (L¹) and N-methylisatin (L²) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf¹), N-acetylsulfanilamide (Sulfacyl, Sf²), Norsulfazole (Sf³), Aethazolum (Sf⁴), and Sulfadimesine (Sf⁵) to form coordination compounds Cu(Sf^1–5)L^1–2X₂ · nH₂O (X = Cl, Br; n = 2–5). All the complexes have a monomeric structure. Thiosemicarbazones L¹ and L² in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf^1–5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70–95°C) and complete decomposition (410–530°C).     

Structure of Charge Transfer Reaction Complexes Formed in Anionic Polymerization of Isoprene

A new mechanism is suggested for the anionic polymerization of isoprene. The key moment of this mechanism is thermal electron excitation of the complex of a living polymer with a monomer to the low lying S₁ (T₁) state involving a charge (electron) and (Li⁺) cation transfer from the terminal unit to the monomer molecule. It is stated that the probability of chemical bonding depends on the spin density on the radical centers of reactant molecules and on the geometry of the reaction complex. The semiempirical AM1 and ab initio 6-31G* quantum-chemical calculations revealed strong interaction for the ground electronic state of the complex (5-10 kcal/mole) and low energies of the excited triplet levels (<10 kcal/mole).     

Partial Saturated Vapor Pressure of Sodium Nitrite Over the System NaNO2-KNO3

The partial pressure of sodium nitrite in the system NaNO₂-KNO₃ was measured at 798, 823, and 848 K. The dependence of the logarithm of the NaNO₂ pressure on inverse temperature is presented. Coefficients A and B of the Clausius-Clapeyron equation and the partial molar heats of vaporization are calculated. The activity and activity coefficient of sodium nitrite are determined. The dependences of ac- tivity and activity coefficient of sodium nitrite and potassium nitrate are presented as functions of composition of the NaNO₂-KNO₃ system. The consistency of the activity coefficients is verified using the Redlich-Kister integral.     

Ductile-to-ductile transition in dispersely filled composites based on thermoplastic polymers

The fracture mechanism for rubber-filled composites based on gutta-percha, LDPE, medium-density PE, and rubber particles has been studied. An increase in the concentration of filler particles leads to a change in the stress-strain behavior of the composites from neck propagation to homogeneous plastic deformation. For the filled composites, the criterion for the ductile-to-ductile transition is the equality of yield and draw stresses. The critical concentration of rubber particles at the ductile-to-ductile transition is controlled by the ratio between the yield stress of matrix polymer and the neck propagation stress. Transition from neck propagation to homogeneous plastic flow of the material is accomplished under two conditions: the breaking strength of the polymer matrix should be higher than the yield stress, and stretching of the composite should not be accompanied by the formation of diamond cracks. The latter condition is fulfilled when the dimensions of rubber particles are below a certain critical value, which is determined by the ductility of the matrix.     

Titrimetric estimation of phosphate, molybdate, tungstate and sulphate with lead nitrate solution, using 1,2-naphthoquinone-2-semicarbazone-4-sulphonic acid (NQS-4S) and 1,2-naphthoquinone-2-thiosemicarbazone-4-sulphonic acid (NQTS-4S) as visual indicators

The use of 1,2-naphthoquinone-2-semicarbazone-4-sulphonic acid and 1,2-naphtho-quinone-2-thiosemicarbazone-4-sulphoic acid as indicators in the titrimetric estimation of phosphate, molybdate, tungstate and sulphate with lead has been examined. The precision, accuracy and applicability of the methods have been evaluated.     

Chemiluminescent determination of reactive hydrocarbons

Summary Chemiluminescent reactions of ozone with several classes of compounds at different temperatures are described. In a reaction chamber in front of a photomultiplier ozone is mixed with the compounds studied such as alkanes, olefins, alcohols, aromatics, C₂H₂, NO, vinyl chloride or H₂S. The chemiluminescent emission is proportional to the concentration of the compound involved. At room temperature only olefinic hydrocarbons respond but at temperatures above 150°C also a response for alkanes, alcohols, CO etc. is obtained. It is suggested that next to the ozonide-excited formaldehyde mechanism the CO-CO ₂ ^* mechanism is responsible for the chemiluminescent emission at high temperature. A detection limit of a few ppb is achieved. Possible applications are a selective gas-chromatographic detector, an air pollution monitor for instance for CO, and a photochemical reactivity monitor.

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Bestimmung reaktiver Kohlenwasserstoffe durch Chemiluminescenz

Zusammenfassung Chemiluminescenzreaktionen von Ozon mit verschiedenen Verbindungsgruppen (hauptsächlich Kohlenwasserstoffe) bei unterschiedlichen Temperaturen werden beschrieben. In einer Reaktionskammer werden die Verbindungen vor einem Photomultiplier mit Ozon vermischt. Es handelt sich u. a. um folgende Verbindungstypen: Alkane, Olefine, Alkohole, Aromaten, C₂H₂, NO, Vinylchlorid, H₂S. Die Emissionsintensität ist proportional der Konzentration. Bei Raumtemperatur sprechen nur Olefine an, die übrigen Verbindungen erst über 150°C. Die Emission bei höherer Temperatur wird neben der Bildung von Formaldehyd auf die Reaktion CO-CO ₂ ^* zurückgeführt. Die Nachweisgrenze beträgt wenige ppb. Als mögliche Anwendungsgebiete werden ein selektiver GC-Detektor, ein Monitor für Luftverunreinigungen (z.B. für CO) sowie ein Monitor zur Messung photochemischer Reaktivität der Luft genannt.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria.     

Reaction of dimethylamines with epimeric (at the 2 and 4 positions) trans-2-methyl- and trans-1,2-dimethyl-4-vinylethynyldecahydro-4-quinolols

A mixture of the corresponding 4-(4-dimethylamino-1,2-butadienyl)- and 4-(4-dimethylamino-1-butynyl)decahydro-4-quinolols, with predominance of the allene components, is formed from each vinylacetylenic alcohol as a result of the addition of diethylamine to epimeric (at the 2 and 4 positions) trans-2-methyl- and trans-1,2-dimethyl-4-vinylethynyldecahydro-4-quinolols. On the basis of the PMR spectra and data on the stabilities of allenic and acetylenic diamino alcohols under the conditions of their formation, it was concluded that the addition of dimethylamine to 4-vinylethynyldecahydro-4-quinolols proceeds simultaneously via two pathways — at the 1,4 and 3,4 positions of the vinylethynyl substituent.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 940–945, July, 1976.The authors thank A. S. Fridman and T. E. Prokof'ev for their participation in the discussion of the PMR spectra.     

Influence of ethanol oxidation rate on the lactate/pyruvate ratio and phosphorylation state of the liver in fed rats.

The effect of the ethanol oxidation rate on the interaction between the phosphorylation state (the [ATP]/[ADP] X [HPO4]2- ratio) and the redox state (the free [NAD+]/[NADH] ratio) of the liver cytosol was studied in intact fed rats. The rate of ethanol oxidation was inhibited to different degrees with pyrazole. The ethanol oxidation rate had no influence on the liver lactate level but correlated significantly with the pyruvate level. Accordingly, a significant correlation was also found between the ethanol oxidation rate and the lactate/pyruvate ratio. The rate of ethanol oxidation correlated significantly with the liver 3-phosphoglycerate level. No change in the glyceraldehyde-3-phosphate level was found. No correlation was found between the ethanol oxidation rate and the glyceraldehyde-3-phosphate/3-phosphoglycerate redox couple. Ethanol administration slightly increased the liver ATP level, but the simultaneous administration of pyrazole eliminated this effect. Other adenine nucleotides and HPO4 2- were not changed. The changes in the rate of ethanol oxidation had no effect on the phosphorylation state in the fed liver. It is assumed that in the fed liver the phosphorylation state is so well stabilized that the redox level has no influence.     

Relationship between the longitudinal relaxation rates of water protons and of well defined paramagnetic centers at low temperature in hydrated vermiculite

A good agreement has been observed between the proton longitudinal relaxation rate in the two and one layer hydrate of the Na-Llano vermiculite, the location of the Fe³⁺ paramagnetic centers within the octahedral and tetrahedral layers of the lattice and the electronic longitudinal relaxation rate using the dipolar electronic—proton spin interaction. The water content influences noticeably the electronic longitudinal relaxation time.