(informed search algorithms)
use problem specific heuristics( )
May be more efficient
At the heart of such algorithms there is the concept
Assumptions made in the derivation of the rate law for enzyme kinetics.
Enzyme concentration is negligible compared to the substrate concentration.
Rate measured is "initial rate " i.e., only a few percent of the reaction is followed
Inhibition of Enzyme Catalysis Uncompetitive Inhibition.
Applying the steady-state approximation to the above scheme, i.e., if the reaction rate is approximately
constant over the time interval concerned then [ES] is also constant:
0 k3 ES I k 3
Steric inhibition of resonance
Gaq relative to
NH4+ (kJ mol1)
Ggas relative to
NH4+ (kJ mol1)
Analysis of the solution data
In passing from I II, drop in pKa is explained on
Steric and Inductive Effects.
Analysed using mean CD, CH bond lengths
In an asymmetric potential
In a symmetric potential
The average CD and CH bond lengths are equal in a symmetric energy well, however, in
an asymmetric potentia
Lifetimes of Reaction Intermediates and Mechanism.
For many nucleophilic substitutions reactions, the rate does not depend on [Nuc]. Hence,
the activated complex does not contain the nucleophile and is only comprised of SM (+
Catalysis, Inhibition and Free Energy
If we use transition state theory in which there is a pseudo equilibrium between ground state and
transition state (K ) then we can write the following equations based on the thermodynamic cycle:
KTS K m
Laser Flash Photolysis (and fast kinetics)
Electromagnetic radiation waves propagating through space involving oscillating electric and
magnetic fields at right angles to each other and to the direction of propagation
electromagnetic radiation can be rega
krel = 100 (relative to chlorocyclohexane)
Winstein studies the tosylate solvolysis
The cyclopropyl carbinyl acetate product rearranged to the -acetate at an acce