Remarkable hydrolysis of phosphodiester by neutral lanthanide(III) DO3A complexes

Bioorganic and Medicinal Chemistry Letters

Volumn 6, Issue 17, 1996, Pages 2063-2068

  Kalesse, Markus ^a   Loos, Andrea ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

LANTHANIDE; METAL COMPLEX;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; HYDROLYSIS; REACTION ANALYSIS;

EID: 0030567872     PISSN: 0960894X     EISSN: None     Source Type: Journal    
DOI: 10.1016/0960-894X(96)00386-1     Document Type: Article

References (29)

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27. 3 for five hours. To remove any trace of free lanthanide ions the cold solution was filtered through a 0.2 μm Spartan filter and titrated first with a strongly acidic ion exchange resin (IRA 120) and consecutively with a strongly basic ion exchange resin (IRA 400) (1 μS; pH = 7.5). Complexes were obtained as white solids after evaporation of water. Spartan 30/A (0.2μm, Brown Rim D) filter are purchased from Schleicher & Schuell, Germany. Elemental analysis and FAB mass spectra confirmed the composition of the products. All kinetic experiments were performed in Millipore water and the pH was checked after every kinetic run.
28. HEPES is the commercial name of N-2-Hydroxyethylpiperazine-N'-2-ethane sulfonic acid and was purchased from Biomol.
29. Kinetic studies: HEPES is the commercial name for N-(2-hydroxyethyl)piperazine-N-2-ethanesulfonic acid and was purchased from Biomol. The pH value of HEPES buffer solutions was adjusted with Metrohm titrator/pH meter (Metrohm 716 DMS Titrino) at room temperature. Molar extinction coefficients of p-nitrophenol were determined under hydrolysis conditions over a pH range from 5.2 to 10.2. Hydrolysis experiments were performed in teflon sealed quarz cuvettes (1 cm path length) which were incubated in an water bath at 50°C ± 0.2 °C. Additionally, in every run a reference cuvette was incubated which only contained buffer and HPNP. Absorbance of p-nitrophenolate was measured at 400 nm against background hydrolysis with a Shimadzu UV-visible UV-1601 dual-beam spectrophotometer fitted with a thermostated cuvette holder. After each hydrolysis experiment the pH of the sample and reference solution was checked (differences ≤ 0.03). Rate constants were reproducible to ± 10%. Every kinetic run was repeated in the presence of stoichiometric amounts of EDTA and no change of hydrolytic activity was observed.