Interfaces and Interphases in Analytical Chemistry

284 Pages·2011·17.3 MB·English

by  Robin Helburn and Mark F. Vitha (Eds.)

Interfaces and Interphases in
1
0
0
w
org 062.f Analytical Chemistry
pubs.acs.k-2011-1
p://1/b
htt02
2 | 0.1
11
2 on June 6, 2017, 2011 | doi:
y 89.163.35.4eb): February
bW
oaded Date (
wnlon
Doati
c
bli
u
P

In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
1
0
0
w
org 062.f
pubs.acs.k-2011-1
p://1/b
htt02
2 | 0.1
11
2 on June 6, 2017, 2011 | doi:
y 89.163.35.4eb): February
bW
oaded Date (
wnlon
Doati
c
bli
u
P

In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
1062
ACS SYMPOSIUM SERIES
Interfaces and Interphases in
Analytical Chemistry
Robin Helburn, Editor
01 St. Francis College
0
w
org 062.f Mark F. Vitha, Editor
pubs.acs.k-2011-1 Drake University
p://1/b
htt02
2 | 0.1
11
2 on June 6, 2017, 2011 | doi:
y 89.163.35.4eb): February
bW
oaded Date (
wnlon Sponsored by the
Doati
blic ACS Division of Analytical Chemistry
u
P

AmericanChemicalSociety,Washington,DC
DistributedinprintbyOxfordUniversityPress,Inc.
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
LibraryofCongressCataloging-in-PublicationData
Interfacesandinterphasesinanalyticalchemistry/RobinHelburn,editor,MarkF.Vitha,
1
00 editor;sponsoredbytheACSDivisionofAnalyticalChemistry.
w
org 062.f Incplu.dcems.b-i-bl(iAogCraSpshyicmaploresfiuermensceersieasn;d1i0n6d2e)x.
pubs.acs.k-2011-1 A1In.SaBSlyNutrifc9a-7c-8Ce-oc0hn-8egm4re1is2sst-er2ys6.-0-IC4.-oH3neg(labrleuksr.snep,saR.po2eb.r)iBn.iIoIl.oVgiitchaal,iMntaerrkfaFc.eIsI-I-.CAomngerreicsasnesC.h3e.mCihceamlSiostcriye,ty.
p://1/b DivisionofAnalyticalChemistry.
htt02 QD506.A1I5532010
2 | 0.1 543--dc22
2 on June 6, 20117, 2011 | doi: 1 2011003051
y 89.163.35.4eb): February TSAthNaenSdpIaaZrpde3r9fo.u4rs8eIndn1fi9on8rtm4h.iastipounbSlicciaetniocnesm—eePtesrmthaenmeninciemoufmPraepqeurirfeomr PenritnstoefdALmiberraircyanMNaatetiroianlasl,
bW Copyright©2011AmericanChemicalSociety
oaded Date ( DistributedinprintbyOxfordUniversityPress,Inc.
wnlon
Doati AllRightsReserved. ReprographiccopyingbeyondthatpermittedbySections107or108
blic oftheU.S.CopyrightActisallowedforinternaluseonly,providedthataper-chapterfeeof
u $40.25plus$0.75perpageispaidtotheCopyrightClearanceCenter,Inc.,222Rosewood
P
Drive,Danvers,MA01923,USA.Republicationorreproductionforsaleofpagesinthis
bookispermittedonlyunderlicensefromACS.Directtheseandotherpermissionrequests
toACSCopyrightOffice,PublicationsDivision,115516thStreet,N.W.,Washington,DC
20036.
Thecitationoftradenamesand/ornamesofmanufacturersinthispublicationisnottobe
construedasanendorsementorasapprovalbyACSofthecommercialproductsorservices
referenced herein; nor should the mere reference herein to any drawing, specification,
chemicalprocess, orotherdataberegardedasalicenseorasaconveyanceofanyright
or permission to the holder, reader, or any other person or corporation, to manufacture,
reproduce,use,orsellanypatentedinventionorcopyrightedworkthatmayinanywaybe
relatedthereto. Registerednames,trademarks,etc.,usedinthispublication,evenwithout
specificindicationthereof,arenottobeconsideredunprotectedbylaw.
PRINTEDINTHEUNITEDSTATESOFAMERICA
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Foreword
The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of
the series is to publish timely, comprehensive books developed from the ACS
sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare
01 developed from symposia sponsored by other organizations when the topic is of
0
w keeninteresttothechemistryaudience.
org 062.f
pubs.acs.k-2011-1 fpoarpaepBrspermfoopareyriaabtgeereeaexnicdnlcguodtmeodpptruoebhbleiesnthsteiavrebfoococoukvs,etrthahegeepbaroonopdkof;sooerdtihnteatrebsrlemesotatfyocbtoheneateadnudtdesideisntocreepv.riSoeovwmieddee
http://021/b comprehensiveness. When appropriate, overview or introductory chapters are
2 | 0.1 added. Draftsofchaptersarepeer-reviewedpriortofinalacceptanceorrejection,
11
2 on June 6, 2017, 2011 | doi: aiannrecdlunmAdoaetsndaauciscncreurptilhtpeeet,dsv.oaonrleluymproeerspi.gariVnedaelribnraectsiamemarercerhap-rrpoeadapudecyrtsifoonarnsmdoafto.prirgeivniaolusrepvuiebwlishpeadpepraspaerres
y 89.163.35.4eb): February ACSBooksDepartment
bW
oaded Date (
wnlon
Doati
c
bli
u
P

In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Preface
An interfacial layer and the chemistry that occurs there are at the heart
of many analytical methods and techniques. From electrochemical sensing to
chromatographytoanalysesbasedonsurfacespectroscopy, interfacesarewhere
the critical chemistry in the method takes place. In this book, we look at ten
01 diverseexamplesofinterfacesandinterphases,newandold,inwhichtheauthors
0
pr design,build,characterizeoruseananalyticallyrelevantinterfacialsystem. The
org 062. topicsareorganizedaccordingtothecompositionoftheinterphase(orinterface)
bs.acs.2011-1 agsroudpisintignsctarfer:om1 aalkmylethchoadi-nbaassesdemcblalisessifi,c2atimona.teriaTlsheostehercotmhapnosailtkioynl-bcahsaeidn
puk-
p://1/b assemblies including gels, submicron sized silica, carbon nanotubes and layered
on June 6, 2012 | htt7, 2011 | doi: 10.102 htimiennactatveehterernLffriaarioqeaccousleesukes,,l.sitwaneaYngdesdeawtis3nthfeoaoilpnrnlwataatrehlsarycelfsotlaoiesmccomlealmdslveeaocctvtrhnoeeeemdlntmohdpipenisoms.mtsterIeeeryndnfsatttoschhafiemriaonbllouailtongtaht-ghyeearectidrfthnseioitvsserieinreglfsexnaluinacqbasmiua,nsilptdida.llenecac.,coyheamefrsdror.opvsmmoauanssitcttoeheidgoesrniaivnnpoiehmfdwysiafetwfaneetrhsriieteanhnrlgeest
35.42 uary 1 the constraints are considerable and the chemistry is harder to control, advances
y 89.163.eb): Febr chhaevmeAibssetrewyn.itmhoarneymbeoaosukr,edti,tlfeoscucasendblearmgeilsyleoandisntgabeilsipzeincgialtlhyewexhiesntintgheiyntecrofnatcaiianl
bW
aded ate ( ecsrotasbsl–icsuhttwinhgatwtohrisdsbloiokke‘isinnteortfaacbeo’uot.r‘Tahniaslyisticnaolt,’asbooiotkmaabyobuetesuqrufaalclyeuanseafluylsitso.
oD
wnlon There may be places where that aspect seeps into a particular discussion on
Doati account of the need to examine or characterize a particular analytically relevant
c
bli interphase. That is the nature of interdisciplinary science. This is a book about
u
P
traditional analytical chemistry and the interfacial layers that comprise or could
comprise some of those methods. In showing analytical chemistry from this
perspective,wehopetodrawpersonsspecializingindifferentmethodologieswho
may be searching for new ways to think about their discipline, both in research
and education.
Acknowledgments
We deeply thank the authors for their patience and their contributions, and
forgivingusthelatitudetopresenttheirworkinthecontextofthisbook’stheme.
Everyone who gave an oral paper in the original small symposium at the 2008
NortheastRegionalMeeting(NERM)oftheAmericanChemicalSociety(ACS)
entitled Analytical Interfacial Science has contributed a chapter. In addition,
ix
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
there are chapters written by persons who were not at the symposium but who
wereinvitedtocontributetothebook. Weespeciallythanktheseindividualsfor
their willingness to be part of this effort. We thank all those patient persons in
the ACS Books division, Jessica Rucker, Bob Hauserman, Sherry Weisgarber,
and especially Tim Marney, who tolerated us throughout the acquisition, design
andproductionphases. Wethankalltherefereesfortheindividualchaptersand
especiallyKimberlyFrederickatSkidmoreCollegeforassistingusatamoment’s
notice. WethanktheDivisionofAnalyticalChemistryforasmallgrantinsupport
oftheoriginalsymposium.
RobinHelburn
1
0
pr0 DepartmentofChemistry&Physics
org 062. St. FrancisCollege
s.acs.011-1 BrooklynHeights,NY11201
b2
puk-
p://1/b MarkF.Vitha
on June 6, 2012 | htt7, 2011 | doi: 10.102 DDDereapskaMertmoUinennievtse,orIfsAiCty5h0em31i1stry
42 y 1
35.uar
163.Febr
y 89.eb):
bW
aded ate (
oD
wnlon
Doati
c
bli
u
P

x
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Chapter 1
The “Interface” in Analytical Chemistry:
Overview and Historical Perspective
R. S. Helburn*
1
0
h0 Department of Chemistry & Physics, St. Francis College,
c
org 062. BrooklynHeights,NY11201
pubs.acs.k-2011-1 *[email protected]
p://1/b
2 | htt0.102 Many of today’s analytical methods and techniques, e.g.–
on June 6, 2017, 2011 | doi: 1 soicnohctlcreuourtmfreasa.cpteaoF,rgatuirntapicpohthnaioisicnen,gibneoiglnuecanatsdrcaoahrcyrthroewammnhsaiedtcrouaegcl,areanrspapihlenyicctatercoasosenlcnduos/moporirncs,o,i–trghnfienaaclvinitolrtilaetvanreftsaifnacegner
42 y 1 is that critical region whose chemistry we design so as to
35.uar enhanceanalyteselectivityandsensitivity. Therearecommon
y 89.163.eb): Febr taheramnegseionfthinetednedseidgnanoafly“tiinctaelrfpauciraplosree.gioInns”thtihsaitntcruotduacctroorsys
bW chapterwehighlighttheobjectivesofasmallsymposiumatthe
aded ate ( NortheastRegionalMeetingoftheAmericanChemicalSociety
oD
wnlon (ACS)entitled“AnalyticalInterfacialScience”whichhassince
Doati expanded into this book. This symposium was an opportunity
c
bli to bring together researchers who specialize in different areas
u
P of analytical chemistry but who share a common interest

in studying, characterizing and ultimately using interfaces
to perform chemical analyses. In this chapter we trace a
brief, non-comprehensive historical trajectory of interfaces in
selected methodologies with an emphasis on common themes
that span techniques in separations, electrochemical systems
andsensing,andtechniquesassociatedwithsurfacemicroarray
and immunoassay. Our discussion parallels the chapter topics
as we provide an overview of interfacial regions composed
of 1 hydrocarbon chain assemblies, 2 gels, layered substrates,
submicron and nanosized materials, and 3 immobilized
bio-reactive agents. The individual chapters are highlighted
throughoutthediscussion.
©2011AmericanChemicalSociety
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Introduction
The field of analytical chemistry encompasses numerous methods and
technologies, many of which involve an interface or interfacial environment
between two adjacent phases and the transfer of analyte or signal between
those phases. Some examples are: 1 the partitioning of solutes between
mobile and stationary phases in liquid chromatography (LC), 2 extraction of
analytes from a sample headspace into a microextraction medium, 3 emission
or reflection-absorption spectroscopy (RAS) of surface confined analytes and 4
analyte interactions at a sensor surface. In each case, it is the chemistry at the
phase boundary and its effect on solute or signal transfer that determines the
efficacy of the method. The intent of this symposium was to convene a small
1 group to talk about a common focus – interfaces and interphases. This is the
0
h0 primary link among the chapters. Each paper involves a system containing a
c
org 062. phase or pseudophase boundary coupled with solute interactions, and where
pubs.acs.k-2011-1 tcahhreeapsotyregsrtasenmaizreeudnwdwreiirttthesntruedisnypeascemtrvtioexsttuyarpneeaoonffarleiynvttiiecerawflacpaeunrdapsoresosepe.paorRcseheaddfoteorrmsaawttesilclahnfindniqdtuhteah-tabtathstheeyde
p://1/b area of analytical chemistry. Interfaces in the context of high vacuum surface
2 | htt0.102 analysiswhilementionedbrieflyinahistoricalcontextarenotpartofthischapter
on June 6, 2017, 2011 | doi: 1 collection. Historical Sketch
42 y 1
35.uar AnalyticalChemistry
y 89.163.eb): Febr Analytical chemistry has always been about the development of methods
aded bate (W atonodlsteacnhdniaqpupersouascehdestothiadtenwtiefyusaendtoqusoalnvteifyqucahleitmatiicvaelsaunbdstqaunacnetsi.taIttiviesacbhoeumtitchael
oD
wnlon problems. As analytical chemists, we think about fundamental chemical and
Doati physical knowledge and then ask how we might exploit a principle or chemical
c
bli reactiontocreateatoolthatsolvesarealandpressingchemicalproblem.
u
P Many physical-chemical theories that were developed in the 19th and early

20thcenturieshavelaidthegroundworkforunderstandingtoday’swellestablished
analyticalmethodsandtechniques. Forexample,thephaserulediscussedinthe
classicpublication“ThermodynamicPrinciplesDeterminingEquilibria”byJosiah
WillardGibbs(1,2)providedafoundationforchemicalseparations. Raoult’sLaw
helped us to understand solute-stationary phase interactions and neutral analyte
activity coefficients (γ∞) in gas chromatography (3, 4). Wolcott Gibbs applied
electrodepositionquantitativelyforthefirsttimein1864, aneventthatfollowed
the work of Michael Faraday (1, 5, 6). Pioneering work on the definition and
measurementofpH,startingasearlyas1906(7–9)wasseminalinleadingtothat
mostimportantofmacroscopicmeasures. Earlyspectroscopicstudiesalsocontain
fundamentalfindingsofrelevancetomodernanalyticalchemistrysuchasquantum
theory(10–13),absorptioncoefficients(ε)(14)andthetheoryofindicators(15).
2
In Interfaces and Interphases in Analytical Chemistry; Helburn, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.