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  • sodium-23 NMR  (4)
  • potentiometry  (3)
  • Monensin  (2)
  • 1
    ISSN: 1572-8927
    Schlagwort(e): N-methylformamide ; nonaqueous solvents ; preferential solvation ; isosolvation point ; sodium-23 NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Sodium-23 NMR chemical shifts and linewidths have been measured for 0.1M NaClO4 in binary mixtures of N-methylformamide (NMF) with a series of other solvents, as a function of the solvent mole fraction. The relative solvent composition at the isosolvation point, the mid-value of the Na-23 chemical shift between those measured in the respective pure solvents, reveals preferential solvation of the sodium cation in many cases. The isosolvation composition correlates well with the relative solvating abilities of the two solvents-as characterized by their donicities-provided that the cation-solvent interactions are of the ‘hard-hard’ type and that they are not complicated by interionic interactions. The variation in the electric field gradient around the sodium nucleus, as the composition of the solvent changes, results in broadening of the resonance line. Maximum broadening occurs close to the solvent mole fraction corresponding to the isosolvation point.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 7 (1978), S. 357-372 
    ISSN: 1572-8927
    Schlagwort(e): Monensin ; antibiotic ionophores ; alkali complexes ; thallium(l) complex ; Silver(l) complex ; stability constants ; entropy of complexation ; enthalpy of complexation ; nonaqueous solvents ; potentiometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Potentiometric and cyclo-voltammetric studies have been carried out on monensin anion (Mon−) complexes with the alkali ions as well as with Tl+ and Ag+ in absolute methanol solutions. The log Kf values obtained for the complexity constants and corrected for the activity effects are: Li+, 3.3±0.1; Na+, 6.72±0.05; K+, 5.18±0.05; Rb+, 4.58±0.05; Cs+, 3.75±0.05; Tl+, 5.31±0.05; Ag+, 8.2±0.2. It is seen that for the alkali, the most stable complex is formed with Na+. The enthalpy and entropy of complexation with the sodium ion were found to be ΔHo=−5.47±0.24 kcal-mole−1 and ΔSo=+12.4±0.7 e.u. The complex, therefore, is enthalpy and entropy stabilized.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 8 (1979), S. 83-95 
    ISSN: 1572-8927
    Schlagwort(e): Monensin ; alkali metal complex ; silver complex ; thallium complex ; potentiometry ; enthalpy of complexation ; entropy of complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The acid-base and complexing properties of a naturally occurring antibiotic ionophore-monensin (MonH)-were studied in anhydrous methanol solutions primarily by potentiometric measurements. The pK a of the acid was found to be 10.30±0.05 at 25°C. Complexes of silver, thallium, and alkali ions with the undissociated ligand were also studied, and their stability constants were determined. The acid dissociation constant of MonH as well as the stability constants of Mon− Na+ and MonH·NaClO4 complexes were determined in the 5–45°C temperature range, and the enthalpy and entropy of the acidity and stability constants were determined from van't Hoff's plots. The formation of MonH and Mon−Na+ species are both enthalpy and entropy stabilized, but the formation of the MonH·NaClO4 complex is enthalpy stabilized but entropy destabilized.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 10 (1981), S. 523-532 
    ISSN: 1572-8927
    Schlagwort(e): phosphonocarboxylic acids ; phosphonoacetic acid ; calcium and magnesium complexes ; enthalpy and entropy complexation ; potentiometry ; cyclic voltammetry ; herpes virus
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The concentration formation constants of phosphonoacetic acid (PAA) complexes with the Ca2+ and Mg2+ ions were determined in aqueous solution at 25°C by potentiometric and coulometric titrations at different ionic strengths and were extrapolated to I=0 in order to obtain thermodynamic values of the formation constants. Complexes were formed by the completely deprotonated K f (ML) and monoprotonated K f (MHL) forms of the PAA anion. The respective values for the complexes are: log K f (CaL)=4.68±0.03, log K f (CaHL)=2.61±0.08; log K f (MgL)=5.58±0.09, log K f (MgHL)=3.0±0.3. The enthalpy and entropy of complexation for the deprotonated Ca2+ and Mg2+ PAA species, determined from the temperature dependence of the log K f (ML), are: ΔH0(Ca) =0.6±0.2 kcal-mol−1, ΔS0(Ca)=21.4±0.6 cal-mol−1-K−1, ΔH0(Mg)=3.0±0.7 kcal-mol−1, and ΔS0(Mg)=35±2 cal-mol−1-K−1. It is seen there-fore, that the complexes are entropy stabilized but enthalpy destabilized. Formation constants were also determined for Ca2+ and Mg2+ complexes with PAA analogs, phosphonoformic and 3-phosphonopropionic acids and the complexation of PAA was also studied at a single ionic strength, with Na+, Ag+, Tl+, Sr2+, Ba2+, Cd2+, Cu2+, and Pb2+ ions.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 6 (1977), S. 299-307 
    ISSN: 1572-8927
    Schlagwort(e): Lithium-7 NMR ; sodium-23 NMR ; cesium-133 NMR ; far infrared ; alkali complexes ; cryptates ; formation constants ; nonaqueous solvents ; membranes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Nuclear magnetic resonances of alkali nuclei,7Li,23Na, and133Cs, as well as far infrared measurements are used to study alkali complexes of a bicyclic diazapolyoxa ligand—the dilactam of cryptand C222. Measurements were carried out in pyridine, tetrahydrofuran, acetonitrile, nitromethane, dimethylformamide, and aqueous solutions. The complexing ability of the dilactam is similar to, but weaker than, that of the cryptand C222. The limiting chemical shifts of the complexed cations were solvent-dependent, indicating incomplete enclosure of the cation by the ligand. Formation constants of Li+ and Cs+ complexes were calculated from the chemical-shift dependence on the ligand/metal ion mole ratio.
    Materialart: Digitale Medien
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  • 6
    ISSN: 1572-8927
    Schlagwort(e): Crown ethers ; sodium-23 NMR ; cesium-133 NMR ; thallium-205 NMR ; nonaqueous solvents ; enthalpy of complexation ; entropy of complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Formation constants for complexes of dibenzo-21-crown-7, dibenzo-24-crown-8 and dibenzo-27-crown-9 with the Na+, Cs+ and Tl+ ions have been determined by multinuclear NMR measurements in several nonaqueous solvents. The measurements of the cesium complexes were carried out at different temperatures and the enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The stabilities of these complexes in solvents of low to medium donicity, —nitromethane, acetonitrile, acetone, methanol, and propylene carbonate, vary in the order Tl+〉Cs+〉Na+. Depending on the relative sizes of the cation and of the ligand cavity, either a three-dimensional ‘wrap-around’ complex or a two-dimensional ‘crown complex’ are formed. For the cesium complexes, the values of ΔH c o and ΔS c o are definitely solvent-dependent and in all cases the complexes are enthalpy stabilized but entropy destabilized. A compensating effect is observed in the variation of the enthalpy and entropy of complexation so that the overall influence of the above solvents on the stability of the complexes is rather limited.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1572-8927
    Schlagwort(e): Solvation ; ion pairs ; hexafluorophosphate ion ; fluorine-19 NMR ; sodium-23 NMR ; nonaqueous solvents
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Fluorine-19 and sodium-23 NMR measurements were carried out on sodium hexafluorophosphate solutions in a number of solvents. In solvents of medium polarity and donicity (e.g., propylene carbonate, acetone, acetonitrile) the 19 F chemical shift moved upfield with increasing concentration of the salt. This behavior is indicative of anion-cation interactions which may be of long-range type, i.e., formation of solvent-separated ion pairs; the possibility of contact ion pair formation, however, cannot be excluded. In solvents of low polarity and donicity (acetic acid, tetrahydrofuran), the salt is essentially completely associated in the 0.1–1.0M concentration range. On the other hand, in solvating solvents with high dielectric constants, such as dimethyl-formamide, dimethylsulfoxide, and formamide, there is very little ionic association in the same concentration range. The above conclusions are supported by 23 Na chemical shift measurements. Potassium hexafluorophosphate solutions do not show any concentration dependence of the 19 F chemical shifts, while for tetra-n-butylammonium solutions the 19 F resonance moves downfield with increasing concentration of the salt.
    Materialart: Digitale Medien
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