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Urease is an enzyme containing a dinuclear nickel active center responsible for the hydrolysis of urea into carbon dioxide and ammonia. Interestingly, inorganic models of urease are unable to mimic its mechanism despite their similarities to the enzyme active site. The reason behind the discrepancy in urea decomposition mechanisms between inorganic models and urease is still unknown. To evaluate this factor, we synthesized two bis-nickel complexes, [Ni2L(OAc)] (1) and [Ni2L(Cl)(Et3N)2] (2), based on the Trost bis-Pro-Phenol ligand (L) and encompassing different ligand labilities with coordination geometries similar to the active site of jack bean urease. Both mimetic complexes produced ammonia from urea, (1) and (2), were ten- and four-fold slower than urease, respectively. The presence and importance of several reaction intermediates were evaluated both experimentally and theoretically, indicating the aquo intermediate as a key intermediate, coordinating urea in an outer-sphere manner. Both complexes produced isocyanate, revealing an activated water molecule acting as a base. In addition, the reaction with different substrates indicated the biomimetic complexes were able to hydrolyze isocyanate. Thus, our results indicate that the formation of an outer-sphere complex in the urease analogues might be the reason urease performs a different mechanism.
Assuntos
Níquel , Urease , Níquel/química , Urease/química , Ligantes , Amônia , Ureia/químicaRESUMO
We herein report a comprehensive investigation on the magnetic, structural, and electric properties of CoO nanoparticles with different sizes by local inspection through hyperfine interactions measured in a wide range of temperatures (10-670 K) by using radioactive [Formula: see text]In([Formula: see text]Cd) tracers with the perturbed angular correlations technique. Small cobalt oxide nanoparticles with the characteristic size of 6.5 nm have been prepared by the wet chemical route that turned out to be essential to incorporate radioactivity tracers during nucleation and growth of the particles. Nanocrystalline samples with 22.1 nm size were obtained by thermal treatments under low pressure of helium at 670 K. The hyperfine data were correlated with X-ray diffraction, ZFC-FC magnetic measurements, and transmission electron microscopy to describe the structure, magnetic properties, size, and shape of samples. An analysis of the temperature evolution of hyperfine parameters revealed that the structural distortion and the magnetic disorder in the core and on the surface layer play an important role in the magnetic behavior of CoO nanoparticles.
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The intermolecular dynamics in the THz frequency range of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by a combined usage of inelastic neutron scattering (INS), Raman, and far-infrared (FIR) spectroscopies and the power spectrum calculated by molecular dynamics (MD) simulations. The collective dynamics of the simulated systems is also discussed by the calculation of time correlation functions of charge and mass currents that are projected onto acoustic- and optic-like motions. The INS and Raman measurements have been performed as a function of temperature in the glassy, crystalline, and liquid phases. The excess in the vibrational density of states over the expectation of the Debye theory, the so-called boson peak, is found in the INS and Raman spectra as a peak at â¼2 meV (â¼16 cm-1) and also in the direct measurement of heat capacity at very low temperatures (4-20 K). This low-frequency vibration is incorporated into the curve fits of Raman, FIR, and MD data at room temperature. Fits of spectra from these different sources in the range below 100 cm-1 are consistently achieved with three components at ca. 25, 50, and 80 cm-1, but with distinct relative intensities among the different techniques. It is proposed as the collective nature of the lowest-frequency component and the anion-cation intermolecular vibration nature of the highest-frequency component. The MD results indicate that there is no clear distinction between acoustic and optic vibrations in the spectral range investigated in this work for the ionic liquids [N1114][NTf2] and [N1444][NTf2]. The analysis carried out here agrees in part, but not entirely, with other propositions in the literature, mainly from optical Kerr effect (OKE) and FIR spectroscopies, concerning the intermolecular dynamics of ionic liquids.
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In the investigation reported in this paper a modified thermal decomposition method was developed to produce very small Er2O3 nanoparticles (NPs). Particles structure, shape and size were characterized by x-ray diffraction and transmission electron microscopy which showed that the synthesis by thermal decomposition under O2 atmosphere produced very small and monodisperse NPs, allowing the investigation of finite-size and surface effects. Results of magnetization measurements showed that the smallest particles present the highest values of susceptibility that decrease as particle size increases. Specific heat measurements indicate that the sample with the smallest NPs (diameter â¼5 nm) has a Néel temperature of 0.54 K. The local structure of particles was investigated by measurements of hyperfine interactions with perturbed angular correlation spectroscopy using 111Cd as probe nuclei replacing the cationic sites. Results showed that the relative population of sites 8b increases in both the core and surface layer of particles.
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A local order-disorder transition has been disclosed in the thermophysical behavior of the ionic liquid 1-benzyl-3-methylimidazolium dicyanamide, [Bzmim][N(CN)2], and its microscopic nature revealed by spectroscopic techniques. Differential scanning calorimetry and specific heat measurements show a thermal event of small enthalpy variation taking place in the range 250-260 K, which is not due to crystallization or melting. Molecular dynamic simulations and X-ray diffraction measurements have been used to discuss the segregation of domains in the liquid structure of [Bzmim][N(CN)2]. Raman and NMR spectroscopy measurements as a function of temperature indicate that the microscopic origin of the event observed in the calorimetric measurements comes from structural rearrangement involving the benzyl group. The results indicate that the characteristic structural heterogeneity allow for rearrangements within local domains implying the good glass-forming ability for the low viscosity ionic liquid [Bzmim][N(CN)2]. This work sheds light on our understanding of the microscopic origin behind complex thermal behavior of ionic liquids.