A new class of cryptand-like ionophore based on a bis calix[4]arene structure has been developed. These molecules proved highly selective for complexation of potassium over all group I metal cations and barium. A range of symmetric and asymmetric calix[4]tubes featuring either alkyl or phenyl substituents at the upper rim have been synthesized in exceptional yield. Alteration of the calix[4]arene upper rim environment enables fine-tuning of the rate of potassium uptake, which can be evaluated through the conformational change on binding by NMR studies. Selectivity of potassium complexation has been demonstrated using NMR and electrospray mass spectral techniques. Molecular modeling studies, derived from crystallographic data, confirm that the potassium metal cation is complexed via the axial route, passing through the calix[4]arene annulus, and provide evidence for complexation rate and selectivity.
The photostability of pirimicarb, (2‐dimethylamino‐5,6‐dimethylpyrimidin‐4‐yl dimethylcarbamate) in aqueous media, under natural and artificial sunlight irradiation conditions, is reported. The pH of the irradiated solutions remained constant during degradation time. The photodegradation mechanism seemed to be similar under both conditions, but the half‐life was found to be about three times longer under natural than under artificial conditions. Four main photo‐products (1, 2, 3 and 4) were isolated and identified by spectroscopic methods. It is proposed that a common photodegradation pathway exists for pirimicarb under both irradiation conditions. The results obtained from the photodegradation of pirimicarb and of its four main products isolated on solid phase permit the construction of a possible photodegradation pathway. Photoproduct 4 (2‐methyl‐formylamino‐5,6‐dimethyl‐4‐hydroxypyrimidine) is here described for the first time.
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