Chemistry Reference
In-Depth Information
Solvent. effects. present. further. dificulties. in. studying. biometallic. compounds..
However,.these.effects.must.be.taken.into.account,.given.that.a.signiicant.fraction.of.
the.human.body.is.composed.of.water.and.that.most.relevant.biomolecular.and.bio-
metallic.reactions.of.physiological.and.technological.relevance.are.(to.some.extent).
solvent.mediated..Water.gives.rise.to.hydrophobic.interactions.that.stabilize.the.core.
of. globular. proteins,. is. thought. to. weaken. and. diminish. electrostatic. interactions.
in. many. biomolecules,. and. ills. the. internal. cavities. of. proteins,. oligosaccharides,.
and.nucleic.acids..Moreover,.water.molecules.can.be.associated.with.the.surfaces.of.
biomolecules,.occupying.certain.more.or.less.well-deined.positions.and.interacting.
with. surrounding. water. molecules. through. hydrogen. bonds. [29-38].. Even. though.
much.effort.has.been.expended.on.studies.of.liquid.water.and.aqueous-phase.bio-
molecules,.the.role.of.water.in.the.coordination.chemistry.of.biometallic.compounds.
remains.poorly.understood.
Experimental. measurements. utilizing. extended. x-ray. absorption. ine. structure,.
x-ray.and.neutron.diffraction.yield.structural.information,.and.nuclear.magnetic.res-
onance,.infrared.and.Raman.spectroscopies.are.used.for.investigating.the.structural.
and. dynamical. properties. of. biomolecules. in. aqueous. solution. [36].. Interpreting.
the.results.from.these.experimental.techniques.can.be.immensely.challenging,.and,.
in. particular,. it. is. dificult. to. produce. direct. measurements. of. the. local. electronic.
structure.of.the.reaction.medium.associated.with.the.fast.dynamics.of.biometallic.
systems..Limited.information.can.be.found.in.x-ray.analysis,.which.has.been.used.
to.determine.pair.correlation.functions..However,.these.functions.are.usually.spheri-
cally.averaged,.and.thus,.details.of.structure.in.aqueous.biomolecule.solutions.are.
dificult.to.predict.accurately.since.important.information.linked.to.the.anisotropic.
and.asymmetric.character.of.the.system.is.lost.[37,38].
Challenges.to.theoretical.and.computational.studies.of.biometallic.systems.are.
relatively.large.molecular.sizes,.long.timescales,.and.a.large.number.of.degrees.of.
freedom.(as.mentioned.above)..Static.irst.principles.calculations.in.the.gas.phase.
and.in.aqueous.solution.using.continuum.models.for.water.have.been.applied.exten-
sively.for.predicting.the.structure.and.function.of.aqueous.biomolecules.and.biome-
tallic.compounds..Even.though.these.ab.initio.calculations.are.relatively.eficient.in.
terms.of.computational.time,.static.gas-phase.calculations.can.capture.neither.the.
impact.of.the.dynamics.nor.the.effect.of.water.on.the.predicted.structures.of.the.
compounds.of.interest..Continuum.water.calculations.ignore.intermolecular.hydro-
gen. bonding. interactions,. which. can. have. a. large. impact. on. the. predicted. struc-
ture.and.conformation.of.most.biomolecules.and.biometallic.compounds..Classical.
molecular.dynamics.(CMD).and.Monte.Carlo.simulations.are.the.most.widely.used.
computational.tools.to.study.biomolecules.and.biometallic.systems.in.aqueous.solu-
tion..Even.though.classical.molecular.simulations.have.been.useful.to.a.great.extent,.
the.accuracy.of.these.simulations.depends.on.the.quality.of.the.force.ield.param-
eters,.and.these.simulations.ignore.quantum.effects.in.predicting.the.structure.and.
function. of. biomolecules. and. biometallic. systems.. In. addition,. CMD. simulations.
neither.capture.bond.forming.and.bond.breaking.events.nor.the.molecular.orbital.
interactions.between.the.iron.ion.and.the.carbohydrate.in.aqueous.solution.
In.our.recent.studies,.we.presented.a.novel.strategy.that.employs.theoretical.cal-
culations,.molecular.dynamics.simulations,.and.mass.spectrometric.experiments.to.
Search WWH ::




Custom Search