New gadolinium complex with efficient hydrolase-like activity: a 100-million-fold rate enhancement in diester hydrolysis.

The synthesis, structure, and hydrolase-like catalytic activity of a new mononuclear gadolinium complex [Gd(L)(NO3)(H2O)3](NO3)2 (1) are reported. A clean two-stage kinetic reaction for hydrolysis of the diester 2,4-bis(dinitrophenyl)phosphate by 1 was followed, and the rate constants were determined. A high DNA cleavage activity was also demonstrated. The active species in the hydrolytic process is proposed based on the X-ray structure, electrospray ionization mass spectrometry analysis, and kinetic and potentiometric equilibrium studies of 1.

Mechanisms of acid decomposition of dithiocarbamates. 3. Aryldithiocarbamates and the torsional effect.

The acid decomposition of some p-substituted aryldithiocarbamates (arylDTCs) was observed in 20% aqueous ethanol at 25 degrees C, mu = 1.0 (KCl, for pH > 0). The pH-rate profiles showed a dumbell shape with a plateau where the observed first-order rate constant k(obs) was equal to k(o), the rate constant of the decomposition of the dithiocarbamic acid species. The acid dissociation constants of the dithiocarbamic acids (pK(a)) and their conjugate acids (pK(+)) were calculated from the pH-rate profiles. Comparatively, k(o) was more than 10(4)-fold faster than alkyldithiocarbamates (alkDTCs) with similar pK(N) (the acid dissociation constant of the parent amine). It was observed that the values of pK(a) and pK(+)were 5 and 8 units of pK, respectively, higher than the expected values from the pK(N) of alkylDTCs. The higher values were attributed to the inhibition of the delocalization of the nitrogen electron pair into the benzene ring because of the strong electron withdrawal effect of the thiocarbonyl group. Comparison of the activation parameters showed that the rate acceleration was due to a decrease in the enthalpy of activation. Proton inventory indicated the existence of a multiproton transition state, and it was consistent with an S to N proton transfer through a water molecule. There are two hydrogens contributing to a secondary SIE, and there are also two protons that are being transferred at the transition state to form a zwitterion followed by fast C-N bond cleavage. The mechanism could also be a concerted asynchronic process where the N-protonation is more advanced than the C-N bond breakdown. The kinetic barrier is similar to the torsional barrier of thioamides, suggesting that the driving force to reach the transition state is the needed torsion of the C-N bond that inhibits the resonance with the thiocarbonyl group and the aromatic moiety, increasing the basicity of the nitrogen and making the proton transfer thermodynamically favorable.