Won't this depend on the relative final concentrations of A and B in the
two experiments? If A going into excess B will have different mass action
considerations that B going into excess A. Even if the final concentrations
of A and B are stoichiometric, the initial stages of the titration will
have very different mass action products for A into B vs. B into A. An
additional wrinkle is the concentrations of A and B relative to the
dissociation constant Kd. The titration curve math gets a little more
complex when the concentration of the species is in the same order of
magnitude as the Kd. There are quite a few examples of bollixed binding
curves in the literature for tight-binding equilibria that ignore the
relationship between Kd and ligand concentrations.  Cooperativity issues
will of course perturb any pure, non-cooperative statistical analysis based
on equilibrium constants.

_______________________________________
Roger S. Rowlett
Gordon & Dorothy Kline Professor, Emeritus
Department of Chemistry
Colgate University
13 Oak Drive
Hamilton, NY 13346
email: [email protected]

On Thu, Oct 3, 2019 at 11:51 AM Bernhard Rupp <[email protected]>
wrote:

> I am not looking for anything yet – I wonder what – if any – the
> consequences of doing it one way or the other would be.
>
> I am reasonably certain that any difference affects the analysis.
>
>
>
> Thx, BR
>
>
>
> *From:* CCP4 bulletin board <[email protected]> *On Behalf Of *Keller,
> Jacob
> *Sent:* Thursday, October 3, 2019 17:41
> *To:* [email protected]
> *Subject:* Re: [ccp4bb] ITC question -dimer vs monomer
>
>
>
> I don’t understand what you are trying to do—are you trying to show, by
> the difference in ITC response, that the predictions you made about the
> oligomerization are true?
>
>
>
> JPK
>
>
>
> +++++++++++++++++++++++++++++++++++++++++++++++++
>
> Jacob Pearson Keller
>
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>
> HHMI Janelia Research Campus
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> *From:* CCP4 bulletin board <[email protected]> *On Behalf Of *Bernhard
> Rupp
> *Sent:* Thursday, October 3, 2019 11:06 AM
> *To:* [email protected]
> *Subject:* [ccp4bb] ITC question -dimer vs monomer
>
>
>
> Hi Fellows,
>
>
>
> please let me ask the respective experts an ITC question: I have 2
> proteins, stable and dialyzed in identical buffer.
>
> A is a monomer and B an obligate dimer. I suspect that eventually a A2B2
> dimer will form.
>
>
>
> Intuitively, it should make a difference whether I titrate the dimer with
> the monomer or vice versa.
>
> In the first case, a momomer would initially meet a lot of free dimers,
> and I would expect that randomly, a AB2 complex
>
> is more likely to form than a A2B2 (let’s disregard any more complex
> colligative/cooperative effects).
>
>
>
> If I drip the dimer into the monomer pool, it is quite likely that the B
> dimer meets 2 free As, and I get right away a higher population of A2B2s.
>
>
>
> Maybe at dilutions of ITC and with sufficient equilibration that is not an
> issue at all (again, absent any cooperative effects that might alter the
> first Kd vs. the second, despite the sites on the dimer are at least
> initially equivalent).
>
>
>
> Can someone guide me towards literature about this or perhaps share some
> first-hand experience?
>
>
>
> Many thanks, BR
>
>
>
> ------------------------------------------------------
>
> Bernhard Rupp
>
> http://www.hofkristallamt.org/
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>
> [email protected]
>
> +1 925 209 7429
>
> +43 676 571 0536
>
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