Chemistry Reference
In-Depth Information
1
First Principles
DFT Studies of
Metal-Based Biological
and Biomimetic Systems
Arturo Robertazzi, Alessandra Magistrato,
Matteo Dal Peraro, and Paolo Carloni
CONTENTS
1.1. Introduction....................................................................................................... 1
1.2. Density.Functional.Theory.and.Its.Application.to.Biological.Systems............ 3
1.3. Discussion.......................................................................................................... 6
1.3.1. Solvent.Effects.on.Nitrogen.Fixation.Biomimetic.Molybdenum.
Catalyst.................................................................................................. 6
1.3.2. Platinum.Anticancer.Complexes......................................................... 10
1.3.3. Catalytic.Mechanism.of.Metallo.β-Lactamases................................. 15
1.4. General.Conclusions........................................................................................ 21
References................................................................................................................ 22
1.1 INTRODUCTION
Metal.elements.play.a.pivotal.role.in.many.aspects.of.living.organisms,.from.the.
stabilization.of.nucleic.acids.(RNA.and.DNA).to.a.variety.of.proteins.
1-5
.One.of.the.
most.peculiar.features.of.metal.elements.is.their.ability.to.be.oxidized.and.bind.to.
(or.otherwise.interact.with).electron-rich.biological.molecules,.such.as.proteins.and.
DNA..Natural.evolution.has.led.living.organisms.to.employ.metal.elements.exten-
sively.in.a.wide.variety.of.tasks..For.instance,.approximately.one-third.of.known.
enzymes.contains.metals.
1,6
.Metal.ions.promote.a.number.of.chemical.processes.
including. bond. cleavage. and. formation,. electron. transfer,. and. radical. reactions.
6
.
These.processes.are.central.to.many.biological.phenomena,.such.as.DNA.synthesis.
and.replication,.cellular.energy.production,.and.O
2
.generation,.sensing.and.trans-
port.
6
. Iron. and. copper. are. essential. elements. in. mammalian. metabolism:. iron. is.
the.metal.constituent.of.heme.in.hemoproteins.such.as.hemoglobin.and.myoglobin.
and.copper.is.relatively.abundant.in.the.ferroxidases.ceruplasmin.and.haphaestin.
and. in. other. enzymes. such. as. cytochrome. c. oxidase.
7
. Magnesium. is,. with. few.
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