IUBio

Reformulation of the 2nd law in kinetic terms

Petr Kuzmic pkuzmic at biokin.com
Thu Jan 29 12:50:14 EST 1998


Pentcho Valev wrote:

> In fact, the second law in this case takes the
> following form:
> 
>     (k+_catalyzed)/(k+)  =  (k-_catalyzed)/(k-)       /7/
> 
> By comparing /6/ and /7/ we see that
> 
>        k-_catalyzed  =  k8(E)                         /8/

This definition of "k-(catalyzed)" cannot stand.  To understand why,
write the original reaction as

        k+
    C <===> A + B               /1'/
        k-

and try your definitions on it.  Compare results with your formal
treatment of 

            k+
    A + B <===> C               /1/
            k-

The results must be invariant.

> At the moment I am a bit lazy [...], but k+_catalyzed should satisfy
> the equation
> 
>        Vforward  =  (k+_catalyzed)(A)(B)              /9/

Not true.  In that case k+(catalyzed) is not a constant, because
V[forward] depends also on the concentration of the enzyme (no matter
how small it is, in particular, negligibly small compared with [A], [B],
[C]).

> Paul Schlosser started deriving something like that
> recently - I assume it is not difficult.

No, it is not difficult indeed.  The formal treatment of the
'specificity number' (which is your k+[catalyzed]) is containd in any
introductory textbook on enzyme kinetics.   (Please note that our
frequent correspondent Athel Cornish-Bowden is in the Guiness Book of
Records for the largest number of introductory textbooks with "Enzyme
Kinetics" in the title).  I admit it: in asking you to define
k+[catalyzed] I was trying to see if an iquisitive dilettante could
briskly arrive at the 'specificity number' from first principles...

I guess I failed: the human propensity for laziness prevailed again... 
:)

                                --Petr
_____________________________________________________________
Petr Kuzmic Ph.D. * BioKin Ltd. * Madison, WI 53708-8336, USA
pkuzmic at biokin.com * http://www.biokin.com * 608.256.1269 fax



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