Abstract:The electrochemical behaviour of haemoglobin denatured using different concentrations of urea was investigated at the liquid|liquid interface. The reverse peak current varied with the concentration of urea, allowing the building of the unfolding curve, which compares well with UV-Vis absorbance results. Thermodynamic parameters, such as the change in free energy of folding in water, w G ∆ , and the index of the compactness of the protein, m, were extracted from the experimental data. The work here presents a simple electrochemical method for the study of protein unfolding by electrochemistry at the liquid | liquid interface.
Spectrophotometric methods have been used to obtain rate laws and rate parameters for the following reactions: with k,, kb, E,, Eb having the values 85 f 5 l./mole.s, 5.7 f 0.2 s-l (both at 298.2'K), and 56 f 4 and 66 f 2 kJ/mole, respectively. (2) BrCN + 31-+ H + + 1 3 -+ Br-+ HCN -d[BrCN]/dt = k,[BrCN][I-] with k, = 0.106 f 0.004 I./mole .s at 298.2'K and E , = 67 f 2 kJ/mole.(3) S(CN)z + 31-+ H + -+ 1 3 -+ SCN-+ HCN d[S( CN)tI/dt = kd[S (CN)zI [I -1 with k d = (3.06 f 0.15) X l./mole.s at 298.2'K and Ed = 66 f 2 kJ/mole. Mechanisms for these reactions are discussed and compared with previous work.205
Pd-Catalyzed Intramolecular Regioselective Arylation of 2-Pyrones, Pyridones, Coumarins and Quinolones by C-H Bond Functionalization. -The regioselective Pd-catalyzed cyclization of a number of heterocyclic substrates without added phosphine ligands is reported. A switch in regioselectivity is obtained by introduction of blocking substituents at the C-3 position of the 2-pyrone. -(NOLAN, M.-T.; BRAY, J. T. W.; ECCLES, K.; CHEUNG, M. S.; LIN, Z.; LAWRENCE, S. E.; WHITWOOD, A. C.; FAIRLAMB, I. J. S.; MCGLACKEN*, G. P.; Tetrahedron 70 (2014) 40, 7120-7127, http://dx.
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