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21.
Prof. Dr. Hans Nowotny Josef Tomiska László Erdélyi Adolf Neckel 《Monatshefte für Chemie / Chemical Monthly》1977,108(1):7-19
By means of vapor pressure measurements using theTorker method (Torsion-Knudsen Effusion Recoil) as well as theKnudsen tanspiration technique in connection with a mass spectrometer, the heats of formation of the following compounds were found to be –6.5±0.7 kcal/g atom (Mn0.366Si0.634), –7.8±0.6 kcal/g atom (Mn0.50Si0.50), –7.3±0.6 kcal/g atom (Mn0.625Si0.375), and –6.6±0.6 kcal/g atom (Mn0.75Si0.25).
Mit 7 Abbildungen 相似文献
Mit 7 Abbildungen 相似文献
22.
Stará IG Alexandrová Z Teplý F Sehnal P Starý I Saman D Budesínský M Cvacka J 《Organic letters》2005,7(13):2547-2550
[reaction: see text] A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Co(I)-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents. 相似文献
23.
Previously unknown polyfluorocyclohexenyl, and acyclic perfluoroalkenyliodine tetrafluorides were prepared in high yields. Perfluorocyclohex-1-enyliodine tetrafluoride was obtained from pentafluoroiodobenzene using XeF2-NbF5 in aHF. The reaction of C6F5I with the weaker fluorooxidant XeF2-BF3 in 1,1,1,3,3-pentafluorobutane (PFB) yielded C6F5IF2, perfluorocyclohexa-1,4-dienyliodine difluoride, C6F5IF4, perfluorocyclohexa-1,4, and 1,3-dienyliodine tetrafluoride as intermediate products on parallel reaction routes. Both perfluoroalkenyl iodides, cis- and trans-(CF3)2CFCFCFI, reacted with XeF2-BF3 in PFB to give the corresponding perfluoroalkenyliodine tetrafluorides, cis- and trans-(CF3)2CFCFCFIF4. Even perfluoroalkyl iodides can be fluorinated by this reagent as was demonstrated by the preparation of C6F13IF4 from C6F13I. Generally, the CFCIFn fragment (n = 0, 2, or 4) in cyclic or acyclic perfluoroalkenyliodine compounds RFIFn did not undergo a transformation to the corresponding perfluoroalkyliodine compound. Furthermore, no perfluoroorganoiodine hexafluorides were detected in reactions with the fluorooxidant XeF2-aHF or BF3 or NbF5. 相似文献
24.
Application of multivariate curve resolution with alternating least squares (ALS) methods to second-order data from capillary electrophoresis diode array detector (CE-DAD) is shown. Second-order data are easily obtained by setting individual data matrix of CE run one in top of the other. Initial qualitative solutions obtained by evolving factor analysis can be further optimized by simultaneous analysis of multiple electrophoresis run data with ALS regression. Quantification is achieved by the comparison of the analyte peak areas with that of pure standards. During the ALS regression procedure, the following constraints were applied: (i) both concentrations and unit pure spectra of the resolved components must be positive; (ii) elution profiles have an unimodal shape; (iii) correspondence exists between common species in the different data matrices; (iv) the pure spectrum of each species is the same in all runs where it is present. The above methods were applied for the determination of dinitrotoluene (DNT) isomeric compounds in overlapping peaks from CE. 相似文献
25.
Jaroslav Stejskal Otakar QuadratIrina Sapurina Josef ZemekAlicja Drelinkiewicz Magdalena HasikIvo K?ivka Jan Prokeš 《European Polymer Journal》2002,38(4):631-637
Silica gel microspheres 7 and 15 μm in diameter were coated with an overlayer of polyaniline camphorsulfonate or hydrochloride during the oxidative polymerization of aniline. Coated silica gel and polyaniline precipitate were separated using a difference in sedimentation rate. In an alternative approach, the microspheres were modified with polyaniline in the presence of 35 nm colloidal silica. This technique prevented the macroscopic precipitation of polyaniline. Coatings of neat, 3-aminopropyl- and octadecyl-modified silica gel with polyaniline hydrochloride were compared. The surface composition of coated microspheres was characterized by X-ray photoelectron spectroscopy. Potential applications of particles in electrorheology, organic catalysis, and in modeling of conductivity behavior in composites are demonstrated. 相似文献
26.
Emmanouil Veroutis Steffen Merz Rüdiger-A. Eichel Josef Granwehr 《Chemphyschem》2022,23(1):e202100602
Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+[OAc]− in protic (D2O) and aprotic (DMSO-d6) solvents has been studied by means of concentration-dependent 1H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d6, the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent-shared ion pair (SIP) configuration was assigned. For [Ch]+[OAc]− in D2O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, 40 % of the cations in DMSO-d6 and 10 % in D2O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d6, both ions were found to be almost equally solvated, whereas in D2O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+[OAc]− in DMSO-d6, the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3–1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes. 相似文献
27.
Lead tetraacetate (LTA) oxidation of the allylic alcohols 1, 10, 14 and 19 leads to the formation of the epoxides 2, 11, 15 and 20 , products of a novel internal addition reaction of the electron deficient alcohol oxygen to the allylic double bond. In some cases ( 10, 14 ) the formation of a new type of acetoxylated enolethers ( 12, 16 ) is observed. The LTA oxidation of the allylic dienols 21 and 29 gives rise to the formation of the epoxyacetates 25 and 33 , products of a similar internal addition reaction. Furthermore, a variety of cyclization products ( 22, 23, 24, 26, 30, 31, 32 and 34 ) has been isolated whose formation requires an isomerisation of the allylic trans double bond to a cis one. 相似文献
28.
Zusammenfassung Eine Methode der Identifizierung von Alkyl- und Arylgruppen organischer Sulfide wurde ausgearbeitet, die die Spaltung dieser Stoffe mit Raney-Nickel zur gaschromatographischen Bestimmung der dabei entstandenen Kohlenwasserstoffe ausnützt.
Die Autoren danken den Kollegen Dr.M. Veea, Ing.J. Petránek und Ing.J. Gaspari für die Überlassung von Proben organischer Sulfide. 相似文献
Summary A method was developed for identifying alkyl- and aryl groups of organic sulfides. The method employs the cleavage of these materials with Raney nickel for the gas chromatographic determination of the resulting hydrocarbons.
Résumé On a mis au point une méthode d'identification des groupes alkylés et arylés des sulfures organiques exploitant la dissociation de ceux-ci par le nickel Raney pour le dosage par chromatographic en phase gazeuse des carbures d'hydrogène qui se forment.
Die Autoren danken den Kollegen Dr.M. Veea, Ing.J. Petránek und Ing.J. Gaspari für die Überlassung von Proben organischer Sulfide. 相似文献
29.
Marius Rebek Josef Schurz Walter Stöger Wolfgang Popp 《Monatshefte für Chemie / Chemical Monthly》1969,100(2):532-539
Zusammenfassung Die vorliegende Arbeit stellt eine Beschreibung von Experimenten dar, die die Erhöhung der Pfropfbereitschaft von trägen Komponenten durch Beimischung von aktiveren zum Ziele hatten.Das Trägermolekül war in allen Fällen Cellulose in Form von hochgradig gereinigtem Zellstoff. Durch die Verwendung von Mischsystemen aus Styrol und Methylmethacrylat gelang es, das trägere Styrol in bedeutend größerer Menge auf die Cellulose aufzupfropfen, als es bei Abwesenheit des aktiven Methylmethacrylats der Fall war.
Nach einem Vortrag, den der erstgenannte der Autoren im Rahmen der Arbeitstagung des Vereins Österreichischer Chemiker am 27. September 1968 in Wien gehalten hat. 相似文献
Grafting Polymerization of Cellulose with Two Vinyl Monomers
This paper describes experiments to increase the grafting of cellulose with components of poor reactivity by mixing them with highly reactive ones. A highly purified wood pulp was used as backbone. Using combinations of styrene and methyl methacrylate it was possible to graft considerably higher amounts of the poorly reacting styrene than in the absence of the highly reactive methyl methacrylate.
Nach einem Vortrag, den der erstgenannte der Autoren im Rahmen der Arbeitstagung des Vereins Österreichischer Chemiker am 27. September 1968 in Wien gehalten hat. 相似文献
30.
Kraus RM Lagoudakis PG Müller J Rogach AL Lupton JM Feldmann J Talapin DV Weller H 《The journal of physical chemistry. B》2005,109(39):18214-18217
We study the interplay between Auger effects and ionization processes in the limit of strong electronic confinement in core/shell CdSe/ZnS semiconductor nanocrystal quantum dots. Spectrally resolved fluorescence decay measurements reveal a monotonic increase of the photoluminescence decay rate on excitation density. Our results suggest that Auger recombination accelerates ionization processes that lead to the occupation of dark, nonemissive nanocrystal states. A model is proposed in the quantized Auger regime describing these experimental observations and providing an estimate of the Auger assisted ionization rates. 相似文献