27/08/2013

Dopaminedetection
(importantneurotransmitter)
EC mechanism

Implantable electrodes

27/08/2013

Commoninterferingspecies
Ascorbicacid
Irreversible

Commoninterferingspecies
Uricacid
Irreversible

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Howdowedetectall3speciesatonce?

Next week

Detectingdopaminecontd..
Modifiedelectrodes

Carbon
paste

Ag
nanoparticles
Carbon paste

Carbon
nanotubes Carbon paste

Ag
nanoparticles
Carbon
nanotubes
Carbon paste
Synergistic
effect

27/08/2013

Canweimproveresolutionbetweensignals?
Differential pulse voltammetry can be considered as a
derivative of linear sweep voltammetry
This technique involves a series of regular voltage
pulses superimposed on the potential linear sweep.
The current is sampled immediately prior to the
application of the pulse and at the end of the pulse and
the difference is recorded. This gives rise to a
differential current response.
This eliminates the effect of the charging current
(remember chronoamperometry)

Inthesemeasurements,the
effectofthechargingcurrent
canbeminimized,sohigh
sensitivityisachieved.
Faradaiccurrentisextracted,
soelectrodereactionscanbe
analysedmoreprecisely.
Reversiblereactionsshow
symmetricalpeaks,and
irreversiblereactionsshow
asymmetricalpeaks.

It is used for electroanalytical chemistry can detect quantities of solute of

the order of 10-8 M

27/08/2013

Binary mixture

Keep DA concentration
the same and vary AA
concentration

Keep AA concentration the

same and vary DA
concentration

Nanostructuredsurfaces electrochemicallymade
Pyramidal,rodlike,and
sphericalgold
nanostructureswere
electrodepositedfrom
aqueoussolutionsof0.1
MHClO4
containing40,4,and40
mMHAuCl4,respectively,
at0.08,
0.08,and0.2 Vvs.Ag/
AgCl,respectively,for2
min.
Shapeiscontrolledby
appliedelectrode
potentialand
concentrationofHAuCl4.

AFMimagesofa)electrodepositedpyramidal,b)rodlike,
c)spherical,and(d)asputteredgoldsurfaces.

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Separation of AA and UA

We observe here
electrocatalytic effects
each electrochemical
reaction is catalysed to a
different extent rates of
electron transfer are
different as well as the peak
positions allows us to
resolve the processes

Keep AA concentration the

same and vary UA
concentration

Vary the concentration of

both AA and UA

27/08/2013

Chronoamperometric detection under stirring conditions AA detection at 10

M additions - electrode held at 0.0 V vs Ag/AgCl

Pyramids > Rods > Spheres : shape dependent electrochemistry

Useelectrostatics
Itisknownthatascorbicacidexistsinits
anionicform(pKa 4.1)anddopamineinits
cationicform(pKa 8.9)atphysiologicalpH7.4
Wecantakeadvantageofthisbymodifying
theelectrodesurfacewithachargedspecies
e.g.Nafion
Nafionisoneofthemostcommonlystudied
cationexchangepolymers

27/08/2013

Uponhydration,Nafionabsorbs
relativelylargeamountsofwater
andcanincreaseitsdryweightby
asmuchas50percentormore
dependinguponequivalentweight,
counterion,andtemperature

ThereforeNafionwithallthisnegativechargewouldrepelanionic
ascorbicacidandattractthecationicdopamine,thereforean
electrodemodifiedwithNafioninabinarymixtureonlyshowsa
signalduetodopamine

DA signal only

In this case we do not necessarily need a nanostructured electrode a smooth one

will suffice