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  • Molecular recognition  (1)
  • Na+ selectivity  (1)
  • molecular devices
  • Self-assembly
  • 1985-1989  (2)
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  • 1
    ISSN: 1432-1424
    Keywords: cryptand ; Na+ selectivity ; temperature ; ionizable mobile carrier ; nonactin ; cation transport kinetics ; lipid membrane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary The kinetics of Na+ and K+ transport across the membrane of large unilamellar vesicles (LUV) were determined at two pH's when transport was induced by (221)C10-cryptand (diaza-1,10-decyl-5-pentaoxa-4,7,13,16,21-bicyclo [8.8.5.] tricosane) at various temperatures, and by nonactin at 25°C and (222)C10-cryptand at 20 and 25°C. The rate of Na+ and K+ transport by (221)C10 saturated with the cation and carrier concentrations. Transport was noncooperative and exhibited selectivity for Na+ with respect to K+. The apparent affinity of (221)C10 for Na+ was higher and less pH-dependent than that for K+, and seven times higher than that of (222)C10 for K+ ions (20.5vs. 1.7 kcal·mole−). The efficiency of (221)C10 transport of Na+ was pH-and carrier concentration-dependent, and was similar to that of nonactin; its activation energy was similar to that for (222)C10 transport of K+ (35.5 and 29.7 kcal · mole−1, respectively). The reaction orders in cationn(S) and in carrierm(M), respectively, increased and decreased as the temperature rose, and were both independent of carrier or cation concentrations; in most cases they varied slightly with the pH.n(S) varied with the cation at pH 8.7 and with the carrier for Na+ transport only, whilem(M) always depended on the type of cation and carrier. Results are discussed in terms of the structural, physico-chemical and electrical characteristics of carriers and complexes.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0570-0833
    Keywords: Supramolecular chemistry ; Nobel lecture ; Macrocycles ; Molecular recognition ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Supramolecular chemistry is the chemistry of the intermolecular bond, covering the structures and functions of the entities formed by association of two or more chemical species. Molecular recognition in the supermolecules formed by receptor-substrate binding rests on the principles of molecular complementarity, as found in spherical and tetrahedral recognition, linear recognition by coreceptors, metalloreceptors, amphiphilic receptors, and anion coordination. Supramolecular catalysis by receptors bearing reactive groups effects bond cleavage reactions as well as synthetic bond formation via cocatalysis. Lipophilic receptor molecules act as selective carriers for various substrates and make it possible to set up coupled transport processes linked to electron and proton gradients or to light. Whereas endoreceptors bind substrates in molecular cavities by convergent interactions, exoreceptors rely on interactions between the surfaces of the receptor and the substrate; thus new types of receptors, such as the metallonucleates, may be designed. In combination with polymolecular assemblies, receptors, carriers, and catalysts may lead to molecular and supramolecular devices, defined as structurally organized and functionally integrated chemical systems built on supramolecular architectures. Their recognition, transfer, and transformation features are analyzed specifically from the point of view of molecular devices that would operate via photons, electrons, or ions, thus defining fields of molecular photonics, electronics, and ionics. Introduction of photosensitive groups yields photoactive receptors for the design of light-conversion and charge-separation centers. Redox-active polyolefinic chains represent molecular wires for electron transfer through membranes. Tubular mesophases formed by stacking of suitable macrocyclic receptors may lead to ion channels. Molecular self-assembling occurs with acyclic ligands that form complexes of double-helical structure. Such developments in molecular and supramolecular design and engineering open perspectives towards the realization of molecular photonic, electronic, and ionic devices that would perform highly selective recognition, reaction, and transfer operations for signal and information processing at the molecular level.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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