Steroid glycosides from the starfishEchinaster sepositus

Two new steroid glycosides, which have been called echinasterosides B₁ and B₂ have been isolated from the starfishEchinaster sepositus. Using chemical transformations (methylation, hydrolysis) and also spectral methods (¹H and¹³C NMR spectroscopy and GLC-MS) the complete chemical structure of B₁ has been established as 15-acetoxy-5-cholestane-3,4,6,8,24-pentaol 24-O[O-(2)O÷ methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (I) and that of glycoside B₂ as 5-cholestane-3,4,6,8,15,24-hexaol 24-O-[O÷(2-O-methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (II).Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Pirodnykh Soedinenii, No. 2, pp. 246–249, March–April, 1987.     

Controlled-potential coulometric studies on fluoride and sulphate complexes of neptunium (VI)

Fluoride and sulphate complexing of Np(VI) has been studied by controlled-potential coulometry at a constant ionic strength. The values of ₁ ^* and ₂ ^* for fluoride complexes were found to be 9.4 and 8.9, respectively, at an ionic strength =0.5. At an ionic strength =1.0, ₁ ^* and ₂ ^* obtained were 6.6 and 10.5, respectively. Sulphate complexing of Np(VI) was studied only at an ionic strength =0.5. The value of ₁ ^* obtained was 5.6.     

Effect of molybdenum catalysis on the perborate-bromide reaction. Kinetics and mechanism and some theoretical considerations

In the presence of molybdenum, both the uncatalyzed and the catalyzed reactions proceed simultaneously. An equation for k_cat was derived and the effect of temperature was described through a temperature function F(T) by the use of the Arrhenius-Eyring equation. A plausible mechanism is postulated and the theoretical background given for the analytical application of molybdenum.

---

. k_cat, -. .

     

Microcalorimetric and FT-IR spectroscopic study of benzene adsorption on α-Fe2O3 and γ-Al2O3

The adsorption of benzene at room temperature on-Fe₂O₃ and on-Al₂O₃ powders was investigated by heat-flow microcalorimetry and FT-IR spectroscopy.On iron oxide a chemisorption-combustion step is followed by a highly exothermic adsorption step, reversible at r.t.Few combustion centres exist on alumina if reducing pretreatment is not carried out. Two reversible adsorption steps are subsequently observed and were interpreted as due to interaction with two different types of surface hydroxy groups.

---

Zusammenfassung Die Adsorption von Benzol an-Fe₂O₃- und-Al₂O₃-Pulvern bei Raumtemperatur wurde mittels Wärmefluß-Kalorimetrie und FT-IR-Spektroskopie untersucht. Beim Eisenoxid folgt auf dem Chemisorptions-Verbrennungs-Schritt ein bei Raumtemperatur reversibler, stark exothermer Adsorptionsschritt. Aluminiumoxid besitzt einige Oxydationszentren, sofern keine reduzierende Vorbehandlung erfolgt. Zwei aufeinanderfolgende reversible Adsorptionsschritte treten auf und werden der Wechselwirkung mit zwei verschiedenen Typen von Oberflächenhydroxylgruppen zugeschrieben.

---

-Fe₂O₃ -l₂₃. - , . , , . , .

---

---

This work was supported by the CNR Progetto Finalizzato Chimica Fine e Secondaria. Prof. Vincenzo Lorenzelli is gratefully thanked for the kind loan of instrumental facilities and helpful discussions.     

Transient phenomena in o-xylene oxidation in a fluidized bed reactor

The effect of stirring a vanadium-titanium-tellurium catalyst on the yield of the selective oxidation products for oxidation of o-xylene in fluidized bed reactors has been studied. It is shown that the stirring of catalyst pellets increases the yield of phthalic anhydride.

---

-- - . , .

     

Studies on catalytically active surface compounds, VIII. On the reaction of VCl4 with aerosil

The preparation and hydrolysis of silica supported vanadium catalysts have been investigated using VCl₄ as a paramagnetic probe. Chemical analysis shows the possibility of the VCl₄ molecule to react one, two, or three hydroxy groups of the surface. The type of reaction is influenced by the temperature of pretreatment of aerosil (TPA). ESR measurements show distortions of the tetrahedral coordination of the (SiO)_nVCl_4–n surface complex, which is strongest for the threefold attachment (n=3) of VCl₄ to the surface. Hydrolysis is accompanied by an increase of the coordination number and leads to highly mobile vanadium species.

---

, VCl₄ . , VCl₄ , . . (SiO)_nVCl_4–n, VCl₄ (n=3). .

     

Complexes of O2? radical ions with palladium and platinum compounds in solutions

Coordination of O ₂ ^– radical ions with palladium and platinum compounds in solutions has been detected by the ESR technique.

---

- O ₂ ^– .

     

Oxidation stability of crosslinked polyethylene. Isothermal DTA method

Isothermal differential thermal analysis has been used to study the thermooxidative stability of two grades of crosslinked polyethylene in the temperature range from 120°C to 230°C. Induction times of thermooxidative degradation were measured from 2 minutes up to 3590 hours. Oxidation Induction time and mechanical failure in oven ageing experiments coincided over the measured temperature range. The degree of crosslinking was not strongly affected by the oxidative reaction. The Arrhenius-plots of DTA results showed curvature at 150°C, so straight line extrapolations from short-term experiments at elevated temperatures to low temperatures and long times are not possible. Thermoanalytically measured residual thermooxidative stability decreased linearly with ageing time and showed great scattering of the results.

---

Zusammenfassung Die isotherme Differentialthermoanalyse ist als Methode zur Abschätzung der thermooxidativen Beständigkeit von Polyolefinen seit längerem bekannt. In der vorliegenden Arbeit wird über isotherme DTA-Messungen an Proben aus vernetztem Polyäthylen im Temperaturbereich von 230°C bis 120°C berichtet, wobei Oxidationsinduktionszeiten bis zu 3590 Stunden gemessen wurden. Die Auftragung der Oxidationsinduktionszeiten in Arrhenius-Diagrammen zeigte für vernetztes Polyäthylen keine für Extrapolationszwecke geeignete Linearität des Logarithmus der Oxidationsinduktionszeiten über der reziproken absoluten Temperatur über weitere Bereiche der Meßzeiten bzw. Prüftemperaturen. Die thermoanalytisch bestimmten Oxidationsinduktionszeiten stimmten mit dem Steilabfall der Reißdehnung in Ofenalterungsversuchen überein während der über den Gelgehalt ermittelte Vernetzungsgrad vom thermooxidativen Abbau nicht signifikant beeinflußt wurde. Somit können aufwendige Ofenalterungsversuche durch experimentell einfache isotherme DTA-Versuche ersetzt werden. Die Messung der thermooxidativen Restbeständigkeit im isothermen DTA-Versuch bei erhöhter Prüftemperatur ermöglicht einen wesentlich deutlicheren Einblick in den thermooxidativen Schädigungszustand eines Polyolefins während der Induktionsperiode des thermooxidativen Abbaus als die Messungen des Vernetzungsgrades oder der Reißdehnung. Die Abnahme der thermooxidativen Restbeständigkeit erfolgt im Fall des vernetzten Polyäthylen in allen Fällen linear über der Alterungszeit.

---

120–230°. 2 3590 . . . 150°, . .

     

X-ray diffraction study of palladium catalysts. Influence of the preparation method on the dispersity of metallic phase

Influence of different methods of catalyst preparation on their phase composition and the crystallite dispersity has been demonstrated.

---

.

     

Acidity and aniline alkylation activity of oxides and supported vanadia oxides

Aniline alkylation activity of simple oxides and supported vanadia oxides are compared from the point of view of acidity and vanadia-support interaction.

---

.

---

---

IICT communication No. 2915     

Oxidative dehydrogenation of ethylbenzene of Fe?Sb?O catalysts

The conversion and selectivity to styrene in the oxidative dehydrogenation of EtPh at 800 K has been foudn to depend on the x=[Sb]/[Sb]+[Fe] ratio in the catalyst, being the highest at x0.8. The observed increase in specific catalytic activity is probably caused by the formation of a solid solution of FeSb₂O₆ in the catalyst.

---

800°, x[Sb]/[Sb]+[Fe] . x=0,8. FeSb₂O₆ .

     

Kinetic parameters of the thermal decompositions of nitritonickelates(II)

Kinetic parameters of thermal decomposition of compounds of general formulaM ₂ ^I M ^II[Ni(NO₂)₆], whereM ^I= K⁺, Rb⁺ or Cs⁺ andM ^II= Ca²⁺, Sr²⁺ or Ba²⁺, were investigated on the basis of the respective thermal curves. Calculations of the reaction order and activation energy carried out by the Coats-Redfern method and by Doyle's method (modified by Zsakó) gave similar results, The reaction order is 2 for all the compounds investigated. In the group of potassium salts the activation energy increases fromM ^II=Ca²⁺ toM ^II=Ba²⁺. In the groups of rubidium and caesium salts, the lowest activation energy is observed whenM ^II=Sr²⁺. Such behaviour of the nitritonickelates is explained in terms of structures and the principle of maximum density.

---

Zusammenfassung Die kinetischen Parameter der thermischen Zersetzung von Verbindungen der allgemeinen FormelM ₂ ^I M ^II [Ni(NO₂)₆] (M ^I= K⁺, Rb⁺ oder Cs⁺ und M^II = =Ca²⁺, Sr²⁺ oder Ba²⁺) wurden auf Grund der entsprechenden thermischen Kurven untersucht. Die an Hand der Coats-Redfern Methode und der durch Zsakó modifizierten Doyleschen Methode durchgeführten Berechnungen der Reaktionsordnung und der Aktivierungsenergie ergaben ähnliche Resultate. Die Reaktionsordnung ist 2 für sämtliche untersuchten Verbindungen. In der Gruppe der Kaliumsalze steigt die Aktivierungsenergie vonM ^II=Ca²⁺ in RichtungM ^II=Ba²⁺ an. In der Gruppe der Rubidium- und Caesiumsalze wird die niedrigste Aktivierungsenergie beiM ^II=Sr²⁺ beobachtet. Dieses Verhalten der Nitritonickelate wird durch die Strukturen und das Prinzip der maximalen Dichte erklärt.

---

₁ ^{2 II}[Ni(NO₂)₆], ^I= ⁺, Rb⁺Cs⁺,a ^II= ²⁺,8r²⁺²⁺. , - ( ), . 2. ^{+ 2+}. ^II=S²⁺. .

     

Effect of acid treatment on the properties of an activated carbon

The enhancement of the activity of a carbon treated with HF is due to the drastic diminution of its inorganic impurities, which produces an increase of the surface area of the carbon, a stronger Pt-C interaction and a higher Pt dispersity.

---

, HF, , , Pt-C Pt.

     

First experiments on transmutation studies of129I and237Np using relativistic protons of 3.7 GeV

First experiments on the transmutation of long-lived¹²⁹I and²³⁷Np using relativistic protons of 3.7 GeV are described. Relativistic protons generate in extended Pb-targets substancial neutron fluences. These neutrons get moderated in paraffin and are used for transmutation as follows:¹²⁹I(n,)¹³⁰I and²³⁷Np(n,)²³⁸Np. The isotopes¹³⁰I (T _1/2-12.36 h) and²³⁸Np (T _1/2=2.117 d) were identified radiochemically. One can estimate the transmutation cross-section (n,) in the given neutron field as (¹²⁹I(n,))=(10±2)b and (²³⁷Np(n,))=(140±30)b The experiments were carried out in November 1996 at the Synchrophasotron, LHE, Dubna, Russia. The investigation has been performed at the Laboratory of High Energies, JINR, Dubna.     

Selectivity of decomposition of highly excited polyatomic molecules

An expression for the relative product yield has been derived on the basis of a simplified non-RRK model of two-channel decomposition of highly vibrationally excited polyatomic molecules. The selectivity of the reaction can be noticeably different from RRK prediction even in the cases where the rate of intramolecular energy redistribution is of the order of 10¹¹–10¹²s^–1.

---

, -RRK , . ; , , , RRK.

     

On the interpretation of differences in mechanisms, kinetics and dynamics of oxidation reactions on metal and oxide catalysts

Langmuir-Hinshelwood type mechanisms with competitive adsorption are suggested to be more typical for metal catalysts, since, unlike on oxide systems, oxidizable substance and molecular oxygen can be adsorbed on the same (reduced) active sites. Therefore, multiple steady states and critical phenomena are more characteristic for catalysis on metals.

---

, - , , () . .

     

The oxygenolysis of 9,10-phenanthrenequinone to copper(II) diphenato complexes by CuX (X=Cl, Br) complexes containing pyridine type ligands

The oxygen dependent cleavage of 9, 10-phenanthrenequinone by CuX (X=Cl, Br) with py, dipy, and phen ligands to well define copper(II) diphenato complexes and evidence for the intermediate Cu–O₂ complexes containing Cu^II and Cu^I are reported.

---

9,10- CuX (X=Cl, Br) py, dipy phen (II), , , Cu–O₂, Cu^II Cu^I.

     

Influence of mechanical activation on decomposition of a chalcopyrite-pyrite mixture in an oxidizing atmosphere

The influence of the addition of pyrite and mechanical activation on an oxidative decomposition of chalcopyrite was studied. The course of the thermoanalytical curves and X-ray identification of the products showed that addition of pyrite affects mainly the endothermic processes taking place in region of low temperatures but does not significantly influence the temperature of CuSO₄ formation and its content in the products of decomposition. Changes in fine and superfine structure of chalcopyrite brought about by mechanical activation at grinding cause the complex of exothermic oxidative reactions to proceed at temperatures as much as 180 deg lower than for a non activated sample. The endothermic effect of these oxidation reactions become more marked and the proportion of CuSO₄ in the products of the oxidative decomposition increases significantly.

---

Zusammenfassung Am oxidativen Zerfall von Chalkopyrit wurde der Einfluss der Zugabe von Pyrit sowie der mechanischen Aktivierung untersucht. Der Verlauf der thermoanalytischen Kurven und Röntgendiffraktionsanalyse der Produkte zeigten, dass die Zugabe von Pyrit hauptsächlich die sich bei niedrigeren Temperaturen abspielenden endothermen Prozesse beeinflusst, nicht aber die Bildungstemperatur von CuSO₄ sowie dessen Gehalt in den Zersetzungsprodukten. Durch mechanisches Aktivieren mittels Feinmahlen hervorgerufene Veränderungen in der Fein- und Superfeinstruktur lassen die Gesamtheit der exothermen oxidativen Reaktionen bei Temperaturen ablaufen, die etwa 180 Grad unterhalb derer für unaktivierte Proben liegen. Die endotherme Färbung dieser Oxidation wird eindeutiger und der Anteil von CuSO₄ in den Produkten des oxidativen Zerfalles nimmt eindeutig zu.

---

. , . , , - , 180° , . - .

     

A thermoanalytical study of treated wools

Previous studies of fibrous keratins have enabled assignments to be proposed for the endothermic processes identified in the relatively complex DTA curve. From this base, the influence of well defined chemical modifications to keratin on their observed DTA curves has been discussed. Wools are specifically treated commercially to improve shrink resistance and machine washability. To achieve these desired characteristics wools are treated, (a) by special oxidative processes, (b) with specific polymers, and (c) by combinations of (a) and (b). The DTA curves of wool samples which have been subjected to each of the three different treatments were reproducibly recorded. The significance of differences between these curves and that for the untreated fibre are discussed. Although characteristic differences in the DTA curves of wools after specific treatments can be distinguished, differential thermal analysis cannot be regarded as a general tool for such treatment characterisation. It is considered that thermogravimetry should offer a greater potential for this purpose.

---

Zusammenfassung Vorangegangene Untersuchungen über faserige Keratine ermöglichten Zuordnungsvorschläge für die in der verhältnismässig komplexen DTA-Kurve befindlichen endothermen Vorgänge. Auf dieser Basis wurde der Einfluss gut definierter chemischer Veränderungen in Richtung Keratin auf ihre beobachteten DTA-Kurven erörtert. Die Wollen werden im Handelsmaßstab spezifisch behandelt um ihre Widerstandsfähigkeit gegenüber dem Eingehen zu erhöhen und ihre Waschbarkeit in der Maschine zu fördern. Um diese erwünschten Charakteristika zu erreichen werden die Wollen a) durch spezielle Oxidationsvorgänge, b) mittels spezifischer Polymere und c) mit kombinierten Verfahren von a) und b) behandelt. Die DTA-Kurven von jedem dieser drei verschiedenen Behandlungen unterworfenen Wollproben wurden reproduzierbar aufgezeichnet. Die Signifikanz der Unterschiede dieser Kurven gegenüber denen der unbehandelten Fasern wird erörtert. Obwohl sich charakteristische Unterschiede in den DTA-Kurven der spezifisch behandelten Wollen beobachten lassen, kann die Differentialthermoanalyse nicht als ein allgemein anwendbares Verfahren zur Charakterisierung solcher Behandlungen betrachtet werden. Es wird angenommen, dass die Thermogravimetrie für diesen Zweck grössere Möglichkeiten bietet.

---

Résumé Des études antérieures sur les kératines fibreuses ont permis de proposer des interprétations sur les effects endothermiques identifiés sur la courbe ATD relativement complexe. Sur cette base, l'influence de modifications chimiques bien définies de la kératine sur les courbes ATD observées est discutée. Les laines, à l'échelle commerciale, sont traitées spécifiquement pour augmenter leur résistance au rétrécissement ainsi que pour améliorer leur faculté de lavage en machine. Afin d'atteindre ces caractéristiques, elles sont traitées soit par des procédés oxydants spéciaux, soit par des polymères spécifiques soit par les deux. Les courbes ATD d'échantillons de laines traitées par chacune de ces méthodes ont été enregistrées de façon reproductible. Les différences observées entre les courbes obtenues avec les fibres traitées et non traitées sont discutées. Malgré des différences caractéristiques, l'analyse thermique différentielle ne peut pas être considérée comme une méthode universelle pour caractériser de tels traitements. La thermogravimétrie pourrait être potentiellement plus adaptée.

---

, DTA. , DTA. , , . : ) , ) ) ) ). DTA , . . DTA , . , .

---

---

Paper presented at the 1^st ESTA, Salford U.K.

---

We wish to thank Precision Processes (Textiles) Ltd., and the International Wool Secretariat for samples and information. Their co-operation is gratefully acknowledged. One of us (WMF) wishes to record her thanks to the I.W.S. for their support of a research studentship.