- Application of Bronsted-type LFER in the study of the phospholipase C mechanism
-
Phosphatidylinositol-specific phospholipase C cleaves the phosphodiester bond of phosphatidylinositol to form inositol 1,2-cyclic phosphate and diacylglycerol. This enzyme also accepts a variety of alkyl and aryl inositol phosphates as substrates, making it a suitable model enzyme for studying mechanism of phosphoryl transfer by probing the linear free-energy relationship (LFER). In this work, we conducted a study of Bronsted-type relationship (log k = βlg pKa + C) to compare mechanisms of enzymatic and nonenzymatic reactions, confirm the earlier proposed mechanism, and assess further the role of hydrophobicity in the leaving group as a general acid-enabling factor. The observation of the high negative Bronsted coefficients for both nonenzymatic (βlg = -0.65 to -0.73) and enzymatic cleavage of aryl and nonhydrophobic alkyl inositol phosphates (βlg = -0.58) indicates that these reactions involve only weak general acid catalysis. In contrast, the enzymatic cleavage of hydrophobic alkyl inositol phosphates showed low negative Bronsted coefficient (βlg = -0.12), indicating a small amount of the negative charge on the leaving group and efficient general acid catalysis. Overall, our results firmly support the previously postulated mechanism where hydrophobic interactions between the enzyme and remote parts of the leaving group induce an unprecedented negative-charge stabilization on the leaving group in the transition state.
- Mihai, Cornelia,Kravchuk, Alexander V.,Tsai, Ming-Daw,Bruzik, Karol S.
-
p. 3236 - 3242
(2007/10/03)
-
- Synthesis and surface-active properties of a series of new anionic gemini compounds
-
The synthesis of a series of new anionic dimeric amphiphiles 1-5 is described. The CMC and both static and dynamic surface tensions have been measured using the Wilhelmy plate technique and the maximum bubble pressure method. Results are compared to those obtained with the corresponding monomeric surfactants and relevant monomeric or dimeric compounds described in the literature. The relationship between the structural features of the different compounds and their properties is discussed. In particular an increase in the length of the connecting group between the two lipophilic chains lowers the CMC of the compounds which is different from results reported in the literature for other gemini compounds. Copyright (C) 1999 Elsevier Science Ireland Ltd.
- Renouf, Philippe,Hebrault, Dominique,Desmurs, Jean-Roger,Mercier, Jean-Michel,Mioskowski, Charles,Lebeau, Luc
-
-
- Dimeric surfactants: First synthesis of an asymmetrical gemini compound
-
The heterodimeric surfactant 1 is synthesized through a 6-step procedure, starting from 1,2-epoxydodecane. The preliminary evaluation of the performances of that asymmetrical gemini representing a new kind of surface-active agents reveals interesting physical properties.
- Renouf, Philippe,Mioskowski, Charles,Lebeau, Luc,Hebrault, Dominique,Desmurs, Jean-Roger
-
p. 1357 - 1360
(2007/10/03)
-