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  • Inorganic Chemistry  (765)
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  • 2015-2019
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  • 1978  (989)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 443 (1978), S. 11-18 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: TlPd3O4 and TlPt3O4 - Ternary Platinum Metal Oxides with Cluster StructureThe crystal structure of the cardinal red oxide TlPd3O4, prepared by the reaction of Pdo with TlNO3 or Tl2O3 at 550°C, has been determined on powder samples by X-ray and neutron diffraction. The structure of the cubic compound (a = 959.6(2) pm; space group Fm3m; Z = 8) contains square-planar PdO4 units which are joined to a three dimensional skeleton by triply bonding oxygen atoms. The cubic and rhombicuboctahedral spaces are occupied by TlIII and TlI cations so that the compound can be formulated as a mixed valency thallium(III)-thallium(I)-oxopalladate(II). The relationship with the structure of the platinum bronzes is discussed.The analogous ternary platinum oxide TlPt3O4 (a = 966.3(2)pm) has been obtained by thermal decomposition of Tl2Pt2O7.
    Notes: Die Kristallstruktur des durch Umsetzung von Pdo mit TlNO3 bzw. Tl2O3 bei 550°C erhaltenen kardinalroten Oxides TlPd3O4 wurde durch Röntgen-und Neutronenbeugung an Pulverproben aufgeklärt. In der Struktur der kubischen Verbindung (a = 959,6(2) pm; Raumgruppe Fm3m; Z = 8) sind quadratisch planare Pdo4- Baugruppen über dreibindige O- Atome zu einem dreidimensionalen Netz verknüpft. Die würfelförmigen und rhombendodekaedrischen Hohlräume des Gerüstes sind von TlIII-bzw. TlI-Kationen besetzt, so daß die Verbindung als valenzgemischtes Thallium (III)-thallium(I)-oxopalladat(II) formuliert werden kann. Die Verwandtschaftsverhältnisse zu den Strukturen der Platinbronzen werden diskutiert.Das entsprechende Oxoplatinat TlPt3O4 (a = 966,3(2) pm) konnte durch thermische Zersetzung von Tl2Pt2O7 erhalten werden.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1180-1194 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New 1,3,2,4-DiazadiphosphetidinesThe 1,3,2,4-diazadiphosphetidines 5a-f are easily prepared by the reaction of chlorobis(dialkylamino)phosphanes with sodium bis(trimethylsilyl)amide. Further oxidation reactions by O2, S8, N3Si(CH3)3, and alkyl halides are tested in detail in the case of 5a. As shown by NMR spectroscopy, 5a-f are obtained from synthesis almost exclusively as cis isomers which on thermal treatment form a mixture of cis and trans isomers. Methoiodide adducts 9a-f show this isomerisation as well.
    Notes: Die Reaktion von Chlorbis(dialkylamino)phosphanen mit Natrium-bis(trimethylsilyl)amid eröffnet einen bequemen Weg zu den 1,3,2,4-Diazadiphosphetidinen 5a-f, deren Erst- und Zweitoxidation durch O2,S8, N3Si(CH3)3 und Alkylhalogenide am Beispiel von 5a ausführlicher untersucht wird. 5a-f fallen bei der Darstellung fast ausschließlich als cis-Isomere an, die thermische Behandlung führt  -  wie NMR-spektroskopisch gezeigt wird  -  zu einem cis-trans-Isomerengemisch. Auch die Methoiodide 9a-f zeigen cis-trans-Isomerisierung.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1655-1658 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2,7-Azadiphosphepines  -  New Phosphorus and Nitrogen Containing Heterocycles1 reacts with 2 moles of 2 to give the bicyclic compound 3 containing the new 1,2,7-azadiphosphepine ring system. Diphosphinoamines 5 can be considered as three-membered segments of the eight-membered ring system 1. Thus the amines 5 react with 2 likewise to give monocyclic 1,2,7-azadiphosphepines 6.
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  • 4
    Publication Date: 1978-09-15
    Description: Injections of adrenocorticotropic hormone (ACTH) into the periaqueductal gray matter of drug-naive rats resulted in a dose-dependent opiate abstinence syndrome characterized by fearful hyperreactivity and explosive motor behavior. Injecting shorter chains of ACTH caused attenuated forms of this behavior. Injections of beta-endorphin at this same site caused opposite behavior: sedative, analgestic, and catatonic. If the effects of morphine are mediated by two classes of receptor) and the other which is not stereospecific and naloxone-insensitive--the endogtor)--and the other which is not stereospecific and naloxone-insensitive the endogenous ligand of the second receptor may be ACTH. The neuropeptides ACTH and endorphin may be part of an integrated neuromodulatory system, and the opiate abstinence syndrome may be the result of an altered interaction between the two receptor systems.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Jacquet, Y F -- New York, N.Y. -- Science. 1978 Sep 15;201(4360):1032-4.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/210506" target="_blank"〉PubMed〈/a〉
    Keywords: Adrenocorticotropic Hormone/administration & dosage/*pharmacology ; Animals ; Cerebral Aqueduct ; Cosyntropin/pharmacology ; Drug Interactions ; Endorphins/administration & dosage/*pharmacology ; Humans ; Injections ; Injections, Intraperitoneal ; Male ; Melanocyte-Stimulating Hormones/administration & dosage/pharmacology ; Morphine/administration & dosage/pharmacology ; Motor Activity/drug effects ; Naloxone/administration & dosage/pharmacology ; *Narcotics ; Rats ; Receptors, Opioid/drug effects ; Substance Withdrawal Syndrome/*chemically induced
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 445 (1978), S. 36-46 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of Lead Monohydrogentriphosphate, Pb2HP3O10By heating of Pb2P4O12 · 2 H2O at 150°C crystalline Pb2HP3O10 is formed topotactically. In these crystals amorphous H3PO4 is included. The monoclinic crystals are fourfold twinned. Space group: Cm; unit cell: a = 6.93 ± 0.01, b = 14.34 ± 0.01, c = 5.97 ± 0.01 Å, β = 135.1 ± 0.1°. The crystal structure was determined by heavy-atom method and refined by least-squares calculations. The P3O105- anion consists of three PO4 tetrahedra connected by common oxygen atoms. The chain has mirror symmetry across a plane passing the middle P atom. Lead is coordinated by eight oxygen atoms. The polyhedra of Pb are connected parallel y and z by common edges. Six P3O105- chains are joined by one lead ion.
    Notes: Beim Erhitzen von Pb2P4O12 · 2 H2O auf 150°C bildet sich topotaktisch kristallines Pb2HP3O10. In diesen Kristallen ist amorphes H3PO4 eingeschlossen. Die monoklinen Kristalle des Pb2HP3O10 sind vierfach verzwillingt. Raumgruppe: Cm; Gitterkonstanten: a = 6,93 ± 0,01, b = 14,34 ± 0,01, c = 5,97 ± 0,01 Å, β = 135,1± 0,1°. Die Kristallstruktur wurde nach der Schweratommethode bestimmt und mit Least-squares Verfahren verfeinert. Das Triphosphatanion, P3O105- besteht aus drei über gemeinsame Sauerstoffatome verknüpften PO4-Tetraedern und ist spiegelsymmetrisch bezüglich einer durch das mittlere P-Atom verlaufenden Ebene. Blei ist gegenüber Sauerstoff achtfach koordiniert. Die Polyeder des Pb sind parallel y und z über gemeinsame Kanten verbunden. Ein Bleikation verknüpft sechs P3O105--Ketten miteinander.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 445 (1978), S. 27-35 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of Lead Cyclotetraphosphate-2-Hydrate, Pb2P4O12 · 2H2OBy heating of Pb2P4O12 · 4 H2O crystals at 100°C, Pb2P4O12 · 2 H2O is formed topotactically. The triclinic crystals are twinned on (010). Space group: P1, unit cell: a = 8.02 ± 0.02, b = 10.58 ± 0.02, c = 7.53 ± 0.02 Å, α = 98.8 ± 0.2, β = 108.7 ± 0.2, γ = 82.6 ± 0.3°. The crystal structure was determined by Patterson and Fourier methods and refined by least-squares calculations. The structure consists of two crystallographically different P4O124- ring anions, point symmetry 1, connected by Pb and hydrogen bonds. Both Pb atoms are coordinated by eight oxygen atoms. The polyhedra of either Pb are interconnected by common edges forming sheets and chains. Pb(1) is joined with four, Pb(2) with five P4O124- anions.
    Notes: Beim Erhitzen von Kristallen des Pb2P4O12 · 4 H2O auf 100°C bildet sich topotaktisch Pb2P4O12· 2 H2O. Die triklinen Kristalle sind verzwillingt mit (010) als Zwillingsebene. Raumgruppe: P1; Gitterkonstanten: a = 8,02 ± 0,02, b = 10,58 ± 0,02, c = 7,53 ± 0,02 Å, α = 98,8 ± 0,2, β = 108,7 ± 0,2, γ = 82,6 ± 0,3°. Die Kristallstruktur wurde mit Patterson- und Fouriermethoden bestimmt und durch Least-squares-Rechnungen verfeinert. Die Struktur besteht aus zwei kristallographisch verschiedenen P4O124--Ringanionen mit der Punktsymmetrie 1, die über Pb und H-Brücken verknüpft sind. Die beiden Pb-Kationen sind jeweils achtfach gegenüber Sauerstoff koordiniert. Die Polyeder der beiden Pb sind über gemeinsame Kanten parallel der x- und z-Achse zu Schichten, bzw. parallel x zu Ketten verbunden. Pb(1) verbindet vier, Pb(2) fünf P4O124--Anionenringe miteinander.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 958-970 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N,N′-Bis(phosphino)(or arsino)-S,S-dialkylsulfodiimidesDesilylation reactions of N,N′-bis(trimethylsilyl)-S,S-dialkylsulfodiimides (1, 2) with chlorodiphenylphosphine yield the title compounds (9, 10), whereas with chlorodialkylphosphines only one trimethylsilyl group is eliminated. A second mol of chlorodialkylphosphine is added immediately to the primary product, yielding ionic materials with a phosphorus-phosphorus bond (4-8). With chlorodimethylarsine no reaction can be observed. From S,S-dialkylsulfodiimides (11, 12) and chlorodialkylphosphines(arsines) further N,N′-disubstituted derivates (13-20) are synthesized for the first time. Some chemical properties and the NMR spectra of the new compounds are described.
    Notes: Entsilylierungsreaktionen an N,N′-Bis(trimethylsilyl)-S,S-dialkylsulfodiimiden (1, 2) mit Chlordiphenylphosphin ergeben die Titelverbindungen (9, 10). Mit Chlordialkylphosphinen wird dagegen nur eine der beiden Trimethylsilylgruppen abgespalten, wobei zwei Chlordialkylphosphine unter Bildung salzartiger Produkte mit einer Phosphor-Phosphor-Bindung (4-8) addiert werden. Mit Chlordimethylarsin wird keine Reaktion beobachtet. Aus S,S-Dialkylsulfodiimiden (11, 12) und Chlordialkylphosphinen(arsinen) werden weitere N,N′-disubstituierte Derivate (13-20) erstmals hergestellt. Einige Eigenschaften sowie die NMR-Spektren der neuen Verbindungen werden beschrieben.
    Additional Material: 6 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 438 (1978), S. 206-212 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of N-Trimethylmetal(IVb) Trialkylphosphine Imines with Hydrogen HalidesInvestigations of the reaction of N-trimethylmetal(IVb)-substituted phosphine imines with hydrogen have been carried out. With one mole of HX phosphonium halides of the general formula [R3P—NH—MMe3]⊕X⊖ (R = CH3, C2H5; M = Si, Ge, Sn; X = Cl, Br, J) are obtained. A second mole of HX causes M—N bond cleavage, yielding aminophosphonium halides, [R3P—NH2]⊕X⊖.
    Notes: Die Reaktion von N-trimethylmetall(IVb)-substituierten Phosphiniminen mit Halogenwasserstoffen wurde untersucht. Mit einem Mol HX wurden Phosphoniumhalogenide der allgemeinen Formel [R3P—NH—MMe3]⊕X⊖ (R = CH3 C2H5; M = Si, Ge, Sn; X = Cl, Br, J) erhalten. Ein zweites Mol HX verursacht die Spaltung der N—M—Bindung, die zu Aminophosphoniumhalogeniden, [R3P—NH2]⊕X⊖, führt.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 447 (1978), S. 249-252 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Silicon-Sulphur Compounds. XXI. On the Nucleophilicity of SilanethiolsThe reaction of silanethiols (RO)3SiSH, (RO)2Si(SH)2, Ph3SiSH with alkyl halides was examined by means of conductometry in water-dioxane solution (1:4) and the nucleophilicity constants evaluated. The mechanism of this reaction was discussed.
    Notes: Die Reaktion der Silanthiole (RO)3SiSH, (RO)2Si(SH)2, Ph3SiSH mit Alkylhalogeniden wurde konduktometrisch in Wasser-Dioxan (1:4) verfolgt und die Nukleophilitätskonstanten bestimmt. Der Mechanismus dieser Reaktion wird diskutiert.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 3711-3718 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies upon the Racemisation of Cysteine-containing PeptidesThe thiosulfate derivatives of natural bovine insulin-A- and insulin-B chains and of several S-tritylcysteine peptides were hydrolysed and the degree of racemisation of the resulting amino acids was investigated by means of gas chromatography. It was found that those amino acids which are N-terminally linked to cysteine undergo racemisation to a high degree. GC-MS and UV spectroscopic investigations indicate that the racemisation occurs during hydrolysis and that it proceeds via a thiazoline derivative c. The method developed is generally applicable to the differentiation between D-enantiomers originally present in the sample and that formed by racemisation during hydrolysis.
    Notes: Die Thiosulfat-Derivate natürlicher Rinderinsulin-A- und Rinderinsulin-B-Ketten sowie einige S-Trityl-Cystein-Peptide wurden hydrolysiert und die Aminosäuren gaschromatographisch auf Racemisierung untersucht. Dabei zeigte sich, daß die jeweils an Cystein N-ständig gebundenen Aminosäuren ungewöhnlich hohe D-Anteile aufweisen. GC/MS-Experimente und UV-spektroskopische Untersuchungen weisen darauf hin, daß die Racemisierung unter den Hydrolysebedingungen erfolgt und über ein Thiazolin-Derivat c verläuft. Damit wurde eine Methode zur Unterscheidung der bei der Hydrolyse auftretenden D-Anteile von ursprünglich vorhandenen D-Enantiomeren-Anteilen erarbeitet.
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