Chemistry Reference
In-Depth Information
the.gas.phase.and.in.water..Our.CPMD.simulations.and.binding.energy.calculations.
show.that.a.single.Fe
3+
.coordinates.to.the.carbohydrate.both.in.the.gas.phase.and.in.
aqueous.solution..The.coordination.of.the.transition.metal.ion.impacts.the.preferred.
glycosidic.linkage.conformation.in.both.the.phases..Speciically,.the.glycosidic.link-
age.preference.changes.from.
g+ > g− > t
.to.
g+ > g− ≈ t
.in.the.gas.phase.and.CPMD.
simulations.demonstrate.that.the.preference.for.the.
g
+.orientation.of.the.glycosidic.
linkage.is.due.to.intramolecular.hydrogen.bonding.
In.the.aqueous.solution,.we.ind.that.the.preference.of.glycosidic.linkage.changes.
from.
g+ > t > g−
. to.
g+ > g− > t
. upon. coordination. to. Fe
3+
.. CPMD. simulations.
clearly.indicate.that.the.conformational.preference.of.the.glycosidic.linkage.of.the.
carbohydrate.and.the.coordination.of.the.metal.ion.are.inluenced.by.intra.and.inter-
molecular.hydrogen.bonds..Our.results.further.demonstrate.that.CMD.simulations.
are.insensitive.to.these.effects.and.suggest.a.need.for.better.force.ield.parameters.for.
the.aqueous.Fe
3+
.ion.and.carbohydrates.
This. study. illustrates. that. irst. principles. studies. including. chemical. reactivity.
calculations,.NPA,.and.CPMD.simulations.can.provide.important.insights.into.the.
structure.and.coordination.chemistry.of.biometallic.complexes.in.the.gas.phase.and.
in. aqueous. solution.. Furthermore,. we. show. that. the. solution. environment. impacts.
the.reactive.sites.of.a.biomolecule.toward.ligands.(metal.ions)..We.are.conident.that.
validated.irst.principles.approaches.in.different.phases.(gas.and.solution).will.help.
us.to.predict.unknown.reaction.mechanisms.of.important.physiological.processes,.
such. as.receptor.and. ligand. interactions. that. are.crucial. to.drug. design,.medicine,.
biochemistry,.and.nanobiotechnology.
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