A continuation of research on the catalytic mechanism of the
phosphoglucomutase reaction is proposed that includes X-ray
diffraction studies on the crystalline enzyme, as well as NMR (1H,
13C, 31P, and 113Cd), kinetic, and isotopic rate studies on
solutions of the enzyme. These studies will focus on the
mechanism that the enzyme uses to produce its large, catalytic
rate effect. An electron density map with a nominal resolution of
2.7 Angstrom unit will be improved by molecular replacement
techniques; the current molecular model will be modified and
refined. Phases from the model plus additional diffraction data
will be used to construct difference density maps of enzyme-
substrate analog complexes after completing an evaluation of
several possible complexes of this types, partly via NMR
techniques. Related studies will explore 1H/1H interactions
between bound substrate and the enzyme in substrate analog
complexes. An attempt also will be made to observe and evaluate
1H/113Cd interactions between the bound metal ion and bound
substrate. 31P-NMR studies on the interactions between the
Cd2+ complex of the dephospho-enzyme and substrate analogs
such as straight-chain 1,4-diol bisphosphates will be continued to
further define how G1c-1, 6-P2 is bound by this form of the
enzyme so that either the 1- or the 6-phosphate group is in
position for transfer to a single acceptor group on the enzyme. A
series of kinetic studies will be conducted with butane-1,4-diol
monophosphate, which acts as an inefficient substrate (phosphate
acceptor) to isolate the effects of pH and identity of the
activating metal ion on the rate-controlling step in this process:
the bond making/breaking step. A determination of the (18 O)
kinetic isotope effect on the reaction (in the reverse direction,
where (18 O)-labelled butane-1,4-diol-P2 is used to phosphorylate
the enzyme) also will be conducted. Studies on how cosolutes
affect the crystal growth of phosphoglucomutase at high salt will
be continued by comparing the effects of polyethylene glycol and
detergents on crystal growth rate. Procedures for reducing the
salt content of such crystals to aid in the binding of substrates
and analogs will be explored. Studies of how conditions used for
data collection affect the quality of X-ray diffraction data also
will be conducted.
Public Health Relevance Statement
Data not available.
NIH Spending Category
No NIH Spending Category available.
Project Terms
X ray crystallographybinding proteinsbutanolschemical cleavagecrystallizationdioldiphosphonatedivalent metalelectron spin resonance spectroscopyenzyme mechanismenzyme structureenzyme substrateenzyme substrate analogenzyme substrate complexglucose phosphateligandsnuclear magnetic resonance spectroscopyphosphoglucomutasepolyethylenes
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