Thermal analysis by EMF-measurements on solid electrolytes

Galvanic cells of the type (C+Cl₂)(NaCl_(s))(MCl_2(s))(C+Cl₂) give e. m. f. 's above 280°, which are due to the formation of ternary chlorides Na_nMCl_n+2. By the change in slope of continuously measured e.m.f.vs. T curves, the temperatures of solid-state reactions in systems NaCl-MCl₂ can be found. This method was applied for the systems of NaCl with NiCl₂, CoCl₂ and CdCl₂, and for KCl-NiCl₂. With the exception of the system NaCl-NiCl₂, all phase diagrams must be corrected.

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Zusammenfassung Mit galvanischen Zellen des Typs (C+Cl₂)/NaCl_(s)/MCl_2(s)/(C+Cl₂) lassen sich oberhalb 280° EMK's messen, die auf der Bildung ternärer Chloride Na_nMCl_n+2 beruhen. Durch die Änderung der Steigung kontinuierlich gemessener EMK- gegen T-Kurven lassen sich in Systemen NaCl/MCl₂ die Temperaturen von Festkörperreaktionen nachweisen. Diese Methode wurde auf die Systeme des NaCl mit NiCl₂, CoCl₂ und CdCl₂ sowie auf das System KCl-NiCl₂ angewendet. Alle Phasendiagramme, mit Ausnahme des Systems NaCl-NiCl₂, mußten auf Grund dieser Messungen revidiert werden.

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(C+Cl₂)/NaCl./MCl₂./(C +Cl₂) 280 °C . . , Na_nMCl_n+2. . . , NaCl-MCl₂. NaCl NiCl₂, CoCl₂, CdCl₂ KCl-NiCl₂. NaCl-NiCl₂,ce .

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This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

EMF-measurements with galvanic bromine cells in the systems RBr/MBr2 (M=Sr,Ba)

The systems RbBr/SrBr₂ and RbBr/BaBr₂ were reinvestigated by DTA and X-ray-crystallography. Additionally to the known compounds RbSrBr₃, RbSr₂Br₅ and RbBa₂Br₅, the phases Rb_2.23Sr_0.885Br₄ and Rb_2.13 Ba_0.935Br₄ were found, which are structural related to the Th₃ P₄ — type. By EMF-measurements the thermodynamic functions G, H and S were determined for all compounds.

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Zusammenfassung Die Systeme RbBr/SrBr₂ und RbBr/BaBr₂ wurden mittels DTA und Röntgenaufnahmen an Kristallpulvern neu untersucht. Zusätzlich zu den schon bekannten Verbindungen RbSrBr₃, RbSr₂Br₅ und RbBa₂Br₅ wurden die Phasen Rb_2,23Sr_0,885Br₄ und Rb_2,13Ba_0,935Br₄, die sich strukturell vom Th₃P₄-Typ ableiten lassen, neu gefunden. Für alle Verbindungen wurden durch EMK-Messungen in galvanischen Feststoffzellen die thermodynamischen Funktionen G, H und S bestimmt.

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RbBr/SrBr RbBBr/BaBr₂. RbSrBr₃, Rbsr₂Br₅ RbBa₂Br₅, Rb_2,23Sr_0,885Br₄ Rb_2,I3Ba_0,935Br₄, Th₃P₄. $ G, H S.

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This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.     

Indirect polarographic determination of phosmet O,O-Dimethyl-S-(phthalimidomethyl)dithiophosphate

Summary An indirect polarographic method for the determination of phosmet was elaborated. It is based on the fact that N-hydroxymethylphthalimide formed by the reaction of phosmet with sulphuric acid is polarographically active and exhibits a behaviour during electrolysis at a Hg dropping-electrode similar to that of phthalimide. The method has been applied to the determination of phosmet in apples. The sensitivity is 0.1 ppm.

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Indirekte polarographische Bestimmung von Phosmet O,O-Dimethyl-S-(phthalimidomethyl)dithiophosphat

Zusammenfassung Das Verfahren beruht darauf, daß N-Hydroxymethylphthalimid, das bei der Reaktion von Phosmet mit Schwefelsäure gebildet wird, polarographisch aktiv ist und sich bei der Elektrolyse mit der Quecksilber-Tropfelektrode ähnlich wie Phthalimid verhält. Die Methode wurde zur Bestimmung von Phosmet in Äpfeln angewandt. Die Empfindlichkeit beträgt 0,1 ppm.

     

Growth factors and gangliosides: a possible new perspective in neuronal growth control.

For many permanent cell lines the transition from a growing (P) to a resting (R) state is reversibly controlled by growth factors present in serum. This P-to-R transition was studied in a neuronal cell line (B104) with respect to the action of serum, dibutyryl cyclic AMP (DBcAMP), gangliosides, and a glioma cell-produced growth factor GGF. In this cell system gangliosides seem to act as differentiation and survival factors. The kinetics of uptake of radioactively labeled gangliosides and survival experiments both support the idea of the stable incorporation of exogenously added gangliosides into the cells. Based on the experimental evidence a new model of cell development is proposed. Thus in addition to the R or Go state, which in this cell system is rather unstable and probably regulated by cyclic nucleotides, we postulate a differentiated D state, which is controlled by gangliosides and which is characterized by its stability (survival time). This D compartment seems to be closer to the in vivo differentiated neuron than does the R or P state. tthe possible mechanisms for the action of gangliosides are discussed.     

Anomalous grazing incidence small-angle x-ray scattering studies of platinum nanoparticles formed by cluster deposition

The size evolution of platinum nanoparticles formed on a SiO2/Si(111) substrate as a function of the level of surface coverage with deposited clusters has been investigated. The anisotropic shapes of sub-nanometer-size nanoparticles are changed to isotropic on the amorphous substrate as their sizes increased. Using anomalous grazing incidence small-angle x-ray scattering (AGISAXS), the scattering from nanoparticles on the surface of a substrate is well separated from that of surface roughness and fluorescence. We show that AGISAXS is a very effective method to subtract the background and can provide unbiased information about particle sizes of less than 1 nm.