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| Sosale Chandrasekhar. |
| The Michaelis-Menten equation (MME) is considered to be the fundamental equation describing the rates of enzyme-catalysed reactions, and thus the 'physicochemical key' to understanding all life processes. It is the basis of the current view of enzymes as generally proteinaceous macromolecules that bind the substrate reversibly at the active site, and convert it to the product in a relatively slow overall sequence of bonding changes ('turnover'). The manifested 'saturation kinetics', by which the rate of the enzymic reaction (essentially) increases linearly with the substrate concentration ([S]) at low [S] but reaches a plateau at high [S], is apparently modelled by the MME. However, it is argued herein... |
| Tipo: Manuscript |
Palavras-chave: Biotechnology; Chemistry; Evolutionary Biology. |
| Ano: 2008 |
URL: http://precedings.nature.com/documents/1637/version/1 |
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| Sosale Chandrasekhar. |
| The current theory of the titled phenomenon is apparently based on an inconsistent use of concentration units, as employed in the derivation of the fundamental equations. Thus, manifestly, whilst the relation between extent of conversion and e.e. is derived with mole fractions, the succeeding kinetic equations employ units of molarity. This invalidates the derivation in the general case. Fortuitously, however, it is applicable in the majority of simple cases, wherein the total number of moles involved in the reaction remains constant. Herein is presented a rigorous approach which is generally valid. |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2012 |
URL: http://precedings.nature.com/documents/7127/version/1 |
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| Sosale Chandrasekhar. |
| It is argued that the titled non-linear effects (NLE) may arise whenever the order of the reaction in the chiral catalyst in greater than 1. In a fundamental departure from previous approaches, this is mathematically elaborated for the second order case. (NLE may also be observed if the chiral catalyst forms non-reacting dimers in a competing equilibrium; practically, however, this implies the in situ resolution of the catalyst.) The amplification of enantiomeric excess by NLE implies a relative (although modest) reduction in the entropy of mixing. The consequent increase in free energy apparently indicates a non-equilibrium process. It is suggested, based on arguments involving the chemical potential, that kinetically-controlled reactions lead to a state... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2012 |
URL: http://precedings.nature.com/documents/6947/version/1 |
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| Sosale Chandrasekhar. |
| It is argued that the Carnot cycle is a highly inaccurate representation of a steam engine, and that the net work obtained in its operation would be zero. This conclusion is also supported by an elementary mathematical approach, which re-examines the work done in the four individual steps of the cycle. An important consequence of this is that the concept of entropy, originally proposed on the basis of the Carnot theorem, may not be a fundamentally valid thermodynamic quantity. Also, the experimental approach generally adopted in the determination of entropy is questionable, and the importance of increasing randomness in natural processes not universally valid. In fact, a more viable basis, at least vis-à-vis chemical reactions, appears to be the... |
| Tipo: Manuscript |
Palavras-chave: Chemistry. |
| Ano: 2008 |
URL: http://precedings.nature.com/documents/1852/version/1 |
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