Incomplete transfer of the O-label indicated that either a portion of diphenyl sulfoxide failed to react with Tf2O on the timescale of the reaction, or the reaction was not completely anhydrous, or an activated sulfoxide intermediate was hydrolysed on work-up with retention of the O-atom.
(6) It is important to consider the timescale of the reaction term (f(c_{b}, alpha_{mathrm{O}_{2}} P_{mathrm{O}_{2}})) which describes the process of dissolved oxygen becoming bound and vice versa.
Given that poor activation or slow transmetallation of the boronate could account at least in part for some of the reduced reactivity observed with certain boronate species (and indeed the overall timescale of the reaction), we felt that the more predictable hydrolysis pathways displayed by these trifluoroborate salts[ 31b] might improve the coupling sequence.
Similar barrier heights are therefore computed for the formation of both (S,E)- 5 ko (Δ G≠calc=14.0 kcal mol−1) and (R,E)- 5 ko (Δ G≠calc=15.6 kcal mol−1) and this, coupled with reversibility of these transformations, means that both enantiomers will be formed over the timescale of the reaction, leading to the unexpected loss of chirality transfer.
There are no simple rules to relate timescales to reaction constants of nonlinear models.
Nanoboron can very quickly be heated relative to micronboron, and on a timescale consistent with the timescale of the Al/CuO reaction, thus allowing it to participate more efficiently in the combustion.
An acceptable time-step in Smoldyn is stated as that at which it is "significantly smaller" than the timescale of the fastest reaction in the system, which we will choose as the time-step that is 10 times lower than the fastest reaction in the system.
§ The timescale of this recombination reaction between the reduced catalyst and the holes in the semiconductor varies between catalysts, taking place in t 50% ∼ 220 ms for Co1, while being slower for Co2 (t 50% ∼ 450 ms) and Co3 (t 50% ∼ 800 ms) (determined from the time constant of the slow hole decay phase, see Fig. S4, ESI † for details of data fitting).
In [20], the authors consider larger systems with three genes, postulating four general requirements for biochemical oscillations: negative feedback, time delay, sufficient non-linearity of the reaction kinetics and proper balance of the timescales of the reactions.
In addition, cellular compartmentalization serves to dampen much, but not all, of the effects of one subnetwork on another, such that kinetic modeling of single compartments would likely capture most dynamics that are fast on the timescale of the transport reactions.
