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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 16 (1987), S. 181-190 
    ISSN: 1572-8927
    Schlagwort(e): Crown ethers ; cryptands ; calorimetry ; potentiometry ; conductometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The formation of 1:1- and 2:1-complexes of the crown ether 12C4 with mono- and bivalent cations was studied in methanol solutions by calorimetric, potentiometric and conductometric titrations. It is shown that not all donor atoms of the ligand 12C4 take part in complex formation. The accuracy of the three experimental methods are checked by comparing the results for the complexation of alkali ions with crown ether 18C6.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 17 (1988), S. 277-286 
    ISSN: 1572-8927
    Schlagwort(e): Acetonitrile ; crown ethers ; glymes ; alkali metal ions ; calorimetric titrations ; potentiometric titrations ; complex formation ; ligand solvation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The complexation reactions of crown ethers with monovalent cations and Ba2+ were studied in acetonitrile solutions by means of calorimetric and potentiometric titration. The reaction enthalpies measured clearly demonstrate the influence of the interactions between 18-crown-6 and the acetonitrile solvent molecules. Changing the donor atoms or other substituents on the ligand molecule can exert a strong influence on the interactions with the solvent. Thus, all the reaction enthalpies measured for the reaction of 15-crown-5 with different cations are higher compared with 18-crown-6. On comparison with results in methanol, an approximate estimation is made of the influence of solvent molecules on the reaction enthalpies measured in acetonitrile. Due to the strong interaction between silver ion and acetonitrile, complex formation is only observed with crown ethers containing additional nitrogen or sulphur donor atoms.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1572-8927
    Schlagwort(e): Crown ethers ; benzocrown ethers ; non-charged complexes ; host-guest complexes ; calorimetric titration
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The formation of complexes between crown ethers and acetonitrile, chloroform, and nitromethane were investigated in carbon tetrachloride at 25°C. A significant influence of the ring size on the selectivity of the host is evident. The host 18-crown-6 forms complexes for which the reaction enthalpy and entropy are quite high. Host molecules with benzene side groups form complexes of lower reaction enthalpy and entropy and therefore the complexes formed are less stable than that of the analogous crown ethers without aromatic groups. Solvent effects on the stability constant K, the reaction enthalpy ΔH, and the reaction entropy ΔS were studied for the complexation of malonitrile by 18-crown-6. The reaction enthalpy and entropy values change in accordance with the dielectric constant of the solvent used, but no overall effect on complex stability with change in solvent dielectric constant was observed.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 23 (1995), S. 167-174 
    ISSN: 1573-1111
    Schlagwort(e): Amines ; amino acids ; liquid membrane ; macrocyclic ligands ; active transport
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The transport of some amines in protonated form was studied (viz. methylamine, dimethylamine, diethylamine andn-propylamine) and α-amino acids (l-leucine,l-methionine,l-isoleucine,l-phenylalanine,l-valine,l-α-alanine andl-cysteine). The following macrocyclic ligands were used as carriers throughout the experiments: 15-crown-5 (15C5), 18-crown-6 (18C6), benzo-18-crown-6 (B18C6), dibenzo-18-crown-6 (DB18C6), diazacrown ether [2.2] (1,7,10,16-tetraoxa-4,13-diazacyclooctadecane) and cryptand [2.2.2] (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane). The active transport, assisted by pH gradient, of amino acids and amines in protonated form as ion pairs in the presence of picrate anion was performed. The experiments suggested the influence of the ligand size, the donor atom type, and the substituents on the transport phenomena.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 7 (1989), S. 581-588 
    ISSN: 1573-1111
    Schlagwort(e): Crown ethers ; cryptands ; solvent influence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The reactions between alkali metal ions and crown ethers, aza crown ethers, and cryptands in propylene carbonate were studied by potentiometric and calorimetric titrations. The most stable complexes formed by macrocyclic and macrobicyclic ligands are when the ligand and cation dimensions are comparable. On comparing the complex stabilities of crown ethers and aza crown ethers of the same size, crown ethers were, on the whole, found to form the most stable complexes, with the exception of the lithium cation. Enthalpic factors are responsible. Substitution of the amino group protons of the aza crown ethers by benzyl groups leads to a high increase in values of the reaction enthalpy. This effect is partly compensated by entropic contributions. The bulky benzyl groups reduce the ligand solvent interactions and induce a ligand conformation with the lone pair of electrons from the nitrogen donor atoms which are more or less directed inside the cavity. The thermodynamic data for the transfer from methanol to propylene carbonate indicate that the ligands containing nitrogen show specific interactions with methanol.
    Materialart: Digitale Medien
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  • 6
    ISSN: 0003-3146
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: A new conception for modification of textile surfaces by permanent fixation of supramolecular components is explained. The principle of selective complexation is illustrated. Cyclodextrins, aza crown ethers, calixarenes, cyclotriveratrylenes and fullerenes are mainly suggested as suitable ligands for that procedure. The chemical structure and the complexation behaviour of the substances are described. Some surface properties which may be obtained with the ligands are especially emphasized.
    Notizen: Ein neues Konzept zur Modifizierung von Faseroberflächen durch permanente Fixierung supramolekularer Verbindungen wird vorgestellt, und das Prinzip der selektiven Komplexierung wird erklärt. Als für die Behandlung grundsätzlich geeignete Liganden werden insbesondere Cyclodextrine, Azakronenether, Calixarene, Cyclotriveratrylene und Fullerene hinsichtlich ihrer chemischen Struktur sowie ihrer komplexierenden Eigenschaften beschrieben. Einige erreichbare Oberflächeneffekte werden hervorgehoben.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2483-2485 
    ISSN: 0009-2940
    Schlagwort(e): Macrocyclic ligand ; Benzimidazolin-2-one ; Complexation ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Complex Formation of a New Macrocyclic Ligand Incorporating Three Benzimidazolin-2-one Units The new macrocyclic ligand 1 composed of three benzimidazolin-2-one-1,3-diyl and three propane-1,3-diyl building blocks has been synthesized. Complex formation constants in water involving Li+, Na+, K+, Mg2+ Ca2+, Si2+, and Ba2+ are discussed. The most stable complex is formed with Ca2+.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 8
    ISSN: 0009-2940
    Schlagwort(e): Carbocycles ; Homocalixarenes ; Calixarenes, Homo- ; Large rings ; Macrocycles ; [2n]Metacyclophanes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: all-Homocalixarenes: Carbocyclic Host Compounds with Intra- and Extraannular Ligand ArmsMethoxy-substituted [2n]metacyclophanes 1-10, obtained by Müller-Röscheisen cyclization, are converted into all-homocalixarenes 11-20 with free phenolic hydroxy functions. The well-soluble cyclic pentamer 11 and octamer 14 with endo-acidic host properties are investigated with regard to guest binding. They exhibit selectivity towards alkaline earth metal ions (Ba2+) in liquid/liquid extraction studies. Some of the macrocyclic oligophenols are transformed into homocalixarenes 21-25 with intra- or extraannular oxapropionate groups. The diester 22 and the tetraester 23 are converted into carbocycles 26 and 27 with two and four free oxapropionic acid groups. Complexation properties of the oligoesters in extraction studies and log K values in water are reported. X-ray structural analyses were performed of the [6]-, [8]- and [4]- homocalixarenes 9 and 21, 14 and 23; the inclusion of solvent molecules is proven.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 9
    ISSN: 0009-2940
    Schlagwort(e): Metallomacrocycles ; Nickel complexes ; Complexation reactions ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactions between alkali and alkaline earth metal ions and nickel(II) macrocycles based on S-alkylated isothiosemi-carbazides with different crown ether cavity size were studied in propylene carbonate by spectrophotometric and calorimetric titrations. Metallomacrocycles 1 and 2 exhibit normal behavior on 1:1 complexation with alkali- and alkaline earth metal ions and resemble in this respect 15C5 and 18C6, respectively. The most stable complexes are formed by these “ligands” when the diameter of the cation and the crown ether hole have approximately the same size. The most striking feature of the complexation processes studied is the formation of 1:2 metal-ligand associates even in the case of the smallest cations. These associates are very different from “normal” crown ether sandwich complexes. In reality, the particle formed is an associate between a 1:1 complex, in which the corresponding metal ion is well accommdated inside the ligand cavity, and a second metallomacrocyclic ligand. Their formation is disfavored by enthalpic contributions. A special kind of “switch” from these associates to normal sandwich complexes takes place in the case of 1, when the cation diameter compared to hole size increases. The macrocycle 2 forms this kind of associates with all akali and alkaline earth ions.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 4297-4302 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Complexation of AgI by Crown Ethers with Different Donor Atoms and Structural Varied Cryptands in MethanolThe complex stability of AgI with mono- and bicyclic ligands 1-6 was measured by potentiometric titrations in methanol. The reaction enthalpies were estimated by means of calorimetric titrations. All examined monocyclic ligands not only containing oxygen as donor atoms form - with one exception - more stable complexes than crown ethers. Ligands with a cavity too small for Ag+ ions are able to complex the cation with a ratio of ligand to cation of 2:1. Reducing the cavity size of cryptands by benzo anellands (4, 5) leads to a small decrease in complex stability. Other structural changes at the bicyclic ligands do not influence the complex formation.
    Notizen: Die Komplexstabilität von AgI mit mono- und bicyclischen Liganden 1-6 wurde durch potentiometrische Titrationen in Methanol gemessen. Mit Hilfe kalorimetrischer Titrationen wurden die Reaktionsenthalpien bestimmt. Alle monocyclischen Liganden, die neben Stickstoff auch Sauerstoff und Schwefel als Donoratome enthalten, bildeten - mit einer Ausnahme - stabilere Komplexe als reine Kronenether. Liganden, deren Durchmesser kleiner ist als der von Ag+, sind in der Lage Komplexe zu bilden, deren Zusammensetzung Ligand zu Kation 2:1 ist. Die Verkleinerung des Hohlraumes der Kryptanden durch Benzo-Anellanden (4,5) führt nur zu einer kleinen Abnahme der Komplexstabilität. Andere strukturelle Veränderungen an den bicyclischen Liganden beeinflussen die Komplexbildung nicht.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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