0000000000312149
AUTHOR
Piero Paoletti
Potential ATPase mimics by polyammonium macrocycles: Criteria for catalytic activity
Abstract A series of polyammonium macrocycles, ranging in size from the 18-membered ring [18]aneN6 to the 36-membered [36]aneN12 were examined as potential ATPase mimics. The rates of hydrolysis of ATP were followed at pH 3.0 and 7.0 using 31P NMR and HPLC techniques. Stability constants as a function of degree of protonation, distribution curves for the ligands as a function of pH, and distribution curves for the mixed species of nucleotides, inorganic phosphate, and macrocycle were also determined. All of the macrocycles catalyzed the hydrolysis of ATP to some extent compared to noncatalyzed hydrolysis. A critical dependence on macrocyclic ring size was observed, with [21]aneN7 being the …
The Role of Macrocyclic Receptors in Organization of Metal Centers
The coordination properties of saturated aza or oxa-aza macrocyclic receptors are strictly dependent on their molecular topology. In order to rationalize the relationship between structural features and binding characteristics of such molecules we have studied the coordination behavior of different macrocyclic or macropolycyclic oxa-aza ligands towards metal cations. Depending on molecular topology, a variety of inorganic chemical species can be lodged inside the receptor’s cavity, such as simple metal ions, complexed inorganic anions, partially hydrated metal cations or binuclear assemblies.
Effect of Nitrogen Methylation on Cation and Anion Coordination by Hexa- and Heptaazamacrocycles. Catalytic Properties of These Ligands in ATP Dephosphorylation
The stability constants of the complexes formed by 1,10-dimethyl-1,4,7,10,13,16-hexaazacyclooctadecane (L) and 1,4,7-trimethyl-1,4,7,10,13,16,19-heptaazacyclohenicosane (L1) with Ni(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+), as well as that for the formation of PbL2(2+) (L2 = 1,4,7,13-tetramethyl-1,4,7,10,13,16-hexaazacyclooctadecane), were determined by means of potentiometric (pH-metric) titrations in 0.15 mol dm(-)(3) NaClO(4) at 298.1 +/- 0.1 K. The enthalpy changes for the formation of Cu(2+) complexes with L and L1 were measured by means of microcalorimetry. These thermodynamic data were compared with those previously reported for L2, 1,4,7,10,13,16-hexaazacyclooctadecane (L3), and 1,4,…
Cascade complex formation by phosphate in the cobalt(II)/[30]aneN10 anaerobic system
Abstract The interaction of phosphate with the mono- and binuclear cobalt(II) complexes of [30]aneN 10 (1,4,7,10,13,16,19,22,25,28-decaazacyclotriacontane) has been studied by potentiometry in 0.15 mol dm −3 NaClO 4 solution at 298.15 K under anaerobic conditions. The stable species [CoH 2 ([30]aneN 10 )PO 4 ] + , [CoH 4 ([30]aneN 10 )PO 4 ] 3+ , [Co 2 H([30]aneN 10 )PO 4 ] 2+ , [Co 2 H 2 ([30]aneN 10 )PO 4 ] 3+ and [Co 2 H 3 ([30]aneN 10 )PO 4 ] 4+ , where the phosphate anion is directly bound to the metal ions or acts as a second sphere ligand, are formed and their stability constants have been determined. The results obtained allowed for the selection of suitable conditions for the study…
Thermodynamic study of the interaction of long open-chain polyazaalkanes with cobalt(II) and nickel(II) ions
Complexation equilibria between the open-chain terminally methylated polyamines 1,14-bis(methylamino)-3,6,9,12- tetraazatetradecane (L1), 1,17-bis(methylamino)-3,6,9,12,15-pentaazaheptadecane (L2), 1,20-bis(methylamino)- 3,6,9,12,15,18-hexaazaicosane (L3) and 1,23-bis(methylamino)-3,6,9,12,15,18,21-heptaazatricosane (L4) with Co2+ and Ni2+ have been studied by means of potentiometric and spectrophotometric methods in 0.15 mol dm−3 NaClO4 aqueous solution at 298.15 K The stability constants for the complexes formed have been determined from e.m.f, data. All these ligands form mononuclear ML2+ complexes of similar stability with Co2+ and Ni2+. Binuclear Co2L44+, Ni2L34+ and Ni2L44+ are also f…
Cation and Anion Coordination Chemistry of Palladium(II) with Polyazacycloalkanes. Thermodynamic and Structural Studies
The interaction of PdCI2 4 - with the macrocyclic ligands of the series [3k]aneNk has been studied both in solution and in the solid state. [18]aneN6 and [21]aneN7 form both mono- and binuclear Pd2+ complexes, whose stability constants have been determined in 0.5 mol dm-3 NaCI at 298.15 K. [21]aneN7 also forms, in solution, a trinuclear species in which an amino group deprotonates to bridge two Pd2+ ions, as observed in the solid state. The crystal structure of the complexes [Pd2([18]aneN6)Cl2][CIO4]2 and [Pd3[21]aneN7)CI3][CIO4]2 ⋅ H2O have been solved by single crystal X-ray analysis. C12H30N6CI4O8Pd2: monoclinic, space group C2/m, a = 10.876(2), b = 18.117(2), c = 7.043(2) A, s = 113.78(…