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Dynamic Electrochemistry Methodology and Application обзор 1994
Dynamic Electrochemistry Methodology and Application обзор 1994
Edmond F. Bowden
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695
James Q. Chambers'
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 361R
nonmathematical and emphasizes concepts. Galus sum- electrodes by Inzelt, and SECM by Bard et al. ( A 4 0 ) . Inzelt
marizes theoretical treatments of the reaction rates for both has also reviewed polymer film electrodes elsewhere ( A 4 1 ) .
soluble couples and amalgam-forming reactions such as Zn2+/ Microelectrodes have been covered thoroughly in a pub-
Zn(Hg). In a review by Saveant of his contributions to our lication of the proceedings of a NATO advanced study institute
understanding of dissociative electron-transfer reactions, he that contains articles from most of the laboratories which
outlines criteria for distinguishing between stepwise and have contributed to the development of this area (A42). The
concerted mechanisms in electrode reactions ( A 2 4 ) . authoritative review by Heinze on this subject is also
Trasatti has reviewed recent theory on the adsorption of recommended ( A 4 3 ) .
organics on electrode surfaces (A25), and Parsons and The latest in the Techniques in Chemistry series deals with
Ritzoulis critically compare experimental results for adsorption the molecular design of electrode surfaces. Nine individual
on stepped surfaces of Pt and Au single crystal electrodes chapters written by active mod squad researchers cover subjects
(A26). In the latter article, the evidence for the assignment such as adsorption on single crystal electrodes, various aspects
of voltammetric peaks in the hydrogen region to hydrogen of redox polymer electrodes, and self-assembled monolayers.
atom adsorption on steps of surface unit cells was clearly The volume, which includes more than 1400 references, is
summarized. A thorough review of UHV techniques as applied tightly edited by Royce Murray, who contributed a highly
toobtain atomic level information about the electrode interface recommended overview chapter (A44). Reviews in this area
at single crystal electrodes has been provided by Soriaga (A27). have appeared elsewhere (A45-A49). The articles by Forster
This treatment is suitable for a graduate student level and Vos on the theory and applications of modified electrodes
introduction to the area. (A45) and by Zagal on electrocatalytic processes at metal-
A substantial analysis of the kinetics of oxygen reduction lophthalocyanine surfaces (A46) are nicely done.
at solid electrodes in aqueous solution has been written by Several reviews treat subjects that strongly overlap elec-
Appleby (A28), and a book has appeared on the electro- trochemistry and the amorphous, but fashionable, area of
chemistry of surfaces from the critical perspective of Professor materials science. The chapter on processable conducting
J. O’M. Bockris (A29). Catalysis of the hydrogen ion polymers in a compilation containing five chapters on nonlinear
reduction by metal surfaces has been briefly reviewed (A30). optics and conducting polymers is especiallynoteworthy (A50).
An IUPAC Commission report has appeared that compiles Mirkin and Ratner have produced a provocative treatise on
kinetic parameters on the C12/C1- electrode reaction (A31). molecular electronics (A.71) and electrochemistry at high-T,
Also the IUPAC Commission report dealing with the superconducting working electrodes, an area where electro-
measurement of real surface areas has been published a second chemistry can contribute to both fabrication and character-
time (A32). This report describes 15 methods, 11 in situ and ization, is the subject of a report (A52). Other reviews treated
4 ex situ, in detail. the structure and physical properties of PEO-type polymer
A variety of ancillary techniques for the study of electrode electrolytes (A53) and the electrochemical synthesis and
processes are treated in a recent volume; included are chapters properties of conducting polymers ( A 5 4 ) . The article by
on ellipsometry, inferometric methods, SERS, Mossbauer Curran et ai. narrowly focused on the various methods by
spectroscopy, photothermal deflection spectroscopy, X-ray which polypyrrole can be employed as a support for electro-
absorption and neutron scattering, impedance spectroscopy, catalytic materials or substituent groups ( A 5 5 ) .
and others ( A 3 3 ) . An introduction to STM and AFM with Recent work toward the development of practical biosensors
emphasis on basic theory and practicalities has appeared that has been reviewed from several different viewpoints (A56-
discusses the application of these techniques to in situ A62). These devices are generally based around a redox
electrochemistry (A34). Scanning tunneling spectroscopy, enzyme coupled with a molecular mediating species entrapped
which can map the surface electronic structure with atomic in an interfacial matrix of some kind. Both amperometric
resolution in the best scenario, was also addressed. and potentiometric detection can be employed. The review
Buttry and Ward have written perhaps the most authori- of Alvarez-Icaza and Bilitewski gave a good summary of design
tative of several recent reviews on electrochemical quartz parameters and their optimization (A56). Thearticleof Wring
crystal microscopy (EQCM) (A35). Hillman et al. also and Hart (A61) concentrated on the chemistry of the
reviewed the QCM technique with emphasis on the detection modification of carbon-based substrates for these devices,while
of mobile species transferred during the redox switching of that of Hilditch and Green had a practical bent describing
polymer films (A36). A review of electrochemical mass disposable electrochemical biosensors in or near to commercial
spectroscopy (ECMS) contains some excellent examples of production (A62).
the use of a thermospray LC/MS interface with an electro- Ewing et al. have reviewed progress on the difficult problem
chemical cell (A37). Solution IR spectroelectrochemistry has of analyzing the contents of single nerve cells with emphasis
also been briefly reviewed (A38). Recent applications of on in vivo electrochemistry and EC detection for capillary
spectroelectrochemistry have been described in a report that electrophoresis where the Penn State group has made major
focuses on the redox chemistry of thin-film interfaces, e.g., contributions (A63).
inorganic semiconductors, oxide and chalcogenide films on Several works have appeared that concern more classical
native metals, dye-modified electrodes, conducting polymer analytical voltammetry. These include a little monograph by
films, and others (A39). Smyth on the voltammetry of biologically important molecules
Volume 18 of the Bard series, Electroanalytical Chemistry, (A64)and reviews of analytical voltammetry theory by Cassidy
contains reviews on electrochemistry in microheterogeneous (A65),adsorptive cathodic stripping voltammetry by van den
fluids by Rusling, charge transport in polymer-modified Berg (A66), the reduction of metal complexes on Hg by
362R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
Tur’yan (A67), and instrumentation for voltammetry by have been some important and useful papers published that
Barisci et al. (A68). In addition, a bookon cyclicvoltammetry deserve mention here.
has been recently advertized (A69). In the latter category, Mirkin and Bard have presented a
In the realm of organic electrochemistry, several important theoretical analysis of quasi-reversible steady-state voltam-
books or reviews have been published in recent years. A revised mograms that allows extraction of the kinetic parameters (ko
and expanded third edition of the Manual Baizer opus has and a ) from a single i-E curve without independent deter-
appeared (A70). To complement this work, a book based on mination of the Eo’value ( B I ) . They gave extensive tables
a symposium in honor of Manny Baizer contains 48 chapters for the wave shape parameters, E114 - E112 and E112 - E3149
organized under the following headings: Mechanism; Reduc- that correlate with given sets of kinetic parameters. Cor-
tion; Oxidation; Mediated Reactions; Biochemical, Biomass relation tables were given both for the case of uniformly
and Natural Products; Modified, Sacrificial/Consumable accessible electrodes, such as a RDE and an U M E hemisphere,
Electrodes; Electrogenerated Bases; Film-Forming Electro- and for a U M E disk. Another procedure that appears to be
polymerization; and Ion-Exchange (A71). Professor Shono easy to implement for the determination of heterogeneous
has written a brief text that features experimental details for rate constants from CV peak separation data is that of
150 electrochemical transformations of specific compounds Lavagnini et al., which only requires intermediate diffusion
(A72). Niyazymbetov and Evans have summarized the use control such that peak currents are evident in the CVs (B2).
of carbanions and heteroatom anions in electroorganic
Exact formalism for the ac impedance of spherical,
synthesis (A73). Recent examples of in situ generation of
cylindrical disk, and ring UMEs was developed (B3). Real
anions and anodic oxidation of anions are given. Commercial
and imaginary components of the impedance, assuming
applications are emphasized in a brief review of the use of
uniform flux at the electrode surface, were tabulated as a
sacrificial anodes in synthetic electrochemical processes
function a2w/D, a dimensionless quantity where a is the
involving C 0 2 (A74). The problem of C 0 2 reduction has also
characteristic dimension of the UME, w is the frequency, and
been treated from several different angles in a collection of
D is the diffusion coefficient of the Ox/R couple. Linear
chapters by different authors (A75). Other reviews have
sweep voltammograms obtained at ring electrodes were
appeared on the electrosynthesis of polymers with emphasis
calculated over 9 orders of magnitude sweep rate and compared
on intermediates (A76) and on the electrochemistry of
to experimental results (B4). Calculation of the theoretical
chlorophyll (A77).
voltammograms required the value of a dimensionless pa-
Two excellent treatments of important topics have been rameter, y = (R2 + R1)/2(R2 - Rl), where R2 and R1 are the
produced by authorities in their respective fields. Wayner outer and inner ring radii, respectively.
and Parker have provided an Accounts of Chemical Research
article on the thermodynamic relationships between bond Oldham has continued his penetrating theoretical exami-
dissociation energies and redox potentials of the derived nation of microelectrode behavior in a very general treatment
radicals and their corresponding ions (A78). A clear descrip- of steady-state voltammetry at UMEs of arbitrary shape (B5).
tion is given here of the way to incorporate voltammetric peak H e showed that the steady-state current depends on three
potential data into the thermodynamic cycles. Koval and factors: the electrode area, an accessibility factor, and a
Howard have presented a thorough review of electron transfer heterogeneity function. A universal equation is given for the
at semiconductor electrode/liquid electrolyte interfaces (A79). i-E relationship.
While the emphasis of this review is on research advances A sophisticated integral equation approach was used by
since 1985, it also serves well as a lucid introduction to the Bender and Stone to treat steady-state mass transport to
terms and fundamental concepts of a complex subject. Gratzel microelectrodes (B6). They gave a numerical solution
has given an account of his research on photoelectrochemical procedure for calculation of the surface flux that is applicable
energy conversion using a “molecular machine” based on thin to the general case of an arbitrarily shaped planar electrode,
films of colloidal Ti02 particles that are sintered together to including both surface and bulk catalytic regeneration reac-
allow for charge carrier transport (A80, ,481). The phe- tions. Multidimensional integral equations were used in
nomenon of room-temperature photoluminescence from porous another mathematically sophisticated approach to UME
Si was reviewed in comprehensive fashion (A82),and a review diffusion problems (B7, B8). The approach was stated to
of photoemission at metal/electrolyte interfaces includes a have considerable advantage over the conceptually simpler
discussion of the cathodic generation of solvated electrons finite difference and finite element digital simulations in terms
(A83). An issue of Electrochimica Acta was devoted to new of computer requirements and execution time. UME con-
trends in photoelectrochemistry (A84). figurations considered were microdisks embedded in an
Finally, two issues of the Journal of Electroanalytical insulating plane of infinite or finite extent, microbands, the
Chemistry have accounts of the scientific careers and useful SECM problem, and an array of inlaid planar electrodes of
complete lists of their publications for two stalwarts of physical arbitrary shape.
electrochemistry: Professors Brian Conway and John O’Mara Brodsky et al. presented closed-form solutions of the
Bockris in Vols. 355 and 357, respectively (A85, A86). diffusion kinetic equation for individual or arrays of UMEs
that were based on a “zero range approximation” (B9). They
6. MASS TRANSPORT achieved excellent agreement between calculated and experi-
Microelectrodes. Theory. The intense activity in the area mental collection efficienciesusing literature data. Conformal
of microelectrode theory has lessened in the last few years. mapping procedures for the digital simulation of diffusion at
Applications of UMEs have mushroomed, however, and there a microdisk have been optimized and improved (BI0, SI]).
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 365R
4-pm Pt working electrode, a 100-pm Ag reference electrode, catecholamines at the femtomole level from individual adrenal
and a 100-pm Pt counter electrode separated by heat-sealing medullary chromaffin cells continues this tradition (B89).
film (B74). Interestingly, both cells that released only epinephrine and
In continuing publications, mostly from the Texas labora- cells that released a mixture of epinephrine and norepinephrine
tory of Bard and co-workers, the versatility of the scanning were identified. Wightman’s group have used UMEs to
electrochemical microscopy (SECM) technique has been monitor the flux of catecholamines from other biological cells
demonstrated. Wipf and Bard made significant improvement during exocytosis (B90). The process was analyzed in terms
in the technique by employing small-amplitude tip-position of diffusive mass transport from a point source. Ewing’sgroup
modulation in combination with lock-in detection of the signal has used platinized carbon microring electrodes to monitor
( B 7 5 ) . This gave unambiguous indication of whether a surface 0 2 concentrations and to perform multiple pulsevoltammetry
was conducting or insulating and markedly improved the in single neuron cells of their favorite pond snails (B91,B92).
contrast between those surfaces. In another study, it was Oxidation currents have also been measured due to generation
shown that information on the tip shape could be obtained of superoxide anions at a carbon UME in contact with a single
from the SECM response at a well-defined flat surface (B76). biological cell (B93),and a Pt on graphite UME was used to
This is important for very small UMEs where conical-shaped monitor oxygen efflux from illuminated algae protoplasts
electrodes are much more easily fabricated than insulated (B94). The release of NO from a single cell was detected
UME disks. SECM theory was developed for the determina- with a carbon fiber UME coated with a polymeric porphyrin/
tion of fast heterogeneous kinetics from steady-state currents Nafion composite film (B95). Adams and co-workers used
(B77, B78). The method, which involves determining the Nafion-coated carbon fibers to detect norepinephrine release
current as a function of potential for fixed values of d / a , and to profile glutamate-evoked ascorbic acid release in the
where d is the separation between the scanning tip of radius brains of freely moving rats (B96,B97). Impedance analysis
a and the conductive surface, should permit rate constants up of 100-pm Pt electrodes covered with biological cell cultures
to 10-20 cm/s to be measured. The technique was applied indicated the formation of pores in the cell membranes upon
to the measurement of the rate constants for the ferrocene+/O application of small applied voltages (B98).
and C& couples (B78,B79). Also SECM, operating in the UME arrays have been employed in innovative fashion.
feedbackand generation/collection modes, was applied to the Electrochemical luminescence, generated by a radical cation
measurement of rates of chemical reactions coupled to electron- plus radical anion annihilation reaction, was examined at
transfer steps for the electrodimerization of activated olefins double-band UME arrays both experimentally and theoreti-
(B80). Simulation of the redox kinetics in the tipsubstrate cally using conformal mapping transformations (B99). For
gap was performed in conjunction with SECM to image the reversible systems the depletion effect in differential pulse
redox enzyme glucose oxidase immobilized on nonconducting voltammetry is minimized for an interdigitated array (IDA)
substrates such as nylon, hydrogel membranes, or a L-B film working electrode operating in the feedback mode (BIOO).
(B81). An IDA electrode, also operating in the collection mode, was
An antimony UME was used with the SECM apparatus shown to be a sensitive detector under conditions compatible
as a potentiometric sensor for hydrogen ion activity (B82). with an enzyme immunoassay (BIOI). Volumes as small as
General theory was developed and applied to give pH images 800 nL were successfully handled in this study. A clever
around a Pt electrode during the reduction of water, a corroding application of an IDA incorporated an electrochemical
AgI disk in cyanide solution, a disk of immobilized urease coulometer in series with an IDA in a solution of a reversible
hydrolyzing urea, and other systems. The SECM technique redox couple. The coulometric process employed was elec-
was used to characterize solid films of AgBr (B83). The trodeposition of a metal, which was followed by ASV analysis
diffusion coefficient of bromide ion in the AgBr matrix was allowing determination of the redox couple at the M level
deduced from the tip current transients produced when the (B102). IDAs have been used to measure apparent electron
tip/substrate pair was pulsed in a thin-layer electrochemical diffusion coefficients in polymeric matrices: good examples
mode. SECM has also been employed to map ionic fluxes of are the study by Nishihara et al. of poly(ethy1eneoxide) (8103)
electroactive species at various porous membranes including and the redox switching of poly(pyrro1e) films (B104).
mica and mouse skins (B84), to detect proton motion at Several papers have addressed theoretical aspects of various
polyaniline film electrodes (B85),to monitor ion release from array geometries. These include a treatment of the overlap
protonated poly(viny1pyridine) films (B86),and to characterize of diffusion layers at microband arrays (B105),cylinder arrays
a 200-nm-thick polymer film (B87). Surface diffusion and closely aligned parallel to a planar electrode (B106),and dual-
desorption processes are readily handled by SECM. In this cylinder UMEs in parallel operating in a biamperometric mode
application, the probing tip, biased at a potential where the with a small imposed voltage difference (B107). The latter
adsorbate is electroactive, yields a current that is a function theory was applied to the titration of ascorbic acid with
of the rate of diffusion through solution, the adsorption/ ferricyanide.
desorption kinetics, and the rate of surface diffusion (B88). Frequencies as high as 20-30 kHz were used for the
The approach was illustrated by detection of H+adsat rutile- generation of electrochemical luminescence by square-wave
(001) and aluminosilicate surfaces. generation of the radical ions at UMEs (B108). A lower limit
In vivo electrochemistry under physiological conditions, on the ion-annihilation rate constant for diphenylanthracene
which was the original motivation for U M E voltammetry, of 2 X 1O9 M-’ s-l was determined. Double-band UME arrays
has provided some of the most impressive applications of UMEs have also been used to generate ECL in a steady-state mode
in analytical chemistry. The detection of the release of of operation (B109).
386R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
Hydrodynamic Methods. Rotated Electrodes. Verbrugge via oxidation of released B r a t the ring electrode (B129),and
has given a theoretical analysis of the RDE convectivediffusion measurement of enhanced D values due to homogeneous
problem for an Ox/R couple that is valid for a wide range of electron exchange in the RDE voltammetry of Ru-EDTA-
Schmidt numbers and Reynoldsnumbers (BIIO).Thecurrent poly(viny1pyridine) complexes (B130).
response was found to be bounded by the Levich equation for On the more applied side, the photographic fixation process
large Schmidt and Reynolds numbers and by the stationary at a AgCl emulsion disk electrode was followed by monitoring
disk response for zero Schmidt or Reynolds numbers. Vieil the flux at a ring electrode (B131),and a novel RRDE method
developed a general mathematical treatment of mass transfer was described for the detection of COz expired in breath from
that quantifies the transition between stationary convective a human subject (B132).
mass transport and time-dependent accumulation at an Compton and Brown have proposed a RDE method to
electrode surface (BI 11). A mass-transfer rate expression is monitor particle size in solution that is based on the
given that can accommodate a variety of experimental enhancement of mass transport in the presence of suspended
conditions such as fractal geometries and transient behavior particles (B133). Others have studied mass-transfer en-
at RDEs. Simulation of transient diffusion and migration to hancement in a dilute suspension of rotating particles under
a RDE during deposition of a metal film gave information on the influence of shear flow (B134),and Gabrielli et al. treated
the current distribution, the effect of inert electrolyte, and the the ac impedance of fluidized-bed electrodes, both theoretically
role of disk size (B112). and experimentally for gold beads in NaOH solution (B135).
Bartlett and Eastwick-Field have written a particularly In the miscellaneous category are papers on the rotating
cogent analysis of limiting currents at a RDE for a generalized ring cone electrode (B136),mass transfer at the entire surface
ECE reaction scheme (B113). of a vertical cylinder electrode (B137),the use of an inverted
The effect of rotation rate on U M E array composite RDEs RDE for the study of gas-evolving reactions (B138),and mass
was studied using composite electrodes of gold and graphite transfer at a RDE with external forced convection (B139).
particles embedded in Kel-F (BI 14). As expected, significant Wall Jet and Channel Electrodes. R. G. Compton and his
enhancement of true current density was seen at the array colleagues have continued their sophisticated analysis of wall
electrode in comparison to solid electrodes; Le., [(i/area),,,,,/ jet and channel electrodes. As will be noted below in the
(i/area),,~id] > 1, where the active area is used to calculate section on electrochemical detectors for FIA or chromato-
the current density. graphic columns, these configurations have real practical
Several researchers have used rotation rate modulation significance.
techniques in various studies. The rotation rate step method The Compton group has presented theory for the transient
of Blauch and Anson (B115)was applied to a silver electrode current response for a simple E step at a WJE (B140) and at
to determine the diffusion coefficients of electroinactive ligands the ring in a wall jet ring disk electrode (8141). The theory
(BI 16). Anodic 0-transfer reactions at several electrodes was experimentally verified in a later study (B142). They
(Pt, Au, Pd, Ir, and glassy carbon) were studied using a current also developed theory for CV at a WJE where the electrode
difference RDE method that diminished the contribution of is substantially larger than the jet. The theory predicts
0 2 evolution to the observed response (BI 17). A key role for transitions from steady-state CVs at slow sweep rates to peak-
adsorbed hydroxyl radicals was deduced in this study. shaped response at fast sweep rates (B143). The roleof radial
Engelhardt et al. have presented theory for hydrodynamic diffusion in the WJE response has been considered in a more
square-wave modulation of a rotating ring disk electrode recent paper (B144).
(B118-B120). The method is useful when there are parallel Compton et al. have presented a general computational
reactions and the ring current of interest is masked by large approach to calculation of i-E curves at channel electrodes
background currents. In the experiments of Schwartz (B121), (B145)and, in a related paper, calculated limiting currents
the rotation rate of a commercial RDE was modulated by a for UME band electrodes in a rectangular flow channel under
sinusoidal or by a square root waveform. Fourier transfor- conditions where convection is the predominant mode of mass
mation then gave the frequency response of the system in a transport (B146). Tait et al. have also tackled the difficult
single experiment. Hydrodynamic impedance has also been problem of a U M E disk electrode in a flow channel using
employed by Deslouis and Tribollet (B122). finite difference simulation (B147). The effect of electrode
Papers continue to be published that exploit the power of size, solution velocity, and channel thickness on the magnitude
rotating electrodes in mechanistic studies. Rotating ring disk of the near-steady-state currents and the time required to
techniques were used to study the MV2+l+Iosystem (MV is reach this condition were determined in the latter paper. A
methyl viologen) in aqueous solution, where surface blocking treatment of the catalytic EC’ reaction at a flow channel
by adsorbed neutral species had to be taken into account electrode is representative of several articles on coupled
(8123). Likewise, Kokkinidis et al. found that electrodepo- chemical reactions under these conditions (B148).
sition of neutral benzyl viologen onto Pt or Hg proceeded by A four-element carbon paste array detector, which consisted
direct nucleation and 3-D growth under mass transport control of different graphite/metal oxide composite surfaces in a wall
(B124). Other studies include chronocoulometric measure- jet configuration, displayed different electrocatalytic sensitivi-
ment of adsorbed intermediates in the oxidation of iodide at ties toward carbohydrates and amino acids (B149). In another
a Pt RDE (B125),voltammetry of adsorbed intermediates in study, the performance of an array W J E assembly was
the HER (B126), the electrocatalytic oxidation of CN- at a optimized (B150).
glassy carbon RDE (B127), the mediated reduction of an Flow- Through Electrochemical Detectors. Electrochemi-
alkyl halide (BI 28), the detection of the anaesthetic halothane cal detectors for chromatographic or FIA columns (LCEC)
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 367R
are routinely employed. Only a fraction of the recent papers Doherty et al., which is based on redox polymer-modified
that present possible advancements in the methodology will electrodes, nicely performs speciation analysis of Fe(I1) and
be cited here. Fe(II1) (B168). One electrode was coated with a Ru-bpy
The WJE configuration is wellsuited to theLCEC problem. polymer (E1p = 0.75 V vs SCE), which mediated the oxidation
Stojanovic et al. evaluated cylindrical wire, thin-layer, and of Fe(II), and the other was coated with an Os-bpy polymer
WJEdetectors with constant and pulsed amperometric (PAD) (E1p = 0.25 Vvs SCE), which mediated the Fe(II1) reduction.
modes of operation for the determination of inorganic arsenic The latter electrode was also used for the FIA of nitrite ion
(B151). In their hands, the WJE had the best LOD. Other with excellent sensitivity and stability of response (B169).
recent examples of WJE LCEC detection can be mentioned Wang et al. employed self-assembled monolayers (SAMs) of
(B152, B153). It can be noted, however, that the impressive n-alkanethiols on Au electrodes to vary the response of LCEC
sensitivity of carbon-fiber detectors, which has been exploited detectors to analytes such as chlorpromazine in urine samples
in the determination of catecholamines in single bovine (BZ70). The SAM-modified electrodes discriminated against
adrenomedullary cells (B154),is difficult to match. small ionic electroactive species and were stable under the
Electrochemical detection has been applied to capillary hydrodynamic conditions of the flow cells. Mark and
electrophoresis with much success. Sloss and Ewing, for colleagues (B171), and others (B172), have found that
example, have improved their methods by enlarging the end conducting polymer film electrodes show improved perfor-
of the capillary to accommodate a larger UME. Problems mance in terms of sensitivity and antifouling properties for
with variation of the capillary/electrode alignment were also the detection of ionic species.
minimized with their new design, which gave detection limits Numerous examples of chromatographic analyses employ-
as low as 11 amol for catechol (B155).Lunte and co-workers ing electrochemical detection can be found in the forests of
have given details on the construction of a complete capillary chromatography literature. Examples of pulse amperometric
electrophoresis system with electrochemical detection (B156). detection include a study of the sulfur compounds cysteine,
They found that a 50-pm-diameter Au(Hg) amalgam UME cystine, methionine, and glutathione, all of which were detected
functioned well as a C E detector for free thiols (B157). Lu in human blood samples using simple LC PAD procedures
and Cassidy evaluated several UMEs in a WJE configuration (8173). PAD and HPLC/MS were employed in comple-
as detectors for capillary electrophoresis columns. Not mentary fashion for the analysis of aminoglyoside antibiotics
unexpectedly, mercury amalgam electrodes gave the best (B174); SO2 has been analyzed in beer by IC with PAD
performance for 14 test metal ions (8158) and PAD at a Au detection (B175);and HPLC of amino acids using PAD had
UME worked well on the anodic side (B159). excellent sensitivity and required little to no sample preparation
Mahoney et al. modified a commercial stationary mercury (BI 7 6 ) . Johnson and co-workers have published two papers
drop electrode apparatus so that square-wave voltammograms refining their PAD methodology. In one, pulsed voltammetry
could be obtained under stopped-flow conditions (B160). at a RDE was used to optimize the potential and time
Rapid-scan voltammetry at a UME detector was shown to parameters for the PAD waveforms (B177), and the second
give theoretical steady-state CVs under chromatographic gives construction details for a simple low-cost LCEC detector
conditions (B161). Trade-offs in sweep rate, UME diameter, employing a gold working electrode (B178).
and flow rate were evaluated. Other examples of LCEC that caught your reviewer’s eye
Two groups have put 16-element LCEC amperometric were a fast-scan voltammetric detection of fullerenes (BI 7 9 ) ,
detectors to good use. In the study of Sparks and Geng, detection of underivatized polypeptidesusing constant potential
detection over a potential window of 0.75 V greatly increased amperometry (B180), and the coulometric detection of
the information content of a single chromatogram (B162).In neurotransmitters and respiratory metabolites in brain tissue
the impressive work of Aoki et al., 80-channel detection was (B181).
achieved by application of a five-step E-staircase waveform Zhu and Curran considered porous flow-through ampero-
with 10-mV step heights to the 16 elements oft he array (8163). metric detectors under conditions of low conversion efficiencies
IDAs operated in the dual-electrode mode were shown to have (B182). RVC electrodes were used to test the theory which
good sensitivities as flow detectors: 100 pM dopamine was predicted that the limiting currents were proportional to the
detected under HPLC conditions (B164). An advantage of 2 / 3 power of the pore diameter. A UME biamperometric GC
this mode of detection is that the component of the current detector was evaluated (B183).
due to redox cycling is flow rate independent.
Descriptions of several novel spectroelectrochemical flow C. ANALYTICAL VOLTAMMETRY
detectors have appeared. Brown et al. used anodic photo- Methodologies. The year 1992 marked the 40th an-
currents at Ti02 to detect species with redox potentials more niversary of the publication of the seminal article by Barker
negative than the valence band edge of the semiconductor at and Jenkins on square-wave polarography. This paper was
the 100-pmol concentration level (B165). Another flow cell reprinted by the Analyst in honor of the event (C1), along
was based on indirect detection of eluents by the decrease in with a retrospective by Barker and Gardner (C2). The
the intensity of electrogenerated luminol chemiluminescence development of square-wave voltammetry (SWV), as well as
(B166). Also, a pulsed flash photolysis amperometric detector other electroanalytical techniques, has continued over the past
was described that appears to have some promise as a general two years. For example, Chin et al. ( C 3 ) reported on the
purpose LCEC detector (B167). mathematicalenhancement ofSWV. Lovricet al. (C4)treated
Several papers have proposed various surface modifications theoretically the use of SWV in cathodic stripping, while
to improve LCEC response. The dual-electrode sensor of Komorsky-Lovric et al. (C5)looked at peakcurrent/frequency
Analytical Chemistty, Voi. 66, No. 12, June 15, 1994 389R
reported. Wang et al. investigated the use of mercury-coated Wang and Tian (C91) developed a mercury-free disposal
carbon foam composite electrodes (C57), vitreous carbon lead sensor based on potentiometric stripping voltammetry
aerogel electrodes (C58), and screen-printed stripping elec- using gold-coated screen-printed electrodes. Xie and Huber
trodes (C59). Frenzel (C60) discussed the attributes and (C92)used constant-current enhanced potentiometric stripping
problems of using mercury films on a glassy carbon support. voltammetry for the analysis of cadmium. Potentiometric
Ultramicroelectrodes have also been applied to anodic stripping stripping voltammetric techniques were also developed for
analysis. A mercury ultramicroelectrode electrode was used the determination of cadmium and lead in whole blood (C93),
by Peng and Jin (C61) to determine lead in a sample-limited copper and lead in tap water (C94), and manganese (C95).
analysis (e.g., 1 mg of hair). Gold fiber microelectrodes were Komorsky-Lovric and Branica (C96)compared potentiometric
used to determine mercury in high-purity gallium arsenide stripping voltammetry and square-wave voltammetry with
(C62)or waters and fertilizers (C63),mushrooms (C64),and respect to the influence of Triton X- 100. Aldstadt and Dewald
selenium( IV) in blood serum (C65). Copper (C66)and lead/ (C97) studied the effect of model organic compounds on
cadmium (C67) were determined in the absence or presence potentiometric stripping voltammetry with a cellulose acetate
of low concentrations of supporting electrolyte. Kouvanes membrane covered electrode.
and Deng (C68)examined the use of an iridium-based mercury Catalytic Methods. The combination of preconcentration
ultramicroelectrode with square-wave anodic stripping vol- of the analyte in stripping analysis and enhancement of the
tammetry. signal by use of a catalytic reaction (dual amplification)
The effectiveness of various methods to remove interfer- provides for a very attractive approach to develop extremely
ences in anodic stripping voltammetry was examined. The sensitive electroanalytical methods. Some examples of this
influence of complexing agents on the effectiveness of methodology have been recently reported. One elegant
electrochemical masking with anionic surfactants was ex- approach is to use a complexing agent that is, itself, an oxidizing
amined by Opydo (C69). The detection of Ga-Zn interme- or reducing agent in the stripping step. This technique was
tallic compounds and its removal with antimony was reported used in the analysis of chromium (C98),molybdenum (C99),
by Cofre and Brinck (C70). Surfactants were used to suppress and thorium (C100) using cupferron as the ligand for
the indium peak in the determination of lead in samples that adsorptive stripping voltammetry as well as the catalytic
contained large concentrations of indium (C71). A photo- oxidizer in the stripping step. In addition to cupferron, organic
chemical process was reported by Barisci and Wallace (C72) hydroxy acids (CIOI) and chlorate (mandelate as the ligand)
for the removal of oxygen in flowing solutions. Photochemistry (C102)were used to determine molybdenum. Iron in seawater
was also used in sample preparation of heavy metals in peat was determined by cathodic stripping with 2-nitroso-2-
(C73),while a digestion method for soil samples was reported naphthol and the use of hydrogen peroxide as the oxidizing
by Fernando and Plambeck (C74). Systematic errors due to agent in the stripping step (C10.3). Bobrowski and Bond
adsorption of metal complexes onto cell components were (C104) combined adsorptive stripping voltammetry of a cobalt
investigated (C75). Sodium and other impurities in alkoxy- complex with the catalytic effect of nitrite on the stripping
silanes were determined by anodic stripping square-wave wave to enhance the sensitivity of the cobalt analysis. The
voltammetry (C76). catalytic reaction, alone, without prior accumulation, was used
Metals are generally the most likely candidates for by Hsieh and Ong to determine molybdenum by differential
determination by anodic stripping voltammetry, but there are pulse polarography (C105), and by Jiang et al. (C106) to
several reports on the determination of organic compounds, determine nitrite.
either directly or indirectly. Cholesterol in blood serum was Derivatization Methods. The efficient conversion of
found to be amenable to anodic stripping voltammetry (C77), electroinactive compounds to eiectroactive materials or to
as were ionic alkyllead compounds in natural waters (C78). change the redox potential of electroactive materials can be
An indirect method for the analysis of NTA and EDTA in exploited to develop new electroanalytical methods. For
natural water by means of a bismuth complex was reported example, reactive organic halides can be determined at low
(C79)* levels via in situ generation of S-alkylisothiouronium salts
The bulk of the reports on cathodic stripping voltammetry (C107) with differential pulse polarography. Similarly,
has involved the determination of halides and chalcogens. For ethanol (CI08),amines ( C I 0 9 ) ,and amino acids (CIIO)can
example, total inorganic iodine in seawater (C80) or a variety be determined via in situ generation of dithiocarbamates.
of sulfur species such as thiols, sulfides, cysteine, and cystine Oxalate can be determined by differential pulse polarography
(C81) were also determined. Wang and Lu (C82) reported after derivatization with o-phenylenediamine (C11I ) . Sul-
on the ultratrace measurement of selenium in the presence of fanilic acid was converted into an azo compound prior to
rhodium. A mercury-coated carbon-fiber electrode was used differential pulse polarographic measurement (CI 12). Somer
for the determination of selenium(1V) in blood serum (C83). and Kocak developed a method for the differential pulse
Smyth et al. (C84) reported on the determination of organic polarographic determination of sulfur dioxide using selenite
and inorganic selenium compounds, while Kotoucek et al. (C113). The reaction of ammonia with formaldehyde was
(C85) determined arsenic. Organic compounds such as used as the basis for the analysis of ammonia in seawater
cytosine 3’-phosphate (C86), thiamine (C87), pentamidine (CI 1 4 ) . The formation of nickel complexes with ampicillin
isethionate (C88), and glutathione in natural waters (C89) and amoxycillin led to a selective differential pulse polaro-
were amenable to cathodic stripping voltammetry. The graphic method (CI15).
adsorption of “reduced COZ”on platinum was the basis of a Analytical Use of Micelles. Micellar and emulsified media
new technique for the determination of carbon dioxide (C90). provide an efficient method for solubilization and transport
Analflical Chemistry, Vol. 66, No. 12, June 15, 1994 377R
Several articles with innovative aspects have appeared of surface crystal structure on interfacial phenomena and the
describing carbon-based working electrodes. DNA-modified study of surface reconstruction reactions. It is now clear from
glassy carbon, immobilized via covalent bonds between numerous examples that surface structure can have remarkable
deoxyguanosine residues and surface carboxylate groups, effects on the mechanisms of a wide variety of electrode
functioned as an electrochemical probe for the complementary reactions. In many cases this has provided great detail on the
oligonucleotide strand (E124). The electrochemical signal nature of intermediates and key steps in these processes. In
was that of C0(phen)3~+/~+ preconcentrated by the double- addition, in the past year or so there have appeared several
strand hybrid structure. McFadden et al. prepared carbon really elegant applications of the new surface microscopies,
electrodes by pyrolysis of natural gas onto Macor, a machinable e.g., STM and AFM, to the study of phenomena at single
ceramic substrate (E125). ET rates on these surfaces for the crystal interfaces.
Fe(CN)63-/4- couple were comparable to those obtained on Platinum(n,n,n). Examples of surface structure-sensitive
conventionally polished GC. A highly active electrocatalytic reactions are the oxidation of small organic molecules such
porous carbon surface for 0 2 reduction was prepared by as glucose (E146), squaric acid (E147), and ethylene glycol
adsorbing anionic Co complexes into oxidized poly(pyrro1e) (E148)at Pt single crystal electrodes in aqueous acid solution.
followed by heat treatment at 820 "C under nitrogen (E126). In the work of Llorca et al. (E146), voltammetric currents
A TEMPO-modified graphite felt electrode was used for the were correlated with edge site processes. Different crystal
efficient electrocatalytic coupling of methylquinolines ( E l 27). faces of a working electrode will display widely different
Wang et al. (E128) evaluated epoxy-composite pellets as activities under identical conditions. For example, Pt( 1 10)
voltammetric working electrodes that were fabricated from was found to be most active for the oxidation of squaric acid
carbon aerogel foams with high surface area and ultrafine (E147) and ethylene glycol (E148), while P t ( l l 1 ) was the
pore sizes (C50 nm). Two groups have used boron-doped most active for the electrooxidation of glycerol in alkaline
diamond films as working electrodes (E129, E130). The solution (E149). For the oxidation of glucose, Tafel slopes
reduction of nitrate to ammonia in alkaline solution proceeded of 120 and 60 mV were obtained on Pt( 11 1) and Pt(100),
withgood Coulombicefficiencyat oneofthesesurfaces (E130). respectively, along with different adsorbed intermediates,
Screen-printed carbon electrodes have been promoted as gluconolactone on Pt( 11 1) and CO on Pt( 100) (E150). On
amperometric sensor electrodes (E131, E132). Conducting the other hand, the oxidation of glyoxylic acid in H2S04(aq)
salt/silicone oil paste electrodes (E133) and metal-dispersed was reported to be mostly insensitive to the structure of Pt
carbon paste electrodes (E134) were found to be electro- single crystal electrodes (E151).
catalytically active. On the cathodic side, in situ electrochemical mass spec-
Studies on adsorbed molecules on graphite electrodes are troscopy (EC-MS) clearly showed that only the Pt(100) face
cited here and in the vast section F below on modified was active for the complete hydrogenation of benzene to C6H12
electrodes. The properties of ruthenium(II1) oxide and cyanide (E152). Benzene was desorbed from the (111) face and
films on carbon substrates for electrocatalytic oxygen atom partially desorbed from the (100) face. Another EC-MS study
transfer reactions has been examined. Mixed-valent also revealed significant differences in the operative mecha-
Ru( II1,IV)-oxo centers were found to show specific reactivity nisms for the oxidation of ethylene on Pt( 11 1 ) and P t ( l l 0 )
toward As(II1) and CH30H oxidation (E135). Pyrolyzed Fe surfaces (E153).
and Co tetraphenylporphyrins and Fe- and Co-crowned Interestingly, oscillatory phenomena have been reported
phthalocyanines were evaluated with respect to electrocatalysis to be structure sensitive. Potential oscillations were seen during
of the 0 2 reduction (E136, E137); covalently attached the oxidation of formic acid on Pt(100), but not on P t ( l l 1 )
Co'Itetraphenylporphyrin on glassy carbon effectively elec- (E15 4 , and during the electrocatalytic oxidation of H2 in the
trocatalyzed the reduction of C02 to C O (E138);an adsorbed presence of Cu(I1) and C1- at Pt( 11 1) and Pt( loo), but not
Cu-phenanthroline complex on graphite electrocatalyzed the at Pt( 110) (E155).
reduction of 0 2 and H202 via an EE mechanism (E139- For inorganic systems, well-defined voltammograms for
E1 41); an adsorbed electroactive alizarin quinone, with the H N 0 2 / N O were obtained at Pt( 11 l ) , but not at Pt( 100) or
ability to complex Fe(III/II) couples, mediated the reduction P t ( l l 0 ) surfaces (E156). Rodes et al. (E157), however,
of 0 2 and H202 at graphite electrodes (E142);and chloro- reported irreversible oxidative adsorption of N O in a CV study
(phtha1ocyanine)rhodium complexes on HOPG underwent a of the reduction of nitrite at Pt( loo), and reduction of N02-
slow solid-state electrodimerization that was coupled to the and NO to NH3 proceeded with an efficiency of >80% at
surface redox chemistry ( E 1 4 3 ) . Finally, in several studies Pt( 100) surfaces (E158). For hydrazine oxidation in acid,
Bond and co-workers have obtained meaningful voltammetry stable irreversibly adsorbed species were found at Pt( 1 lo),
of water-insoluble compounds by mechanically transferring while reversible adsorption, without charge transfer, occurred
them to solid graphite electrode surfaces where surface redox on Pt(100) and P t ( l l 1 ) (E159). Nishihara et al. found
reactions could be carried out in aqueous electrolyte solutions competitive adsorption with H+ on both terrace and step sites
( E 1 4 4 , E145). for the oxidation of hydrazine at Pt(332) and P t ( l l 1 ) in H2-
Single Crystal Surfaces. On the basis of the number of SO4,aq) ( E I 6 0 ) .
papers and their volume, surface electrochemists have been The adsorption of HS04- (E161, ,5162) and phosphate
busy researching a variety of well-defined single crystal ions (E163)on Pt was sensitive to the surface geometries. The
electrodes in the last two years. Interlaced with diligent effort hydrogen region electrode process in NaOH(,,) was found to
at characterization of the interfacial structures and mechanistic be strongly dependent on the exposed crystal planes at Pt
phenomena are two major themes: documentation of the role low-index and stepped surfaces ( E l 6 4 ) . Adsorbed Pd atoms
300R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
produce a surface species, probably adsorbed chloride, that used to follow the electrochemical formation of PEO (E282),
inhibited hydrogen adsorption (E266). while S T M images of poly(N-methylpyrrole) were noisy,
Only negligible electrocatalysis was seen for the oxidation probably because the STM tip typically was buried in the
of methane when surface oxides and/or silver were deposited poorly conducting polymer film (E283).
on Ru(001) electrodes (E267). Wang et al. have described Sugimoto et al. used the Bard SECM technique in a direct-
a neat procedure for the preparation of Ni( 11 1) surfaces for scanning mode to obtain images of a Prussian blue film
electrochemical study. The surfaces, which were formed under electrode that showed cracks and grain boundaries at the
UHV conditions, were protected with a layer of adsorbed CO submicrometer level (E284). Engstrom et al. employed SECM
prior to transfer to solution and electrochemical stripping of to map the local electron-transfer kinetics of reactions
the C O (E268). The UPD of T1 and Pb on Cu( 111) films occurring at kinetically heterogeneous Pt disks or epoxy
evaporated on mica surfaces was reported (E269), and an impregnated RVC electrodes (E285). Several other applica-
AFM study of potential-controlled oxygen adsorption on tions of the SECM technique have been cited above in the
Cu(100) has appeared (E270). STM images were obtained sectionon UMEs. The improvement in the technique involving
of the silicon( 11 1) hydride phase that was revealed when an small-amplitude modulation of the tip position seems especially
oxide layer was removed under potential control in HFg,) important (B75,E286). This permits automaticdetermination
solution (E271). of whether a surface is insulating or conducting.
Surface Imaging Techniques. As is evident in the previous Among the many applications of STM to electrochemistry
section, surface electrochemists have been applying the various are several reports of STM images of dissolving electrodes
surface microscopies to the study of electrode interfaces since (E287, E288), of metal particles deposited in the pores of
the initial introduction of these techniques. The student anodic aluminum oxide films (E289),and of electrochemically
wishing a more complete compilation of references on this grown organic semiconductors (E290). In situ STM/Echem
topic should scan citations from the above sections on UMEs of silver electrodes revealed time-dependent smoothing of the
and single crystal electrodes. The articles mentioned here are surface during redox cycles (E291), and the fractal dimen-
perhaps more technique oriented, although the distinctions sionality of Au and Pt electrodeposits was determined (E292).
are often arbitrary. STM images of DNA molecules have been obtained on
Vogel et al. published beautiful S T M images of Pt single Au(ll1) surfaces under potential control (E293). This
crystal electrodes subjected to the “iodine procedure” both in particular application, and related methodology (E294),
air and in electrolyte solutions (E272). The images, which promises to become popular in molecular biology fields.
were in accord with previous LEED ex situ results, were Fluorescence imaging of electrode surfaces was achieved
obtained using a noncommercial STM apparatus, details of by generation of OH- in weakly buffered solutions of
which were given. A prospectus for STM/electrochemistry fluorescein. Thus, reduction of H2O or 02, the latter at
has been published that contains many examples and impres- cathodic corrosion sites, converted the dye into a strong
sive STM images (E273). Schmickler and Widrig presented fluorescing species and produced images of the electrode
some theoretical considerations of the STM/Echem experi- surface (E295). Miller et al. imaged L-B monolayer films
ment (E274). The Poisson-Boltzmann equation was solved of a Ru-bpy surfactant by observing ECL with a sensitive
for a sphere-plane configuration as a model for the tip- CCD camera (E296). Finally, local ac impedances were
substrate geometry (E275). obtained by measuring the potential difference between two
Techniques for STM tip sharpening and related applications microelectrodes in a probe assembly (E297).
were extensively reviewed (E276). A combination of normal PolycrystallineElectrodes. An interesting comparison of
sharpening procedure under ac voltage with the tip oriented chronocoulometry, radiochemistry, and Raman spectroscopy
downward, followed by further sharpening with the tip oriented applied to the measurement of pyridine adsorption on gold
upward, was found to be effective for tungsten tips. Oxide electrodes has appeared (E298). Agreement was found
layers on tungsten tips are easily removed in concentrated H F between surface concentrations determined by the first two
(E277). Details were given for the preparation of STM tips techniques, but chronocoulometry, where double-layer, not
with reduced capacitive currents for use in a differential faradaic, charge densities were measured, gave the better
conductance mode of operation (E278)and for electrocoating precision. Adsorption of HS04-, C1-, and I- on Pt was
STM tips with polyacrylic carboxylic acid (E279). measured by three in situ methods: radiotracers, FT-IR, and
Surface microscopes have been used in novel ways to ellipsometry (E299). Bell-shaped adsorption isotherms were
characterize and/or to spatially modify film electrode inter- reported for 20 organic compounds on Pt (E300),and the Epzc
faces. For example, Murray’s group has reported a procedure values and capacitance minima for Au were measured in
to produce spatially patterned, laterally heterogeneous polymer- NaF(,,) using a piezoelectric technique (E301). An extensive
modified electrodes using in situ AFM (E280). They used set of double-layer data at various metal electrodes in DMSO,
an AFM tip to “nanodose” a defect in a thin film of insulating DMF, PC, AN, MeOH, and H 2 0 was collected and used to
poly(pheny1ene oxide) (PEO). The defects were then filled analyze metal/solvent interactions and the interfacial solvent
by electropolymerized conducting polymers. Yang et al. structure (E302).
proposed a STM technique to measure the thickness of polymer Among the papers on the oxidation of methanol at solid
films on conducting substrates. The plot of tip current vs tip electrodes are a study at mixed oxides of Pt and Sn (E303),
displacement exhibited linear regions due to (i) approach to a study of the effect of Ru deposition where RuOHad,
the surface, (ii) penetration through the film, and (iii) contact intermediates were proposed (E304),a study of the effect of
with the substrate (E281). In situ AFM was successfully adsorbed Sn atoms (E305), a detailed examination of the
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 381R
process at Pt-Ru alloys (E306), and a report of the use of tions were period, 58 s; current, f 2 . 5 PA; and emf, f 5 0 mV
hydrophobic nickel electrodes coated with fine particles of (E330).
tetrafluoroethylene (E307). In situ FT-IR spectra revealed The formation and growth of metal oxide films have been
several intermediates in the process at Pt, including three studied by a variety of methods including voltammetry, ac
forms of adsorbed CO, a COH species, and a CH-containing impedance, and EQCM. These include investigations of Pt
species (E308). Surface-enhanced Raman spectra also have electrodes (E331-E336), gold electrodes (E337-E340), and
been obtained for this system (E309). Pd electrodes (E341, E336). EQCM data indicated that the
The surface electrochemical behavior of three isomeric gold dissolution rate upon E cycling in H2S04(aq)was 550
pyridyl hydroquinones at polycrystalline Pt (and at P t ( l l 1 ) ) ng/h (E337).
was dependent on the orientation of the adsorbed monolayers
In the miscellaneous category, the relationship of area to
(E310). Oxidation of ethylene glycol gave different product
volume of dendritic Ag deposits on polycrystalline Pt was
distributions on Au, Pt, and Ni electrodes (E311). FT-IR
found to exhibit fractal behavior with area = k ( ~ o l ) ~where
/~,
spectra indicate C2 solution intermediates in route to oxalate
and carbonate ions on gold electrodes, while formate was
D = 2.50 f 0.03 (E342). This value is consistent with a
formed to the greatest extent on Ni. The electrocatalytic self-similar fractal surface. Finally, a description of a guillotine
oxidation of toluene was seen at coatings of deposited hydrated electrode, which was tested on A1 electrodes in aqueous
platinum oxides on Pt, Ni, Ti, Fe, and glassy carbon supports solution, was noted (E343).
(E312). Two pathways were described for the oxidation of Miscellaneous Electrodes. Several reports have appeared
phenol at Pt: one occurring at the inner Helmholtz plane, that featured superconducting working electrodes. Plots of
where ring cleavage took place, and one occurring at the outer cdl vs T for two T1-based high-T, superconductors immersed
layer, where a mixture of products was formed (E313). in fluid electrolyte solutions displayed abrupt changes in the
Squaric acid oxidation on Pt gave extensive formation of toads region of Tc ( E 3 4 4 ) . An increase in faradaic current was
and COz products over a wide potential range (E314). observed for high- Tc superconducting electrodes in contact
Oxidation of surface mercaptoethanol films at Au proceeded with Ag+ ion conductors at low temperatures ( E 3 4 5 ) . A role
by multiple pathways (E315). was suggested for Cooper pairs crossing the double layer and
Evidence was presented to indicate that the first monolayer participating in the electrode reaction. A quasi-reversible,
of adsorbed thionine is electroinactive at Pt. On sulfur- almost irreversible, CV for the ferrocene+/O couple was
modified Pt, however, the first layer of adsorbed material is obtained at a Bi-Pb-2223 superconducting UME at 102 K
electroactive (E316). In similar fashion, sulfur adlayers on (E346). Kuznetsov developed theory explaining the increase
Pt changed the irreversible phenothiazine oxidation into in current in the Tc region for superconducting electrodes
reversible CV behavior (E317 ) . (E347).
RDE and QCM measurement gave new insights on the Conditions were given for the anodic electrosynthesis of
well-studied iodine/iodide system at Pt in H2S0qaq)(E318). millimeter-sized crystals of Bao.sKo.4BiO3with Tc values of
Michelhaugh et al. found that even submonolayer coverages 30.5 K (E348). Superconducting thin films of Y-Ba-Cu-0
of adsorbed iodine gave fast kinetics for the quinone/ and T1-Ba-Ca-Cu-0 were electrodeposited at negative
hydroquinone couple, which they took to indicated selective potentials in DMSO solution (E349). Electrochemical Li-
ET at iodine surface sites (E319). Anodic 0-atom transfer doping of high- Tcsuperconducting films resulted in an increase
electrode reactions were proposed for the oxidation of I- to in a lattice constant and/or the T, value (E350). Electro-
IO3- at Pt, Au, Pd, Ir, and glassy carbon (B117),for anodic polymerization of aniline on the surface of YBa2Cu3O,-a
reactions at PbOz electrode doped with acetate (E320), for produced a film with protective properties (E351). More
the oxidation of oxysulfur anions at PbO2 (E321),and for the interestingly, redox cycling of poly(pyrro1e) coated on thin
determination of As(II1) at Pt where a key role was assigned
superconducting films reversibly changed the Tc value by
to PtOH (E322). Anodic Cl2 evolution at Pt was reported to
almost 15 K (E352). The Cu(III/II/I) system was examined
take place on an oxide-freesurface in anhydrous trifluoroacetic
at the latter surface (E353), and Ma et al. successfully
acid (E323).
electrodeposited Cu contacts onto a superconducting substrate
Oscillating phenomena continue to stimulate electrochem- (E354).
ists, who have usually fingered CO,d, as a key intermediate
in their mechanistic speculations (E3244E327). Wolf et ai. Several interesting working electrode materials containing
modeled the oscillating electrochemical reduction of peroxo- titanium have been studied in the last two years. Titanium
disulfate by a system of nonlinear differential equations based diboride, an electroconductive ceramic, exhibited a wide
on a Nernst diffusion layer treatment for a diffusion current potential window and was used for the reduction of C02
term and a Butler-Volmer expression with a Frumkin (E355). Ebonex, a conducting ceramic mainly composed of
correction for the charge-transfer term (E328). Good agree- the Magneli phase of titanium oxides Ti407and TiS09,coated
ment between theory and experiment was obtained. The with PbO2, was found to be a suitable anode for ozone
potential oscillations seen in the galvanostatic oxidation of generation (E356). A previous report from Pletcher’s group
formic acid on Pt were directly coupled to frequency oscillations had described conducting titanium oxide ceramic electrodes
in the EQCM experiment (E329). Finally, a true ac battery (E357). Polycrystalline thin films of cubic BaTi03 were
was based on an ingenious concentration cell that consisted prepared on Ti metal substrates by several methods, including
of two mass-coupled oscillating half-cells. Typical specifica- an electrochemical anodization in Ba(OH)2 solution (E358).
382R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
F. MODIFIED ELECTRODES Donnan partitioning at the membrane/diffusion layer inter-
Charge Transport in Polymer Films. Several important face.
papers on this topic have appeared in the last two years. Impedance techniques have been refined for the analysis
Attention is also called to the review of Inzelt, who has surveyed of charge transport in polymer film electrodes and successfully
theory and experiment up to ca. 1992 (A40). Fritsch-Faules applied, notably by Pickup and Albery and their respective
and Faulkner simulated lateral charge transport in a thin film co-workers. Ren and Pickup have published several studies
of redox centers electrostatically held in a polymer matrix where they used a transmission line equivalent circuit to
( F I ) . Their model allowed for partitioning between the film analyze charge transport in ion exchange polymers based on
and solution, which opened two diffusional paths for the ions poly(pyrro1e) (PPy) (F9-FI 1). They employed a porous
in the charge transport process. In a nice experimental study, electrode model and generally found that ion mobility limited
they determined the concentration profiles in methyl- the charge transport. A good example is their study of polymer
quaternized poly(viny1pyridine) (PVP) films containing the films of 3-methylpyrrole-4-carboxylicacid, where ion mobility
Fe(CN)&/”couple by means of potentiometric measurement was lo3faster than electronic conductivity (F9). The results
at arrays of 4-pm-wide Au electrodes in contact with the film were interpreted using a two-phase model in which ion
(F2). The concentration profiles under steady-state current transport was due to counterions in the polymer phase and
flow between flanking electrodes were linear. The calibration excess electrolyte in the pores. Fletcher also used a porous
curve relating potential to concentration was established by electrode model to interpret impedance data for conducting
chronocoulometry in a companion paper (F3). The behavior polymer electrodes (F12, F13). In a similar fashion the
was found to be Nernstian in spite of (i) different extent of transmission line model of Albery and Mount was based on
partitioning of ferri- and ferrocyanide, (ii) oxidation-state- a porous electrode with organic polymer and aqueous pore
dependent mass transport, and (iii) nonideal CV behavior. phases (F14). Resistances were obtained due to bimolecular
The charge transport was dominated by diffusion of the redox electron exchange and anion buildup in the film. In another
species through solution since the diffusion coefficients were treatment of polymer film ac impedance, they proposed a
2-3 orders of magnitude greater in solution than in the film. transmission line model in which there were separate resistive
The experiments of Larsson et al. (F4) on PVP films containing rails for the cation and for the anion (F15).This would apply
Fe(III/II) redox sites either directly bound to pyridine groups to the common situation when electron motion along the
on the polymer or electrostatically bound to quaternary polymer backbone is faster than ion conduction in the pores.
pyridinium sites relate to this model. In the former situation, Mathias and Haas have developed theory for ac impedance
the apparent charge-transfer diffusion constants (DcT)were of redox polymer films under conditions where either electron
almost 100times smaller than in the more typical ion-exchange hopping or ion migration is slow relative to the other (F16).
polymer. They assumed Donnan exclusion permitting only one mobile
The dynamics of electron hopping in assemblies of redox ion in the film. These authors have studied PVP films
centers has been treated in a major contribution that is containing Os(bpy)z centers under conditions of four bathing
pertinent to charge transport in fixed-site redox polymers (F5). electrolytes where the charge transport was via electron and
The authors found that when physical motion of the redox anion motion only (F17). (This paper gives a nice summary
centers was either nonexistent or much slower than electron of the procedures for extracting parameters from raw
hopping, charge propagation was fundamentally a percolation impedance data.) In contrast to the above situations, ion
process, in which electron hops occur between a random transport in these films was found to be much faster than
distribution of redox center clusters. In another paper, Blauch electron hopping, even for large anions such as toluene-
and Saveant modeled the charge transport by random walk sulfonate.
of electrons through redox molecules in square and cubic The impedance response of poly(pyrro1e) bilayers, with
lattices (F6). Below a critical concentration, finite cluster perchlorate and poly(styrenesu1fonate) counterions, indicated
size makes charge transport impossible. Further, in their that the redox reaction was outside-inside, i.e., began at the
treatment, the mean-field physical diffusion model of Dahms polymer/solution interface (F18). This was consistent with
and Ruff was shown to be inapplicable to systems in which a porous electrode model and with the redox polymer model
the contribution of physical diffusion to charge transport is of Albery et al. (F19). On the other hand, a chronopoten-
small compared to that of electron hopping. Rapid bounded tiometric study concluded that an inside+mtside mechanism
diffusion in systems where the redox centers are irreversibly was operative for lightly doped PPy (F20).
attached to the supramolecular structure, on the other hand, Sharp et al. gave a clear account of the interpretation of
gives rise to mean-field behavior when it exceeds the rate of impedance data for Nafion film electrodes containing
electron hopping. O~(bpy)3~+/*+ and substituted ferrocene couples (F21). The
In another approach, Mohan and Sangaranarayanan dependence of the redox conductivity on the overall oxidation
incorporated an exponential dependence of electron hopping state of the film, in their view, was in agreement with an
rates on distance into a generalized diffusion/migration ion-pairing model in which electron hopping took place
equation for redox film charge transport (F7). Also Deiss et between, for example, a neutral Os(I1) site and a positive
al. published a quitegeneral digital simulation of redox polymer Os(III)+ site. Forster and Vos have reported correlations
CVs (F8). Their calculation accounted for mass transport by between DCT and the heterogeneous electron-exchange rate-
diffusion and migration, electron hopping by a Saveant ( k o )for two redox polymers containing Os(III/II)-bpy sites
mechanism, homogeneous reactions in the film, heterogeneous (F22, F23). The effect of the extent of loading of
reactions and C,-Jat the membrane/electrode interface, and O~(bpy)3~+/*+ in Nafion was significant when the amount of
Analytical Chemistry, Vol, 66, No. 12, June 15, 1994 383R
Os was greater than one-third of the available anionic groups gels ( F 4 1 ) . In spite of high gel viscosities, high diffusivity in
necessary for charge neutrality in the oxidized state. In this thecontinuous aqueous phase was invoked to explain the data.
case, the CVs exhibited two waves: a reversible surface wave Electrocatalysis at Modified Electrodes. This subject, a
for the Os(III/II) couple and an irreversible wave at greater raison d'stre of modified electrode research, has seen relatively
potentials that involved ejection of the complex from the film little theoretical activity in the last two years. The general
(F24). The ejection was elegantly verified by SECM using treatment of electrocatalysis at polymer-modified electrodes
a UME probe positioned above the film. containing microparticles stands out however ( F 4 2 ) . Equa-
Mao and Pickup used RDE voltammetry of ferrocene to tions were derived for the flux as a function of the number
measure the potential profile across a substituted poly(pyrro1e) of particles per unit volume, the film thickness, the substrate
film. The gradient was nonlinear, which they took to indicate and mediator concentrations, and the particle radii. Eight
nonmetallic conductivity where the charge transport process cases were described, along with the respective flux equations,
is driven by a concentration gradient of oxidized sites in the that differed in the reaction orders with respect to the above
polymer matrix ( F 2 5 ) . experimental variables. In a second paper on metal oxide/
Aoki and Heller measured apparent electron diffusion Nafion composite amperometric sensors, the kinetics were
coefficients in a cross-linked redox polymer that contained cast in the context of the Michaelis-Menten formalism (F43).
Os(bpy)2 redox sites. In their interpretation of the data, they Anson and Xie have addressed several important aspects
invoked hydration effects that were induced by counterions, of data analysis for the estimation of rates of cross-reactions
ionic strength changes, or protonation of basic groups on the that occur during electrochemical catalysis at polymer-
polymer backbone (F26). Water transport was noted in modified electrodes using the Koutecky-Levich equation (F44,
EQCM studiesof PVPfilms containing Os(III/II)-bpy centers F45). In a later paper, a modified kinetic model, which
(F27) and poly(viny1ferrocene) films (F28, F29). Slow assumed an array of film mediator couples with a Gaussian
structural changes for related polymer films were seen when distribution of Eo' values, was developed (F46). When the
the electrodes were transferred between perchloric and parameters of the distribution were selected to fit the i-E
toluenesulfonic acid solutions (F30). For poly( l-hydroxy- curve for the non-Nernstian surface wave of the mediator
phenazine) films, the typical featureless CV was shown to couple, significant improvement in the agreement between
involve two ion-exchange coupled steps: one with proton experimental and calculated currents was obtained for several
transport and the other with anion uptake and solvent loss cases involving redox couples in Nafion coatings.
(F31). Hydration effects were also noted for the solid-state Numerous articles continue to be published on various
charge transport in hexacyanoferrate films with fixed polymer-modified electrodes designed to be catalytic for
Fe(III/II) sites ( F 3 2 ) . specific processes. The ones cited here will be organized in
An equivalent circuit proposed for the interpretation of terms of the electrode reaction catalyzed and not by the nature
impedance data at redox polymer electrodes contained two of the polymer matrix. Electrocatalysis of 0 2 reduction was
capacity terms: one for the substrate/polymer interface and achieved at a porphyrin ligand coordinated by four Ru(NH3)5
one for the polymer/solution interface (F33). Also the effect groups in Nafion (F47), and by metal phthalocyanines in
of surface roughness of the substrate on the impedance of various matrices (F48-F50). Cobalt(I1) complexes in Nafion
polymer films has been considered ( F 3 4 ) . The combination ( F 5 1 ) and Prussian Blue/poly(aniline) (F52) films catalyzed
of ac impedance spectroscopy and "electromodulated optical the reduction of C02. Electrocatalytic reduction of nitrite
transmittance spectroscopic impedance" was used by Amemiya took place at quite positive potentials at PVP films containing
et al. to study charge transport in polymer film electrodes Os-bpy complexes (F53, F54);a mixture of N20, N2, NH2-
(F35, F36). OH, and NH3 was obtained at thin polymeric films of an
Hillman and Bruckenstein have pointed out the important iron(II1) protoporphyrin (F55).Oxyanions such as chlorate
role of slow solvent transport in several studies of the redox and bromate were reduced at conducting polymer electrodes
kinetics of permselective polymer films. Electron transfer, doped with molybdate species (F56,F57). Poly(pyrro1e) films
solvent uptake, and polymer reconfiguration in a cube scheme were robust enough to mediate the reduction of dichromate
were incorporated into a general model (F37). Often observed in acid (F58).Electrocatalytic films for the reduction of the
phenomena such as "break-in" processes, charge and mass disulfide bond in cystine (F59)and for the Cu(II/I)-mediated
trapping, structural changes with redox cycling, and variation reduction of cytochrome c and tyrosinase (F60) have been
of charge transport rate and Eo' values with time were described. Substituted poly(pyrro1e) films with Pd(I1) and
encompassed by their theory. For a polythionine redox film, Rh(II1)-bpy centers were used, respectively, for the hydro-
the kinetics were described in terms of a scheme of squares genation of organic compounds (F61) and the catalysis of
involving electron, proton, and solvent transfer (F38). The hydrogen evolution (F62). Catalytic activity was imparted
EQCM data showed that the coupled motion of electrons and to insoluble liquid crystal films of a cationic surfactant on
protons preceded the rate-limiting solvent transfer in both graphite electrodes by vitamin B I Zhexacarboxylate (F63).
anodic and cathodic steps. One of the later papers in the On the oxidation side, several different polymer film
general Bruckenstein and Hillman treatment of the EQCM electrodes have been used for the electrocatalytic oxidation
experiment has appeared in the last two years (F39). Proton of NADH (F64-F66). Pyrrole-substituted Mn tetraphen-
transfer was also shown to be involved in the charge transport ylporphryrins were precursors to catalytic polymer films for
process operative in thin ubiquinone-Qlo films ( F 4 0 ) . the epoxidation of alkenes and the oxidation of thioacetamide
A two-phase model was employed to explain the surprisingly (F67). Ru(V/IV)-oxygen complexes in Nafion and poly-
large electrochemical diffusion coefficients in polyacrylate (pyrrole) films mediated the oxidation of alcohols (F68,F69).
Analytical Chemistty, Vol. 66, No. 12, June 75, 1994 38SR
release of ferroceniumcations from cyclodextrin film electrodes capacitive potential regions. One group has coined the term
was dependent on the degree of ionization of fixed carboxylic “cyclic deflectogram” for these experiments (F138). Chen et
sites on the polymer ( F 1 1 8 ) and a poly(pyrrole)/cyclodextrin- al. used a flow cell with downstream electrochemical detection
modified electrode exhibited some size exclusion selectivity to verify release of Fe(CN)& from oxidized PPy (F139) and
(F119). controlled release of ATP from PPy was monitored by UV
Several novel analytical applications of ion-exchange absorption spectrophotometry (F140).
polymer electrodes have appeared in the last two years. A Nonuniform CdS particles were electrochemically gener-
Nafion film electrode was used to preconcentrate a cobal- ated and incorporated into PPy/PSS membranes (F141).PPy
tocenium-labeled amphetamine, acting as a hapten, prior to films containing a tetraaza [ 14lannulene-Cu pendant group
SWV analysis in a homogeneous electrochemical immunoassay were demetalized to produce a film that efficiently extracted
procedure (F120, F121). A dual-electrode FIA/LCEC metal ions from solution (F142).
detector was based on in situ formation of metal complexes Ionophore Films. UME studies of charge transport in
formed by the electrochemically controlled release of a poly(ethy1ene oxide) films have continued to appear (B103,
pyrrolidine dithiocarbamate ligand from a poly(pyrro1e) film F143-FI46). Other examples can be found in a collection of
(F122). Nitrosoamine, in the protonated form, was precon- short papers presented a t a symposium on polymer electrolytes
centrated into Nafion-modified electrodes and analyzed by (F147).
voltammetry (F123). Electrodes modified with quaternized For the TCNQ0I-I2- redox couples in PEO, the apparent
PVP films plus ion-exchanged Fe(CN)64-, Mo(CN)g4-, or diffusion coefficients were enhanced by electron transfer
IrC163- species were used to preconcentrate and determine between redox partners (F143). Long-range electron transfer
Ag(1) (F124), and a hydrophobic poly(dimethyldially1- a t distances up to 1.6 nm was invoked to explain the data. For
ammonium chloride) film was used in a three-electrode the case of a bis(fulva1ene)diironsalt in a low molecular weight
amperometric oxygen sensor (F125). Electrochemical “tran- poly(ethy1ene glycol)/LiC104 medium, however, physical
sistors” featured gates consisting of protonated PVP, which diffusion dominated electron hopping in the charge transport
concentrated electroactive anionic complexes from solution. process (F148). U M E steady-state currents of ferrocene in
Drain currents for these species were turned on when the gate PEO matrices were found to vary with the chain length of the
was polarized in the Eo’ region for each complex (F126). polymer molecules (F149).
It is common for polymer films synthesized from conducting Intriguing electroactive ionophores were synthesized by
polymer-type precursors or for redox polymers to have ion- attaching oligo(ethy1ene glycol) chains to tetrathiafulvalene
exchange properties that dominate their response. Several and Co-bpy complexes (F150). Voltammetry a t very slow
studies of systems of this nature will be cited, although their sweep rates of the neat room-temperature liquids, which was
classification as ion-exchange, redox, or conducting polymer- well-behaved due to the lack of natural convection in the high-
modified electrodes is arbitrary in several instances. viscosity media, was used to determine apparent self-diffusion
Anion-exchange polymer films were prepared by the coefficients.
oxidation of pyrrole monomers substituted in the 3-position Voltammetry in COz supercritical fluids was performed
with cationic groups (F127) and the oxidation of a pyrrole- using a U M E coated with PEO/LiCF3S03 to impart con-
substituted pyridinium salt in the presence of 3-methyl- ductivity to the film (F151). Glassy carbon electrodes coated
thiophene (3-MeTP) (F128). A poly(pyrro1e) copolymer with with Kryptofix-222 gavevery sensitive ( 10-l2 M level) square-
a propanesulfonate arm was permselective to K+ a t low wave peaks for the selective determination of H g in natural
coverage ( F 129),and a poly(o-phenylenediamine) redox film waters (F152). Other applications include the direct electron
was permselective to I- and Br- (F130). However, PPy films transfer to a ferredoxin a t a phosphatidylcholine-modified
in aqueous acid solution were not permselective to CI- with Au electrode (F153),the irreversible reduction of retinal at
both K+and H + contributing to the charge transport process phospholipid-coated Hg electrodes (F154),and the diffusion-
(F131). FT-IR was used to follow ion incorporation into PPy controlled CV of amphophilic viologen cations a t lipid
films containing entrapped dodecyl sulfate anions (F132). electrodes (F155).
Perchlorate ions were excluded, while carbonate ions were In a more theoretical vein, the galvanostatic charging and
slowly incorporated from aqueous solution. For poly(pyrrole)/ discharging of a (-)Li/solid polymer electrolyte/porous
poly(styrenesu1fonate) (PPy/PSS) bilayers, EQCM data electrode cell was modeled with a high degree of sophistication
indicated that oxidation involved cation transport a t low (F156). Input parameters for thesimulation included (among
potentials, and anion transport a t high potentials ( F 1 3 3 ) . others) the diffusion coefficient of Li in the solid matrix, the
Redox cycling of a sulfonated PPy film effected modulation total concentration in the solid, the conductivity of the solid.
of the surface pH of the film/KCI(,,, interface between pH the electrode porosity, the exchange current density, and the
5.6 and 8.2 (F134). Anomalous CV reduction peaks in the thicknesses of the separator and the porous composite electrode.
initial negative-going potential sweep for PPy films in water Nahir and Buck analyzed the current/time transients, which
and CH3CN were shown to be due to cation uptake by the exhibited potential-dependent, limiting values a t short times,
film ( F 1 3 5 ) . obtained in a chronoamperometric study on PVC membranes
Ion motion and release by polymer films has been monitored containing valinomycin (F157). Their model was based on
by several different methods including observation of the a fixed-site membrane with a permeable charged species.
deflection of a HeNe laser beam a t PPy/solution interfaces Redox Polymer Films. Several quite interesting studies
(F136, F137). Interestingly, ion transport across the PPy/ with ferrocene polymers have been described. Albagli et al.
solution interface took place both in the faradaic and in the reported the electrochemical behavior of ferrocene-containing
386R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
homopolymers and block copolymers that had polydispersities of that of the TTF and PT units. Thio-substituted quinones
as low as 1.05 (FI58). The oxidative deposition of these adsorbed on Au and Pt(Hg) provided a simple means of
polymers from solution depended on the molecular weight modifying electrode surfaces (FI79).
and also could be controlled by the size of a nonelectroactive Redox polymers with molecular weights up to 20K were
block in the polymer chain. A polymer with a ferrocene- covalently attached to Pt, ITO, and n-Si electrodesvia siloxane
silane backbone displayed surface electrochemistry consistent bonds at one end of the polymer chain. The interface structure
with two successive oxidation steps, at different potentials, was disordered, as indicated by the surface coverages which
involving fractions of the ferrocene repeat units (FI59). An were only 2% of that of a close-packed monolayer of
EQCM study of ferrocene-derivatized siloxane polymer film alkanethiols (FI 80).
revealed significant dependence on the anion of the supporting Prussian Blue and films continue to attract attention as
electrolyte (FI60).Electrochemicalcontrolof a polymer phase exemplified by the long-term stability study of Stilwell et al.
transition was reported for a novel acrylamide-vinylferrocene (F181).The pH of the electrolyte solution was the critical
copolymer film (FI61).Above and below the phase change factor, with redox cycle lifetimes greater than los easily
transition temperature, the film was either shrunken or swollen, achieved for pH 2-3. The voltammetry and chrono-
respectively, in aqueous solutions. amperometry of thin films of silver ferricyanide featured
Intriguing porphyrin polymers with an alternating one- asymmetric CVs and exponential current decay (FI82).
dimensional structure of oligothiophene electron donor units Kulesza et al. carried out Prussian Blue voltammetry in the
spaced apart by phosphorus porphyrin electron acceptor units absence of liquid electrolyte using a simple two-electrode,
were electrosynthesized (FI62). Photoirradiation markedly large glassy carbon/UME configuration (FI83). Other
increased the conductivity of the materials. Deronzier et al. studies of similar systems have been published in the last two
have reported further on their procedure for electropolymer- years (FI84-FI89).
ization of substituted pyrroles possessing electroactive groups Electrochromism and Pattern Formation in Polymer
such as metallotetraphenylporphyrins(FI63).PPy films were Electrodes. There have been several advances in the related
prepared cross-linked by entwined 1,lO-phenanthroline com- areas of electrochromics and pattern formation at modified
plexesofCu(I), Co(II), Zn(II), and Ag(I), which weretethered electrodes. Since these applications tend to cut across the
to the PPy backbone by alkyl spacer arms of variable lengths ordinary lines of classification for modified electrodes, they
(FI64). In another intricate variation on this theme, redox- will arbitrarily be collected into a separate section.
active Fe&d2+ centers were immobilized on L-cystine-deriva- Yoneyama and co-workers have produced impressivelyhigh
tized PPy (FI65). The electropolymerized films were reduced quality light image formation in a poly(ani1ine) (PAn)/TiO2,
chemically to give ionic pendant cysteinyl(su1fide) groups that PAn/TiOz, film (FI90,F191). A poly(ani1ine) image of a
ion-exchanged the Fe-S boxes. human subject is shown in the publications from Yoneyama’s
Bommarito et al. established that the ratio of Os to Ru in laboratory. Illumination of the film was performed in pH 7
copolymers of poly(viny1bpy) was markedly dependent on the phosphate buffer containing methanol as a hole scavenger
method of polymerization (FI66). In a companion paper, under conditions of low PAn conductivity to prevent image
molecular weight and size effects on the transport properties spreading. The yellow images of reduced PAn were easily
of the metal polymers were investigated (FI67).A photoredox erased by polarizing the films at 0.5 V vs SCE. Images in
procedure has been devised for the synthesis of poly(viny1bpy)- metal-bpy polymer films were also produced by a combination
Ru(I1) films on transparent surfaces (FI68). of photochemistry and electrochemistry (FI92). In this case,
Several papers describing the electrochemistry of viologen a spatially controlled image of the original mask was produced.
polymers have appeared (F169-FI72). One of the more Poly(ani1ine)-methylene blue-Nafion composite film elec-
interesting concerned the trapping of electronic charge at trodes, which had been further modified with Ru(bpy)32+,
negative potentials by sulfonated anthraquinone anions that developed images upon illumination (FI93).
were electrostatically bound to a polymer containing viologen In another approach, procedures were given for the
cation units (FI69). The trapped charge could be released photoproduction of very small, patterned tungsten nuclei in
by pH change to alkaline conditions, which lowered the quinone a microlithographic resist consisting of phosphotungstic acid
Eo’ value, or by the use of redox mediators in solution. The and poly(viny1 alcohol). The nuclei served as nucleation sites
E l p value of the pendant viologen polymer of Katz et al. was for the subsequent electroless deposition of Ni. Features with
dependent on the ionization state of the poly(acry1ic acid) dimensions on the order of 0.3 pm were formed (FI94).
backbone (FI72). Another method for creating microstructure and patterned
Other polymer redox films of interest were a poly- images in polymer films involved photochemical ligand loss
(aminonaphthalene) used as a pH sensor for pH of greater from metal redox polymer films containing tetramethyl-bpy
than ca. 4 (FI 73),poly(pheny1)s with pendant ethers or poly- complexes of ruthenium. The photochemical reaction created
(ether)s (FI74),and a quinone polymer film prepared by the “voids” that could be filledvia reaction with osmium phosphine
electrooxidation of 5,6-dihydroxyindole at glassy carbon complexes (FI95).Brumfield et al. also created patterns in
(FI75). Films of electrooxidized 5-carboxyindole were polymer films by deposition of conducting polymers into defects
insulating in either the fully oxidized or fully reduced states, that had been formed in insulating films with an AFM tip
but conducting when partially oxidized (FI 76). Redox (E280).
polymers with a tetrathiafulvalene functionality were based A novel display device was based on the pH change, induced
ona poly(thiophene) backboneor a 1,3,5-benzenecore (FI77, by the oxidation of a PPy film in NaCl(,,), that caused a
F178). In the former case thevoltammetry was a superposition reversible flocculation of a poly(L-lysine) microgel (Fl96).
388R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
and poly(o-toluidine) (F254). Let it be noted that 1992 was (bipolaron) states, both of which were shown to be charge
a good year for the electrosynthesis of poly(parapheny1ene) carriers (F279). (See the Accounts of Chemical Research
(F255-F262). article by Tolbert for a good molecular-based view of the
Several studies have appeared on the electrosynthesis of chemical basis for conductivity in organic metals (F280),)
bickey ball films (8'2634265). Jehoulet et al. found that Differential pulse voltammetry of a novel electrically
films fully reduced to a (260- state were poor electronic conductive butylphthalocyaninato silicon polymer was inter-
conductors, while partially reduced films displayed enhanced preted in terms of the bandwidth and structure of the solid-
electronic conductivity (F263). Reduction took place with a state molecular orbital (F281). The two DPV peaks were
large structural reorganization and intercalation of the correlated with maxima in the'density of states of the valence
supporting electrolyte cation. band.
Electrochemical Characterization. There have been sev- Theory for conducting polymer voltammetry incorporated
eral spectroelectrochemical studies ofoligothiophene molecules the Butler-Volmer equation in order to take into account slow
with four to eight thiophene units linked at a-position. These electron transfer at the polymer/metal interface (F282).
molecules exhibited EE behavior coupled to a-dimer formation Doblhofer argued that, since the potential of solvated
of the radical cation to form a diamagnetic species (F266- conducting polymer systems such as PT remains relatively
F270). A significant aspect of this observation is that the constant as they are oxidized, they are best described as redox
a-dimer dication, and the corresponding a-dimer radical polymers (F283).
cation, are possible alternative structures for the bipolarons Several interesting experimental and theoretical treatments
and polarons, respectively, in "doped" organic metals of the of the pH-driven conductor to insulator transition for PAn
PT type. The sexithiophene CVs obtained by Bauerle et al. films have appeared. Donnan potential expressions and
(F270) revealed a 2+/+/0/-/2-/EEEE system with a 2-V electroneutrality were employed to explain the pH dependence
separation between the anion and cation formation waves. Xu of the transition for PAn and PAn/poly(vinylsulfonate)
and Horowitz boldly predicted the chain length of PT by mixtures and the effect of NaCl concentration on the
comparison of its oxidation potential to an extrapolated value conductivity of emeraldine films (F284, F285). Another
obtained for oligomers with four to six thiophene units (F271). treatment of the PAn protonation equilibria required only
Guay et al. have also looked at thiophene oligomers with up one apparent pK, value (ca. 5 ) to account for the experimental
to seven thiophene rings (F272-F274). For molecules with conductivity/pH curve (F286). Theory for order-disorder
orthogonally fused thiophene oligomers, there was no indica- transitions in binary alloys was applied to benzenoidquinonoid
tion of a-dimer formation in the oxidized forms. and quinonoidquinonoid segments in PAn (F287), and a
A very nice comparison of the electrochemistry of a model for PAn oxidation and protonation was presented that
conducting polymer as a thin film and in solution was made accounted for the interactions between the positively charged
by Jozefiak et al. on high molecular weight-substituted protons and polarons in a one-dimensional chain (F288). On
polyacetylenes (F275). The thin-film voltammetry of these the experimental side, EQCM of PAn revealed significant
molecules was well-behaved, showing oxidative and reductive mass changes only in the pH interval between 1 and 3 where
doping steps separated by ca. 2 V. The cis-polyacetylene film the reduced form is practically unprotonated and the half-
voltammetry was irreversible indicating rapid cis to trans oxidized form is protonated (F289).
isomerization following electron transfer. In contrast, the Applications. An informative review of the use of
solution CVs did not exhibit well-defined peaks, which the conducting polymer electrodes in batteries has appeared in
authors attributed to multiple, highly coupled redox states which fundamental problem areas with regard to com-
having a greater degree of conformational and rotational mercialization were identified (F290). PPy and poly(N-
freedom than in the solid state. methylpyrrole) have been compared with an eye to use as a
Only a few of the many studies on the electrochemical positive electrode. The latter material cycles 0.6 V more
redox switching of conducting polymer films will be mentioned positive than PPy, but loses Coulombic capacity upon cycling
here. The CV and ac impedance study of Duffitt and Pickup (F291). Gravimetric charge densities up to 270 A h kg-l
on PPy indicated that a nonequilibrium state of PPy containing were determined for PAn in propylene carbonate/LiClOp
excess electrolyte and solvent was formed upon reduction and solution (F292).
reoxidation of PPy in CH3CN (F276). Changes in the ionic The incorporation of metal particles into conducting
resistance of the films were explained by slow transport of salt polymer films has been a strategy explored for a variety of
and/or solvent out of the films. Son and Rajeshwar reported electrocatalytic applications. Recent examples include Pb02/
a significant role for 0 2 in the redox switching of PPy. In the PPy (F293),Pt/PAn (F294),Pd/(PAn or PPy) (F295),and
presence of oxygen there was a direct transition to a bipolaron Pt/PPy (F296, F297) composite film electrodes. A good
state, while in a nitrogen atmosphere a neutral to polaron to exampleis thearticleof Chen et al., whostudied the permeation
bipolaron transition was observed (F277). Van Dyke et al. of H2 and 0 2 into composite films of PPy containing
showed that the insulator to conductor transition for PPy could nanometer-sized Pt particles (F297). Conditions for the
be extended by ca. 0.7 V in the negative direction by treatment preparation of PPy films containing homogeneous distributions
of the PPy films with degassed NaOH solution (F278). The of W 0 3 and 0.4-pm Ti02 particles have been given (F298,
effect was rationalized by the relative affinities of the PPy F299).
cationic sites for OH-and BF4- ions. Spectroelectrochemistry Two interesting applications of conducting polymers as
of 3-MePT indicated that two redox processes were operative membranes stand out. Martin and co-workers reported that
for the formation of radical cation(po1aron) and dication- oxidized PPy membranes, supported in the pores of a
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 389R
polycarbonate membrane, could transport electrons across of the film, the surface concentration of the adsorbate, the
the membrane between a donor/acceptor pair, while simul- supporting electrolyte, the solvent dielectric constant, and the
taneously transporting ions to maintain charge neutrality Epzc( F 3 1 4 ) . Correction procedures that take into account
(F300). More interestingly, they also demonstrated that the potential a t the “plane of electron transfer” were described
glucose oxidase could exchange electrons with the membrane that are similar to Frumkin $2 corrections for irreversible
and drive the oxidation of glucose in a transmembrane manner. electron-transfer reactions. The electric field strength in a
Nafion/PAn and free-standing PAn membranes have been SAM a t a roughened Ag electrode was measured by observa-
used as porous gas diffusion membrane electrodes for the tion of the Stark effect on the fluorescence spectra of a dye
oxidation of SO2 and N2H4, and for the reduction of NO2 and molecule in the film (F315). A value of ca. 4 X lo4 V/cm
0 2 (F301). was found at a point in the diffuse region of the double layer.
The volume change that takes place when polymer films The nature of a S A M interface was also probed by measure-
are redox cycled is the basis for possible servomechanical ment of redox potentials of viologen groups positioned a t
devices, in which a conducting polymer film is firmly attached different locations with respect to the interface. One conclu-
to an electroinactive substrate, e.g., commercial adhesive tape sion of this study was that hydration of the viologen dication
in one example (F302). The curvature or bending of such was the principal factor in determining the Eli2values (F316).
strips has been studied by several groups (F303-F305). The Kitamura reported spike-like voltammetric peaks, indicative
dimensional changes, driven by proton or redox doping, were of attractive interactions in the adsorbed state, were dependent
largely reversible for PAn films; values of percent elongation on the alkyl chain length for N,N’-dialkylviologen cations a t
up to ca. 10% were reported for oriented films in the H g electrodes (F317). Creager and Weber calculated the
perpendicular direction to the draw axis (F305). A velocity effect of ions on the potential distribution, and the resulting
of 5 X m/s was reported for the propagation of the oxidized effect on electron-transfer rates, across a monolayer (F318).
zone on a PAn strip (F306). Electron tunneling through thiol SAMs a t gold electrodes
Conducting polymer diodes and transistors are other has been a popular topic. Becka and Miller reported that the
curiosities that continue to attract attention. McCoy and tunneling coefficient, 1.08 f 0.20 per CH2 group, was almost
Wrighton configured two conducting polymer “gates” as a independent of the potential and the redox couple in solution
push-pull amplifier such that there was no crossover distortion (F319). On the other hand, for redox molecules as different
when the output current went through zero (F307). Fox as ubiquinone and Fe(CN)63-, Takehara et al. found a marked
discussed ways to control directional charge transport in difference in the effect of n-alkanethiol SAMs on the electron-
electroactive polymer arrays, including some voltammetry on transfer kinetics (F320). A careful and detailed study of
PT/PPy and PPy/PT bilayers (F308). Buck et al. have electron-transfer kinetics of pentaammine(pyridine)Ru com-
discussed the analogies and differences between liquid/solid plexes tethered to gold via an alkanethiol linkage provided
polyelectrolyte diodes and conventional solid-state semicon- evidence for the existence of a small fraction of fast electron-
ductor diodes (F309). They gave conditions for the chemical exchange centers that dominated the currents a t low over-
mimicking of p-n junctions involving ion-exchange and redox potential (F321). Analysis of the data for molecules with
polymers. The experimental study of Han et al. on Nafion (CH?)lo-l* tethers suggested that through-bond tunneling, as
bilayers supported their ideas (F310). These workers reported opposed to through-space tunneling, was the mechanism of
diode behavior for a Nafion bilayer prepared by sandwiching electron transfer. Curtin et al. also investigated the effect of
two films together at 150 OC in a mechanical press-one film the length of the tethering arm on the low-temperature CVs
was loaded with F e ( ~ h e n ) 3 ~ +and
, the other with Fe- obtained on ferrocene thiol SAMs (F322). The influence of
hen)^^+/^+. Others have reported diode-like behavior for film thickness on electron-transfer rates was very clear for an
junctions such as poly(bithiophene)/Si and PPy/poly- electrode covered with multilayer films of a metal phosphonate
(p-phenylenevinylene) (F31I ) . structure (F323). Obeng et al. reported “b1ocking”properties
Chemically deposited PPy has been used as a precoat for of rigid rod thiols on Au (F324). In other studies Finklea and
the metalization of printed circuit boards ( F 3 1 2 ) . Electro- co-workers obtained nearly ideal CV surface waves for
deposited PPy on carbon fibers improved the bonding between electroactive thiols containing pendant p y R ~ ( N H 3 ) 5 ~ + / ~ +
the fibers and an epoxy resin matrix (F323). redox centers on gold electrodes (F325, F326).
Self-Assembled Monolayers. The surface chemistry of Electrodes modified with self-assembling molecules with
self-assembled monolayers, especially of alkanethiols bonded terminal acid/base or ionic groups can enhance or suppress
to well-defined gold surfaces, is a field to itself which has selected electrode reactions, depending on the state of the end
blossomed in the last decade. The ability to manipulate inter- group. For example, rates of cationic couples such as
facial structure via the chemistry of SAMs is unprecedented. R u ( N H ~ ) ~ ~and + / anionic
~+ couples such as Fe(CN)63-/4- a t
There are now a significant number of modified electrode SAMs with terminal ionic groups were affected in markedly
studies in which the interface exhibits novel phenomena due different ways by solvent effects (F327). The effect of pH
to its microstructure in either the lateral or perpendicular on the response of SAMs has been reported for the latter
direction. couples a t thioctic acid-coated electrodes (F328), for
Several research groups have addressed the question of Fe(CN)63-/4- at 4-pyridyl sulfide electrodes (F329),and for
how the potential gradient across a SAM affects charge carboxylic thiol SAMs on a Q C M surface (F330). SAMs of
transport and the voltammetric response at a SAM-modified HS(CH2),C02H on Au discriminated against ascorbate anions
electrode. Smith and White showed that non-Nernstian wave in the voltammetric analysis of dopamine, with n = 5 giving
shapes were a function of the thickness and dielectric constant the optimum differentiation (F331). Related to these studies
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 301R
thin poly(acry1amide) films on carbon fiber electrodes with was published by Wilson and Turner ( G I 5 ) . A general
number-average molecular weights up to 430 000 (F375).The biosensor review was given by Ivnitskii et al. (G16), which
reversible, cooperative complexation of surfactants in a included reference to numerous Russian language papers.
polymer gel was the basis of a device that converted Hilditch and Green reviewed the topic of disposable elec-
electrochemical energy into mechanical energy (F376). trochemical biosensors and discussed requirements that are
Modified electrodes with permselective and electrocatalytic needed for commercial viability (GI7).
properties were prepared by casting cellulose acetate films, Several books on biosensors that include chapters on
which had been hyrolyzed in base to provide porosity, over amperometric sensors were recently published, but your
electrodeposited Pt and Pd surfaces (F377). Christie et al. reviewer has, regrettably, yet to examine them except for Table
found that poly(viny1 chloride) gave better selectivity than of Contents listings. Among these is the second volume in the
cellulose acetate as a barrier membrane in amperometric Adcances in Biosensors series edited by Turner ( G I 8 ) . This
sensors for H202 and phenolics (F379). volume appears to contain a number of chapters of interest
to amperometric biosensor scientists. Another book, edited
G. B I OELECTROCHEM I STRY by Nakamura et al., is concerned with immunochemical assays
Books and Reviews. Smyth wrote a new book that surveys and biosensors (GI 9) and includes two chapters on ampero-
the voltammetric analysis of a large number of small organic metric biosensors and electrochemical immunoassay.
and inorganic molecules of biological importance (GI). The use of chemically modified carbon-type electrodes was
Schultz and Taniguchi edited the proceedings volume for the reviewed by Wring and Hart (G20) with an emphasis on
Fifth International Symposium on Redox Mechanisms and mediation reactions in biosensors.
Interfacial Properties of Molecules of Biological Importance, Bilayer lipid membranes were reviewed for electrochemical
held in May 1993 (GZ). This is an excellent collection of sensing applications by Nikolelis and Krull ( G Z I ) and for
richly diverse, high-quality papers that give a clear sense of bioelectronic devices in a comprehensive review of BLMs by
the state of bioelectrochemistry as of 1993. The electro- Ottova-Leitmannova and Tien (C22).
chemistry and spectroelectrochemistry of proteins, enzymes, Small Molecules of Biological Importance. Our ability to
small molecules, membranes, and cells, as well as new concepts efficiently oxidize and reduce small biological molecules a t
and techniques, are covered. Volume 221 of the Methods in electrode surfaces carries important ramifications. From a
Enzymology series will be of great interest to metalloprotein biochemical perspective, this ability opens the way for powerful
chemists as it covers physical and spectroscopic methods for investigations of the redox energetics and dynamics of these
probing metal ion bioenvironments. Of special interest to molecules in the context of biological function. From an
electrochemists are the three chapters by Stankovich and co- analytical perspective, efficient redox conversion obviously
workers on EPR spectroelectrochemical titrations of redox provides a basis for sensitive voltammetric or amperometric
enzymes (G3),Armstrong and co-workers on the voltammetry detection of the molecules per se. Furthermore, for those
ofadsorbed metalloproteins ( G 4 ) ,and Hill and Hunt on direct particular molecules serving as enzyme cofactors, their
and indirect enzyme electrochemistry (G5). electrodic behavior can assume paramount importance with
A brief yet succinct overview of the electrochemistry of regard to designing amperometric biosensors. Because many
biopolymers (proteins, polynucleotides) was provided by Cox small molecules of biological importance are organic species,
and Przyjazny (G6). Ewing et al. discussed aspects of they typically do not undergo clean facile electron-transfer
performing analytical chemistry (electrochemistry, separa- reactions a t metal electrodes. Large redox overpotentials and
tions, identification) in microenvironments, specifically single electrode fouling tend to be standard fare, and thus, numerous
nerve cells (G7). The roleof voltammetric methods in research investigations over the years have sought to minimize these
and development of pharmaceuticals was reviewed by Kauff- factors through mediation and electrocatalytic strategies. This
mann and Vir6 (G8). Volk et al. discussed the application of trend continued during the past two years. In the coverage
electrochemistry/mass spectrometry for the elucidation of that follows, we have not included studies of pharmaceuticals
biological redox mechanisms (G9). or investigations of complex chemical reactions coupled to
Many reviews and some books relating to amperometric electrolysis. Our emphasis is decidedly interfacial. Porphyrin-
biosensors were published over the past two years. In several modified electrode studies directed toward catalysis of 0 2 are
excellent reviews, the crucial issue of coupling enzymatic also not included.
reactions to current-carrying electrodes was addressed Substantial interest continued with regard to the electro-
authoritatively. Encompassing reviews regarding enzyme/ chemistry of nicotinamide adenine dinucleotide (NAD/
electrode coupling were provided by Ikeda (GIO) and Bour- NADH). The oxidation of N A D H is a pivotal component in
dillon (GI!).Gorton et al. reviewed the topic of biosensors the design of dehydrogenase-based enzyme electrodes. Typi-
based on apparent direct electron-transfer reactions of per- cally, however, unmediated NADH oxidation proceeds a t large
oxidases (GI2). In another very informative review, Heller overpotentials with comcomitant electrode fouling. Kuhr et
reviewed his and others’ work on redox “wiring” of enzymes al. described a most interesting and potentially useful CV
to electrodes (G13).Redox “wiring” was also covered by study of NADH oxidation at carbon fiber microelectrodes
Boguslavsky et al. in their article, which was more narrowly (G23). By using judicious electrochemical pretreatment (to
focused on ferrocene-derivatized siloxane and ethylene oxide minimize N A D H adsorption) in combination with fast 100
polymers (G14). V/s scan rates (to minimize electrode fouling), reproducible
A very timely review article on glucose oxidase, with an electrooxidation of N A D H was achieved at bare carbon fiber
emphasis on properties important to biosensor development, surfaces. The application of this approach to the development
392R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
of hydrogenase-based microelectrodes was also considered. automated optimization of all waveform parameters for the
In past years, some very successful mediators have been pulsed amperometric detection of several representative
developed by Gorton and others specifically for NADH carbohydrates (G36). Wang's group has been developing
oxidation. Perhaps the best one, Meldola blue, was incor- chemically modified electrodes for HPLC and FIA deter-
porated successfully by Hale et al. into a siloxane polymer mination of various biological compounds. Accounts were
structure that is easily deposited on electrodes by evaporation given of the design and characterization of a Prussian Blue
(G24). A more complicated approach to the mediated electrode for glucose detection (G37) and a polymer film
oxidation of NADH involves the incorporation of a second electrode containing nickel (0xy)hydroxide catalyst for car-
enzyme, e.g., diaphorase, specifically to oxidize NADH, with bohydrate and amino acid oxidations (G38). The oxidation
the mediator then oxidizing thediaphorase (G25). Yet another of glucose can also occur readily at organic conducting salt
potential solution to the problem at hand is direct electro- electrodes as shown by Zhao and Lennox for TTF/TCNQ
catalytic oxidation of NADH on electrochemically grown (G39). Electrodes based on HMTTeF-TCNQ (where HMT-
conducting polymers, although few have been found to date TeF represents hexamethylenetetratellurafulvalene)(G40)
that function in this capacity. Two promising candidates were exhibited especially good versatility for a number of other
reported on, namely, poly(indo1e-5-carboxylic acid) (G26) important oxidations including glutathione, cysteine, dopa-
and poly(thionine) (G27). mine, and ascorbate. This latter electrode is considerably
Reduction of NAD+ to NADH, also a difficult reaction, more resistant to dissolution than TTF/TCNQ. These and
is important synthetically in bioreactors but less so from an other papers from this group shed considerable light on the
analytical standpoint. The incorporation of rhodium com- biological oxidations that occur at organic conducting salt
plexes in polymer film electrodes resulted in the catalysis of electrodes.
this reaction with good selectivity for 1,4-NADH and without The interaction of amino acids with copper has also been
the formation of NAD dimers (G28,G29). Catalyticreduction examined electrochemically. Weber's group, in efforts to
of NAD+ by hydrogenase at platinum electrodes was also develop detection schemes for nonelectroactive peptides, have
described (G30). exploited the biuret reaction, which produces electroactive
Basic electrochemical investigations of catechols and Cu(I1)-peptide complexes. The influence of tyrosine, an
catecholamines on carbon-type electrodes emphasized vol- electroactive amino acid, on the electrochemical response was
tammetric discrimination capabilities. Such studies are of addressed in a recent report (G41).
direct relevance to in vivo neurochemical studies, which are An amperometric sensor was described by Malinski and
reviewed under In Vivo and Cellular Electrochemistry. Taha for the detection of nitric oxide (G42),a molecule whose
Tokuda and co-workers investigated the effects of electro- biological importance has only begun to be appreciated in the
chemical pretreatment on the oxidation of dopamine (DA) past few years. This sensor, which is constructed by elec-
(G31). Discrimination against DOPA and DOPAC, but not tropolymerization of a Ni-porphyrincatalytic filmon a carbon
ascorbic acid, can be achieved by employing a "mild" fiber electrode, had a detection limit of 10 nM. Furthermore,
pretreatment. Caution against the indiscriminate use of it was sufficiently miniaturized, 0.5-m fiber diameter, to
"strong" pretreatments for DA detection was given. Over the monitor N O release from a single cell.
last few years, McCreery's group has provided much valuable Several other important molecules were the subject of
insight into carbon electrode voltammetry. Of relevance to significant investigations. The electrochemistry of the co-
this section is a detailed investigation of theirs concerned with enzyme pyrroloquinolinequinone (PQQ) was found to be
the adsorption of catechols on glassy carbon surfaces (G32). reversible under acidic conditions at bis(4-pyridy1)disulfide-
Whereas DA, 4-methylcatechol, and DOPAC all adsorb modified gold electrodes (G43). The oxidation of biliverdin,
strongly on fresh-fractured GC, the interaction is weak on a key intermediate derived from bile metabolism, was examined
polished surfaces apparently due to impurity adsorption. by thin-layer spectroelectrochemistry and its formal potential
Electrochemical pretreatment leads to adsorptive preference was reported (G44). Hemin adsorbed on pyrolytic graphite
for DA, a cation, due to oxidation of the GC surface. Reverse electrodes was examined in-depth by UV/visible electro-
differential-pulse voltammetry was used by Matysik et al. in reflectance (G45). The adsorption and voltammetry of
a study aimed at discriminating among a serious of catechols ubiquinones was examined at the mercury electrode (G46).
(G33). Nafion coatings are frequently used with carbon Flavins and related compounds were explored electro-
electrode studies of neurotransmitters to electrostatically chemically in both solution and monolayer formats. Verhagen
discriminate against ascorbate and other anions. A new and Hagen described somevery nice electrochemistry of flavin
electrostatic approach was described by Malem and Mandler adenine dinucleotide (FAD) at glassy carbon electrodes (G47).
in which COOH-terminated alkanethiolate self-assembled High electron-transfer rates were measured for adsorbed FAD,
monolayers on gold were effective in discriminating against which appeared to act as a surface mediator for the subsequent
ascorbate during the detection of DA (G34). reaction of diffusing FAD. The electrochemical behavior of
The direct oxidation of carbohydrates, alcohols, and amino solution FAD (and also a ubiquinone) was examined by
acids is now performed routinely at noble metal electrodes Takehara et ai. at gold electrodes covered by n-alkanethiolate
due to the efforts of Dennis Johnson and co-workers. In the self-assembled monolayers (G48). FAD was able to partition
latest chapter, Vandeberg and Johnson report on the pulsed into the monolayer, but its electron-transfer rate decreased as
electrochemical detection of the sulfurous compounds cysteine, film thickness increased, apparently due to increased ET
cystine, methionine, and glutathione, at picomolar detection distance. Nakashima et al. incorporated flavin molecules into
limits (G35). Lacourse and Johnson have described an synthetic lipid bilayers on gold electrodes (G49). In this study,
394R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
Clearly there is a growing recognition of the potential of this forms for docking basic cytochromes appears promising. In
approach for investigating protein energetics and dynamics, a CV and impedance study of horse cytochrome c adsorbed
duein part to thecontinued maturing of the technique. Indium on Au/S(CHz)l&OOH, the electron-transfer rate was found
oxide electrodes were used in a combined electrochemical/ to be consistent with predictions from nonadiabatic Marcus
spectroscopic (CD)/calorimetric (DSC) study of cytochromes theory (G80). Collinson et al. demonstrated the covalent
c from a variety of vertebrate species, as described by attachment of electroactive cytochrome c to SAM/Au
Hawkridge and co-workers (G68). Conformational stability electrodes using carbodiimide coupling in conjunction with
of the cytochromes was linked to differences in amino acid electrostatic orientation (G81). In a related study, Cooper et
sequences and the physiological temperature of the source al. described the quasi-reversible voltammetry of cytochrome
organism. Barker and Mauk utilized CV in conjunction with c covalently attached to the N-acetyl cysteine-modified gold
edge-plane pyrolytic graphite electrodes to examine the electrode via carbodiimide chemistry (G82). Cytochrome
alkaline form of cytochrome c and some variants (G69). They CISAM electrodes were used by Reeves et al. to demonstrate
reported the first measurement of the formal potential of the the application of square-wave voltammetry to quasi-reversible
alkaline form of cytochrome c and gave a complete thermo- surface species (G83). There were a number of other quite
dynamic description of the pH-dependent redox cycle involving interesting cytochrome monolayer studies. Ueyama et al.
the native and alkaline forms. McLendon and co-workers demonstrated vectorial electron transfer across a flavolipid
measured the formal potential of guanidine hydrochloride- L-B monolayer-modified electrode to an adsorbed layer of
unfolded cytochrome c and determined a 10 kcal/mol cytochrome c (G84). Cytochrome c was also found to be
difference in stabilization energy between the reduced and electroactive when adsorbed to electrodes modified by a
oxidized forms of the protein (G70). Independent confirmation composite layer consisting of a triblock polyanion and a cationic
of this result was given by Pielak and co-workers (G71) and lipid (G85).These layers showed a marked pH dependence
extended to urea denaturation conditions. Both of these studies of the cytochrome response.
made use of the bis(4-pyridyl) disulfide-modified gold Prior spectroscopic and spectroelectrochemical studies have
electrode. Cysteine-modified gold electrodes were used in contributed importantly to our understanding of electroactive
the first example of a high-pressure protein electrochemical protein monolayers and it seems a sure bet that this area will
experiment (G72). A determination of the difference in molar continue to intensify. Using SERS, Hobara et al. showed
volume between ferri- and ferrocytochrome c confirmed that that cytochrome c immobilized by adsorption on the bis(4-
ferrocytochrome c has a more compact structure. Initial pyridyl) disulfide/silver electrode exhibited a native 6cLS
electrochemical reports appeared for the following small configuration and formal potential, in contrast to its behavior
electron-transfer proteins: Achromobacter cycloclastes at bare silver or bis(Cpyridy1) disulfidelgoldelectrodes (G86).
pseudoazurin (G73),a blue copper protein from Alcaligenes Visible absorption spectra of ferri- and ferrocytochrome c
faecalis (G74), and cytochrome c‘ from Rhodospirillum monolayers on tin oxide electrodes, reported by Collinson and
rubrum (G75). This latter paper also presented some Bowden (G87),also supported a native conformational state
interesting results bearing on the role of promoters for for the protein on this electrode material. Mantele and co-
cytochrome electrode reactions. Reports also continued to workers described FT-IR thin-layer spectroelectrochemical
appear in which electron-transfer proteins serve the role of characterizations of cytochromes utilizing unmediated elec-
mediators for complex enzyme systems, thus allowing bi- trochemistry at modified gold minigrid electrodes. This
molecular interactions and catalytic reactions to be investi- technique, which provides reduced minus oxidized difference
gated in a physiologically relevant manner. Electrochemical spectra, should complement Raman techniques nicely in
studies of this type were conducted on the 66-kDa hexaheme providing detailed structural information associated with redox
enzyme nitrite reductase from Desulfouibrio desulfuricans changes in metalloproteins in solution. In one of their papers,
(G76), another nitrite reductase from Alcaligenes faecalis a detailed characterization of horse cytochrome c redox
(G77), and Desulfouibrio gigas hydrogenase (G78), an 89- chemistry in terms of secondary structure as a function of pH,
kDa molecule containing one nickel and three F e S centers. temperature, and electrode promoter was provided (G88). In
Electrochemistry of protein monolayers is a subject that another paper, detailed structural changes associated with
is continuing to generate increasing interest. Although the redox chemistry of tetrahemic cytochromes c3 were
scattered reports can be found in the literature from a decade described (G89). This technique is well-suited to proteins
or more ago, it is only within the last several years that the which can be prepared at reasonably high concentrations,
potential of this approach has become more evident. During typically millimolar or greater.
the last two-year period, Armstrong’s group continued their Myoglobin and Hemoglobin. The prospects for the direct
work with ferredoxins adsorbed on aminocyclitol-modified electrochemistry of these oxygen carriers improved signifi-
pyrolytic graphite electrodes. Their CV study of the kinetics cantly during this time period. Sample purity was previously
of thiolate ligand binding to the (3Fe-4S) cluster of the protein established as an important element in achieving myoglobin
ferredoxin I11 from Desulfouibrio africanus (G79) is an voltammetry at indium oxide electrodes. Tominaga et al.
excellent example of the capability of monolayer electro- demonstrated quantitatively that surface hydrophilicity of the
chemistry for probing the coupling of ligand exchange and indium oxide electrode is also a crucial factor in this reaction
electron transfer. Bowden’s group continued their studies of (G90). They achieved quasi-reversible cyclic voltammetric
cytochrome monolayers emphasizing elucidation of electron- responses for both sperm whale and horse myoglobin at highly
transfer kinetics and mechanisms. The use of COOH- hydrophilic In203 surfaces prepared by extensive detergent
alkanethiolate self-assembled monolayers (SAMs) as plat- sonication. An earlier paper from the same group had
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 0 395R
described their initial voltammetric results for the horse Kinnear. In one study they successfully immobilized elec-
myoglobin species (G91). The redox energetics, electron- trocatalytically active fumarate reductase in self-assembled
transfer kinetics, and ligand dissociation kinetics of monolayers on gold electrodes using a dialysis procedure
horse metmyoglobin and cyanomyoglobin were explored by (GIOI). Electrochemistry and electrocatalytic functioning
Hawkridge and co-workers a t the indium oxide electrode of E. coli fumarate reductase in micellar media was also
surface (G92). Only the six-coordinate species Mb(II1)L (L described although the electrode coupling in this case was
= CN-, HzO) were found to undergo facile electron transfer, mediated by decylubiquinone ( G I 0 2 ) .
with the cyano form exhibiting a considerably enhanced E T Additional evidence supporting the existence of direct
rate. Rickard and co-workers described thin-layer spectro- interfacial electron transfer was provided for a number of
electrochemical measurements of redox potential as function other redox enzymes, including the following two reports on
of pH and heterogeneous E T rates for hemoglobinon an indium hydrogenase. Bianco and Haladjian reported that hydrogenase
oxide electrode (G93). Finally, polyethylene oxide-modified from Desulfovibrio vulgaris (Hildenborough) transfers elec-
myoglobin was found to be stableand electroactive (irreversible trons directly a t pyrolytic graphite electrodes in the presence
ET a t indium oxide) in a PEO oligomer medium (‘394). of polylysine (G103). At small overpotentials, reversible
Other electrodes besides indium oxide have been developed hydrogen electrode behavior could be observed. Direct electron
in past years for use with the globins. Hemoglobin was found transfer of hydrogenase (Thiocapsa roseopersicina) was also
to be electroactive at polymerized Azure A film electrodes reported to occur a t cadmium sulfide particles under
(G95) and at thionine-modified electrodes (G96). These two illumination (G104). The redox properties of human and
electrodes were each capable of driving both the reduction bovine copper-zinc superoxide dismutase (SOD) species as a
and oxidation directions of the Fe(III)/Fe(II) hemoglobin function of pH, single site mutations, and inhibitors were
conversion. characterized by direct electrochemistry a t gold electrodes
Enzymes: Unmediated Electrochemistry. Achieving elec- using 1,2-bis(4-pyridyl)ethene as a promoter (GI05, G106).
trical communication between redox enzymes and electrodes Shinohara reported the direct electrochemistry of the 40-
continues to be one of the most interesting and promising kDA flavoenzyme sarcosine oxidase a t textured titanium
areas of protein electrochemistry. Articles concerned with dioxide semiconductor electrodes (GI07).
establishing enzyme/electrode interfacial communication have Efficient enzyme/electrode electron transfer is critically
been selected for this subsection. Those articles focusing more important for the functioning of amperometric biosensors. A
on electrocatalytic aspects can be found under Enzyme survey of publications on “wired”enzymes, enzymes entrapped
Electrodes. in electronically conductive materials, and mediated coupling
An important activity that continues to flourish is the of enzymes for sensors, can be found in the section on Enzyme
unmediated electrochemistry of native unmodified redox Electrodes. To conclude the present section, we highlight
enzymes, including integral membrane proteins. Complexes three reports of unmediated electrochemistry of unmodified
originating from the mitochondria of various species were the enzymes of particular importance to bioanalysis. Zhao et al.
topic of several accounts. The terminal complex, cytochrome reported that when horseradish peroxidase is irreversibly
oxidase, was immobilized electroactively into a membrane adsorbed on colloidal gold particles, direct electron transfer
environment on n-octadecanethiol-modified gold electrodes between the heme and the gold takes place ( G I 0 8 ) . The
using a cholate dialysis procedure (G97). Voltammetry electronic coupling may be related in some manner to the
consistent with direct electron transfer between the electrode curvature of the gold substrate; the same behavior was absent
and oxidase was observed, as was the catalytic turnover of for planar electrodes. lkeda et al. described some interesting
solution cytochrome c. Salamon et al. reported that bovine observations regarding direct electron transfer between de-
cytochrome oxidase directly transfers electrons when incor- hydrogenases and various electrodes (G109). Alcohol dehy-
porated into lecithin bilayer-modified indium oxide electrodes, drogenase and D-glUCOnate dehydrogenase from bacterial
the two observed voltammetric processes being assigned to membranes, upon being irreversibly adsorbed on bare metal
the heme a and CUAcenters (G98). Spinach cytochromef. or carbon electrodes, showed significant electrocatalytic
another integral protein, was also found to be electroactive at activity in the absence of mediators. Finally, a promising
the same type of electrode. Armstrong and co-workers example that highlights the possibilities for trace voltammetric
described the direct electrochemistry of Escherichia coli detection of sulfur-containing proteins was presented.
succinate dehydrogenase (hydrophilic portion of complex 11) Adenosine deaminase was detected at a reported limit of 2
immobilized by adsorption on edge-oriented pyrolytic graphite ppb using adsorptive stripping square-wave voltammetry at
electrodes (G99). Unusual “diode-like’’ behavior was observed mercury electrodes (GI I O ) .
under conditions of linear potential scan, as evidenced by the Other Studies ofproteins and Enzymes. A powerful FT-
severe retardation of the reverse reaction, fumarate reduction, I R thin-layer spectroelectrochemical technique was utilized
as the driving force was increased. Using the same monolayer to provide the first vibrational IR spectra for the primary
approach, a detailed description of the chemically reversible electron donor of photosynthetic reaction centers from
electrochemistry of E . coli fumarate reductase was also given Rhodobacter sphaeroides and Rhodopseudomonas viridis
( G I 0 0 ) . Redox potentials for the FAD and (4Fe-4s) centers (GI I I ) . Redox-driven difference spectra were generated using
were obtained, and a turnover number of 840 s-l for direct electrochemistry a t a gold minigrid electrode. In a
electrocatalytic fumarate reduction reported from RDE second study, FT-IR spectroelectrochemistry and photo-
measurements. Other electrochemical experiments with chemistry were employed to provide unprecedented insight
mitochondrial enzymes were published by Monbouquette and into the interactions of the quinone electron acceptors in the
396R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
R. sphaeroides reaction center (GI 12). Both mediated and onstration and characterization of new materials, concepts,
direct electrochemistry were exploited in this study. Stank- or strategies. The reader should note that Janata’s chapter
ovich and co-workers described a very nice application of on sensors in this same issue (GI26) includes comprehensive
mediated EPR spectroelectrochemistry to the redox thermo- coverage of amperometric biosensors. Furthermore, in odd
dynamics of electron-transfer flavoprotein-ubiquinone oxi- years, amperometric biosensors are included in the Application
doreductase (ETF-QO), an iron-sulfur flavoprotein from the Reviews issue, most recently by Wang in the Clinical
inner mitochondrial membrane (GI 13). Three overlapping Chemistry chapter (GI27).
redox potentials associated with the two redox centers were Glucose sensors based on the glucose oxidase catalytic cycle
resolved, making possible the first complete thermodynamic continued to dominate the amperometric biosensor field over
description of electron transport from fatty acid oxidation the last two years. The availability and stability of this enzyme,
substrates to the mitochondrial respiratory chain. Mediation as well as its obvious application in the monitoring of diabetes,
was also used in an investigation of Fe(II1) reduction in ferritin have been key factors in its popularity. An informative review
performed using thin-layer spectroelectrochemistry (GI 14). article on glucose oxidase was cited earlier (G15). A new
An in-depth investigation of mediator/enzyme kinetics was development that is sure to have major impact on the glucose
reported by Coury et al. for sulfite oxidase, a molybdoheme, sensor field is the recently reported crystal structure of partially
in reactions with several organic mediators (GII5). deglycosylated glucose oxidase from Aspergillus niger at 2.3-A
Sagara et al. described an interesting method for the resolution (GI28). One other comment of general interest is
determination of molar absorptivities of electron-transfer the oft-discussed application of glucose sensors for in vivo
proteins using optically transparent thin-layer spectroelec- monitoring. Although impressive advances have been made
trochemistry (GI 16). This method, which conveniently does in the development of glucose sensing devices, a number of
not require accurate knowledge of protein concentration, was imposing problems stand in the way of their implementation
applied to C-type cytochromes. as long-term implantable devices, as succinctdy reviewed by
A few papers of note also dealt with the interfacial behavior Reach and Wilson (GI 29).
and electrochemistry of proteins not normally the subject of Theory. Albery and co-workers continued their analysis
redox electrochemical studies. Randriamahazaka and of steady-state amperometric biosensor behavior with con-
Nigretto carefully examined the adsorption behavior of tributions concerning enzyme/electrode coupling via homo-
thrombin, a protease from the blood-clotting cascade, on geneous solution mediators (GI30), which is of relevance to
carbon paste electrodes for a wide range of experimental the mechanism of conducting organic salt electrodes, and also
conditions (GI 17). Subsequently, a voltammetric assay for multienzyme sensors (G131). The mechanisms attendant to
thrombin was developed based on the ability of irreversibly the functioning of organic salt enzyme electrodes were also
adsorbed thrombin to cleave an electroactive label from its addressed from a different viewpoint (GI32).
substrate (GI 18). Roscoe et al. investigated the irreversible Two theoretical sensor studies in which the enzyme catalysts
adsorption behavior of a whey protein, @-lactoglobulin, on are incorporated into polymer films were given. In one, the
platinum electrodes as a function of temperature and pH steady-state response of glucose oxidase/poly(pyrrole)- (PPy-)
(G119). A SERS examination by Reipa et al. of insulin based sensors was extended to include the case where a PPy-
adsorbed on silver electrodes indicated that binding to the oxidizable mediator (benzoquinone) was present in the film
electrode occurred primarily via ionized tyrosine and carboxy (GI33). In the other, steady-state and transient responses
terminal ends at potentials positive of the pzc (G120). The were provided for mediated enzyme electrocatalysis within
adsorption of human serum albumin on tin oxide electrodes both electronically conductive and insulating polymer films
was characterized in a careful experiment by Asanov and (GI 34).
Larina utilizing total internal reflection fluorescence spec- Finite-volume modeling was applied to evaluate the
troelectrochemistry (GI 21). transient response behavior of various electrode configurations,
Photobioelectrochemistry. In addition to some funda- including the case of a free enzyme layer confined by a
mental studies on reaction centers cited in the preceding semipermeable membrane and for enzyme immobilized on
section, there were some other projects of interest. Katz either size of a polymer membrane adjacent to the electrode
and co-workers examined chemical aspects of Pt and Pt- (GI35). Explicit-point modeling of transient and steady-state
amalgamated electrodes in relation to quinone mediation of responses was performed for the case of fully soluble enzyme
adsorbed photosynthetic reaction centers (G122, GI23). (glucose oxidase), substrate (glucose), and mediator (GI36).
Photoexcitation of Ti02 particles was used to drive the Digital simulation was also used to model the case of
superoxide dismutase catalytic cycle via photogenerated submonolayer coverage of an enzyme whose interaction with
superoxide (GI24). Finally, soluble mediators were used as its substrate releases a redox label that can be detected
electron donors in photoelectrochemical characterization of electrochemically (GI 37). The intended applications are in
pigments in thylakoid membrane fractions (GI25). assaying proteases in turbid samples and for characterizing
Enzyme Electrodes. The design and development of certain components from the blood coagulation system.
amperometric biosensors in which enzyme reactions are Pardue and co-workers presented two alternative measure-
coupled to amperometric or voltammetric electrodes was the ment schemes to the usual nonequilibrium steady-state current
single largest subject area reviewed in terms of number of measurements. Utilizing a thin-layer cell configuration,
papers considered. Papers selected for citation in the present complete reaction of substrate in a small fixed volume gives
document generally displayed either an emphasis on funda- rise to equilibrium-based measurements of concentration
mental scientific advancement or an emphasis on the dem- (GI 38),which can extend the linear dynamic range and reduce
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 397R
dependence on certain experimental variables. In another oxidase is oxidized by the hydrogen peroxide generated by the
study, transient currents measured a t short times were used reaction of a second enzyme with the substrate. This strategy
with appropriate theoretical models that predict the steady- can be used with difficult-to-“wire” enzymes such as choline
state currents that would result at longer times (G139). oxidase for detection of choline. Evidence supporting the
Glucose oxidase entrapped within an osmium-based redox feasibility of a trienzyme sensor incorporating acetyl-
polymer film on a glassy carbon electrode was employed as cholinesterase was also reported (G152). Michael’s group
the experimental system in these two studies. also demonstrated that Os-PVP/peroxidase sensors could be
Lyons et al. described a theoretical model for a hetero- used to detect H202 in CO2-based fluid near its critical point,
geneous thin-film sensor in which Michaelis-Menten kinetics the first example of its type (G153).
apply to substrate/product conversion a t dispersed catalytic Glucose oxidase sensors based on entrapment within other
particles within a Nafion film (C140). Although the system redox polymers was also reported. Ferrocene-based polymers
examined was dopamine oxidation, the theory also has for this purpose were described by several groups. These
relevance to enzyme electrodes. included ferrocene-substituted polylysines (GI 5 4 , polymers
Tatsuma and Watanabe reported theoretical descriptions based on ferrocenylenemethylene structure (GI 5 3 , ferro-
for the case of monolayer and bilayer enzyme electrodes in cenylsiloxane-ethylene oxide copolymers (GI 56),ferrocenyl-
which a soluble mediator is responsible for enzyme/electrode acrylamide-acrylic acid copolymers (G157),and commercially
communication. Both transient (G141) and steady-state availablepoly(viny1ferrocene)(G158). The latter two papers
(G142) responses were described and compared with results also discussed theoretical considerations regarding steady-
using glucose oxidase sensors. state sensor response. Other reported redox polymers that
Redox “Wired” Enzymes. Some important developments were successfully used to wire glucose oxidase included a
were reported that bear upon the mechanism of electron tetrathiafulvalene-substitutedsiloxane polymer (G159) and
transfer to the FAD sites in glucose oxidase. Mikkelsen, polymercapto-p-benzoquinone (GI 60).
English, and co-workers provided an insightful characterization The second major focus in developing polymeric enzyme
of ferrocene-modified glucose oxidase molecules (GI 4 3 ) .They sensors has been the entrapment of enzymes within polypyrrole
concluded that the location of lysine modification sites results and other conducting polymers, which was first described by
in long-range ferrocene-to-flavin intramolecular electron Foulds and Lowe in the 1980s. An advantage of this approach
transfer as the rate-limiting factor in electrochemical conver- is the ability to prepare the polymer/enzyme film by a one-
sion. This view is supported by the available crystal structure step electropolymerization, which is attractive from a com-
for the enzyme (G128). Another pertinent paper of funda- mercialization perspective. The functioning of conventional
mental interest, although not dealing specifically with “wiring”, polypyrrole-type enzyme electrodes is not as straightforward
is the detailed voltammetric study reported for the glucose/ as for the redox polymer film electrodes. Typically, the PPy
glucose oxidase reaction mediated by one-electron reagents matrix appears to function primarily as a three-dimensional
(G144). Apparently the mediator forms a precursor complex support for the enzyme with electrochemical communication
with glucose oxidase in a site near the flavin. Interesting occuring via internal redox of a mediator (e.g., oxidation of
experimental measurements of mediator complexation with H102) or cosubstrate species. During this two-year time
glucose oxidase were reported for hydroquinonesulfonate period, polypyrrole was clearly the material of choice for most
(G14.5, G146). researchers, usually in combination with glucose oxidase, which
Polymer Film Electrodes. Since Degani and Heller’s generates H202 that is oxidized at the substrate electrode.
seminal papers on ferrocene-modified glucose oxidase in the Rotating ring disk studies by BClanger et al. examined, among
1980s, the redox “wiring” approach to coupling enzymes and other factors, the effect of PPy film thickness and glucose
electrodes has flourished, especially as regards entrapment of concentration (G161). The catalytic reaction was found to
the enzyme within redox polymer films. Heller’s review is a mainly occur a t the PPy/solution interface except a t high
good introduction to this area (G13). It is now possible to glucose concentration. In an interesting study, Cooper and
prepare three-dimensionally stable polymer films that provide Bloor coimmobilized catalase with both glucose oxidase and
a friendly hydrogel microenvironment for enzymes as well as glucose apooxidase to investigate the mechanism of the PPy
good electrical communication with the substrate electrode. biosensor (GI 62). They concluded that electron transfer
Aoki and Heller reported fundamental measurements of between PPy and entrapped enzyme is very inefficient.
electron-transfer diffusion coefficients for osmium( II/III)/ Significant rates of electron transfer were noted, however,
poly(viny1pyridine) (Os-PVP) hydrogel films as a function of when a small electron-transfer protein, cytochrome c, was
thedegree of diepoxide cross-linking (G147). “Redoxepoxies” entrapped within PPy (G163), In other studies, Tatsuma et
of the Os-PVP type have been quite successful for entrapping al. prepared horseradish peroxidase/PPy electrodes (G164)
redox enzymes in the construction of reagentless biosensors. and bienzyme PPy electrodes that contained both peroxidase
Heller’s group reported several examples including horseradish and glucose oxidase (G165). A role for the PPy in enhancing
peroxidase sensors for hydrogen peroxide and NAD(P)H electrochemical communication between the electrode and
detection (G148), oxidase sensors for detection of L-cu- enzymes was proposed.
glycerophosphate and L-lactate (G149), and a glucose de- Coentrapment of electron-transfer mediators along with
hydrogenase sensor for glucose detection (GI 50). Bienzyme enzymes in conducting polymers was described by several
sensors based on Os-PVP polymers were also described by the groups. In the case of glucose oxidase amperometric sensors,
same group (G151) as well as by Michael and co-workers the rationale for using a mediator is avoidance of the HzOz
( G 1 5 2 ) . In these devices, Os-PVP-wired horseradish per- product. The high potentials needed to oxidize H201 are
Analytical Chemlstry, Vol. 66, No. 12, June 15, 1994 401R
Other platinum-based microelectrodes included those for Can electrodes communicate with intact livingcells? Using
cholesterol and cholesterol ester, in which enzymes were mediators, the answer is “yes”, as has been demonstrated
adsorbed on a porous carbon composite supported on a periodically in the past. The ability to establish lines of
recessed-tip 50-km Pt wire (G234), and a glucose sensor electroenzymatic communication between electrodes and
utilizing monolayer glucose oxidase immobilized in a poly- whole cells suggests new approaches for enzyme biosensors as
(phenol) film on 25-pm Pt wires disk electrodes (G235). well as for microbiological research. Along these lines, Ikeda
Other Enzyme Electrode Studies. For convenience, a et al. have reported mediated bioelectrocatalytic reactions of
number of other significant reports concerning various aspects Gluconobacter industrious immobilized on carbon paste
of amperometric biosensors are collected together here. For electrodes (G246, (3247). In the presence of ferricyanide as
the many workers developing biosensors based on the elec- mediator, both glycerol and fructose were oxidized at high
trooxidative detection of HzOz, the paper by Zhang and Wilson rates, apparently by dehydrogenases in the cell membranes
describing detailed studies of this reaction a t Pt and Pt/Ir (G246),and in the presence of p-benzoquinone as mediator,
electrodes should be important (G236). The reaction at neutral the oxidation of glucose proceeded (G247). Earlier, an
pH is not fully understood; the studies reported here example of a bulk yeast carbon paste electrode due to Kulys
concentrate on physiological buffer conditions pertinent to was cited (G221).
biosensor operation. Experimental variables (pH, tempera- A novel photoelectrochemical device was developed and
ture, electrode conditioning) were found to exert a strong characterized by Cohen and Weber for potential applications
effect on the reaction, and the use of a protective cellulose in automated immunoassay and biosensors (G248). Using
acetate membrane was found to be advantageous. an optical fiber, the device is able, via an O z / R ~ ( b p y ) 3 ~ + /
A significant contribution to the understanding of organic light reaction, to generate H202, which can then be detected
conducting salt electrodes was due to Lennox and co-workers amperometrically a t a gold ring electrode. In their paper, the
(G237) in a detailed electrochemical study of TTF/TCNQ device was used as a sensor to detect catalase a t subnanomolar
and hexamethylenetetratellurofulvalene(HMTTeF)/TCNQ. concent ration.
Both silicone oil and polystyrene binders were used. Their Martin and co-workers reported a self-contained sensor
results support the homogeneous mediation mechanism for concept in which the internal solution components and
the electrooxidation of ascorbate, NADH, and reduced glucose electrodes are confined to one side of an ultrathin film
oxidase. An evaluation of background currents gave evidence composite membrane (G249). The glucose/glucose oxidase
for the view that these salts undergo dissolution even at system was used as a test system.
potentials at which they are normally considered to be stable. The concept of using bilayer lipid membrane properties in
Wilde et al. described results of a CV investigation of charge combination with enzymatic reactions as a basis for chemical
accumulation a t TTF/TCNQ electrodes operating in glucose sensing was described by Nikolelis et al. (G250). The presence
oxidase biosensors (G238),a phenomenon apparently due to of acetylcholine resulted in small transient currents across
the surface accumulation of a reduced species as a result of BLMs incorporating acetylcholinesterase. The signal arises
glucose oxidation. Xanthine sensors based on the im- from a change in double-layer properties attributed to
mobilization of xanthine oxidase on TTF/TCNQ/silicone oil generation of hydrogen ion by the enzymatic reaction.
substrates were reported by Korell and Spichiger (G239). The entrapment of active glucose oxidase in sol/gel matrices
Exploiting hydrophobic interactions during immobilization was reported by Audebert et al. (G251). Voltammetric
resulted in the best performance. Sim analyzed the steady- monitoring in the presence of ferrocene mediator and glucose
state kinetic behavior of an ethanol sensor based on the was used to evaluate the activity of enzyme. Ellerby et al.
confinement of alcohol dehydrogenase between a membrane described the entrapment of functional proteins (cytochrome
and an N-methylphenazinium (NMP)/TCNQ electrode c, superoxide dismutase, myoglobin) in porous, optically
(G240). transparent, sol/gel matrices (G252). Although not an
Several additional studies were reported that focused on electrochemical study, this study could suggest possibilities
mediator development. In a detailed study, Fraser et al. for the design of electroenzymatic experiments and sensors.
examined a series of mediators comprised of tris(4,4’- Polynucleotides and Nucleic Acids. Palecek and col-
substituted-2,2’-bipyridine) complexes of Fe(II), Ru(II), and leagues, to whom we owe much of our knowledge of
Os(II), as electron acceptors for glucose oxidase (G241). It polynucleotide interactions at electrode surfaces, discussed
was concluded that the overall charge on the mediator was the voltammetry of various types of DNA a t H M D E and
critical, with + 5 providing optimum electron-transfer kinetics, carbon electrodes (G253, G254). By exploiting the strong
apparently due to interaction with the anionic active site of affinity of DNA for these surfaces, the analysis of nanogram
the enzyme. Effective heterogeneous mediation of tyrosinase or lower quantities in sample sizes of 5 L becomes possible
and cytochrome c was achieved through the incorporation of using adsorptive transfer stripping voltammetry methods.
a tetradentate Cu(II)/Cu(I) complex in a Nafion overlayer Characterization by this method of various forms of DNA,
on glassy carbon (G242). Other mediators reported during i.e., calf thymus, plasmid, single-strand vs double-strand,
this time period included nickelocene, which operates at a denatured, and supercoiled, is described in these two papers.
lower potential than ferrocene for glucose sensors (G243),the Supercoiled DNA was found to resist denaturation on the
water solubilization of T T F by complexation with 2- mercury surface in the potential range of -0.1 to -1.5 V vs
hydroxypropyl-0-cyclodextrin(G244),and a dimethyl(meth- SCE (G254).
y1thio)-substituted tetrathiafulvalene (MTTTF) for use in Covalent immobilization of polynucleotides on electrodes
glucose sensors (G245). was also reported. Maeda et al. affixed disulfide-modified
Analytical Chemktry, Vol. 66, No. 12, June 15, 1994 407R
solvents (D2O and H2I80) to trace the origin of intermediates theory for surface waves and OTTLE cells (146). The
and products of the electrode reactions (114). relationship between the d(ABS)/dt vs E curve and the
An on-line EC/MS study of 0 2 reduction under conditions corresponding voltammetric parameter is one of equivalence
of a methanol fuel cell allowed parallel reactions to be sorted in most situations.
out (115). Information on the reductive pathways for CH3- A spectroelectrochemical sensor for Cl2 based on a planar
CC13 a t the Pt/H2S04 interface (116) and for nitrite at optical waveguide was described (147). This novel device
graphite-supported CuO electrodes (11 7) was obtained. A employed a thin Lu-biphthalocyanine film on IT0 that could
porous Ni-plated Teflon membrane allowed the electroless be electrochemically reset to the reduced state. Oxidation of
Ni-P deposition to be followed by mass spectroscopy (118). the film by dissolved chlorine, which was monitored at 950
The oscillatory reaction involving bromate, malonic acid, and nm, resulted in an integral signal that was linear in the 0-30
the Ce4+i3+couple was followed by potentiometry and mass ppm range. The transmittance changes were detected using
spectroscopy. The production of COz(,) tracked the potential a transverse magnetically polarized evanescent wave. Wave-
oscillations in this system (119). length modulation spectroscopy was used to obtain spectra of
Several simplified designs of differential EC/MS interfaces methylene blue and Co tetrasulfonated phthalocyanine couples
have appeared (120,121). on graphite electrodes (148).The instrument described had
Articles continue to appear in which X-ray methods have a resolution of ca. 0.002 absorbance unit.
been used to probe the electrode/solution interface. These Several papers on experimental aspects were noted. A
techniques can give detailed specific information, i.e., bond simple procedure was given for the synthesis of SnO2 and the
lengths, in the best of circumstances, but require access to a preparation of SnO2-coated I T 0 glass electrodes (149). An
synchrotron radiation source. Two new descriptions of cell optically transparent carbon film electrode, with electro-
designs for in situ X-ray spectroelectrochemistry were noted chemical properties similar to glassy carbon, was prepared by
(122, 123). The latter employed transmission geometry the pyrolysis of an aromatic anhydride on a quartz substrate
through a drop of solution maintained on the electrode surface (150). The general method of modifying I T 0 electrodes of
by capillary action. Chen et al. deserves mention again (F88). Salbeck has
Adlayer formation via UPD of metals are well-suited to published two standard designs for thin-layer cells, in one of
study by X-ray methods. Recent systems examined include which only Teflon components contact the solution (151,152).
theUPDofPbandThonAu(l11)(124),CuUPDonPt(lIl) Shimazu et al. performed simultaneous UV/visible spectro-
(125) and Pt( 100) (126),Cu deposition on carbon-supported electrochemistry and QCM (153). Optically transparent
Pt (127),Ag UPD on Au( 11 1) (E234),and iodine adsorption contacts to the quartz crystal were used in a transmission
on Pt single crystal electrodes (128). In the UPD study at mode configuration.
Au( 11 l ) , it was found that the Au-Pb distance was potential Fluorescence spectroelectrochemistry was shown to be a
dependent, while the Au-Th distance was not (124). I n the sensitive method for the detection of intermediates and
surface EXAFS study of Cu UPD, chloride ion was shown to products of electrode reactions (154,155).These authors gave
play an important role in the ordering of the adlayer (125). details of their flow cell, which was used with a commercial
In situ X-ray methods have been used to follow intercalation luminescence spectrometer. Littig and Nieman also obtained
reactions of Moo3 (129),Li,CoOz (130), and V6OI3 (131) excellent sensitivity with an electrochemical FIA chemi-
electrodes. In situ X-ray spectra demonstrated the conversion luminescence method (156). Electrochemical reduction of
of cu-PbOz to the p-form on Pt substrates (132) and the 0 2 to H202 triggered the chemiluminescence of acridinium
formation of Cu20 layers by the reduction of Cu02’- in esters in a flow cell giving a LOD in the 10-fmol range. The
concentrated KOH (133). In situ XANES of Fe-26Cr sophisticated fluorescence imaging of electrode surfaces cited
stainless revealed peaks for Cr(V1) that could be correlated above can also be mentioned here (E115, E295).
with the transpassive voltammetric wave (134).Near-edge Two simple cell designs for luminescence spectroelectro-
EXAFS spectra demonstrated that disulfide bond scission chemistry have appeared (157,158).
occurred upon electroreduction of a sulfur polymer (135). Articles on ECL that were noted included a report that
In situ X-ray methods have monitored surface roughness ultrasonic radiation markedly enhanced the ECL intensity in
ofPt(l11) andAu(IOO)electrodes(Z36.137)andtheformation the R~(bpy)3~+/0xalate system (159)and the observation of
of oxides on dispersed Pt/C fuel cell electrodes (138). the ECL of perylene in a room-temperature molten salt (160).
Spectroelectrochemistry in the UV/visible region of the A weak photoemission seen during the evolution of 0 2 a t Pt
spectrum is routinely practiced in the characterization of in water was assigned to the recombination of singlet oxygen
inorganic, organic, and biological redox couples. On the molecules (161).
theoretical side, Wei et al. have published several papers on FT-IR spectroelectrochemical studies on adsorbed C O
spectroelectrochemistry under “long-path-length’’ conditions, continue to give detailed information on the interfacial
i.e., with the light beam parallel to the working electrode structure and electrode reactions. The spectra of Roth and
(139-143). One of the papers contains theoretical expressions Weaver indicated a terminal coordination of C O over a wide
for derivative linear sweep and derivative cyclic voltabsorp- potential range at Pt/nonaqueous interfaces (162).Bands in
tometry, e.g., expressions for d(ABS)/dE],k, under thin-layer the ATR-IR spectra of CO on Pt were assigned to a linearly
conditions (140). The case of semiinfinite linear diffusion bonded C O and possibly a multiply bonded species (163).
was also addressed. The catalytic EC’ mechanism has also FT-IR spectra of CO on Ni electrodes in KOH(,,) indicated
been treated under these conditions (144,145). Zamponi et oxidation via bridge-bonded C O to generate carbonate ions
al. have presented derivative linear sweep voltabsorptometry (164).Cation effects on the IR spectra of C O adsorbed on
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 409U
In situ Raman spectra of Zn-phthalocyanine films on Au A fast EQCM apparatus was used to study ion-exchange
and glassy carbon electrodes were obtained with a confocal reactions of poly(pyrro1e); a resolution of a few nanograms
spectrometer. A significant aspect of this study was that the in a measuring time of 1 ms was achieved (1132). The EQCM
irradiated spot on the electrode surface had a diameter of less experiment was performed with 30-MHz AT-cut quartz
than 1 ym (1117). crystals that had been chemically milled to produce a thin
Simonet and co-workers have used spin traps to detect disk surrounded by a thick quartz ring (1133). The resulting
radical intermediates in the electrochemical reduction of high-frequency operation afforded significantly increased
several species (1118,11 19). For the reduction of (C6Hs)dP+ sensitivity.
in nonaqueous solvents, it appeared that the CsH5' radical
was not an intermediate. ESR was also used to follow the J. INSTRUMENTATION
intercalation of lithium into V2O5 cathodes (1120). The time Circuit diagrams have been published for an instrument
frame accessible in the ESR-electrochemistry experiment was that simultaneously measured the electrode potential and the
ca. 1 s in the study of Dunsch and Petr (1121). resistance of an electrolyte solution ( J I ) and for several
13C N M R spectra were obtained for I3C-enriched C O on potentiostats (J2-J4). The single op amp potentiostat of
Pt-black surfaces under potential control (1122). Line Amatore and Lefrou allowed for ohmic drop compensation at
narrowing and chemical shifts were seen associated with sweep rates up to 300 kV/s. An instrument for digital ac
changes in the CO bonding at the surface. Another original voltammetry has also been described (J5).
spectroelectrochemical study was the in situ determination of A Fourier transform impedance spectrometer, which
atomic magnetic susceptibility using a nonspinning cell that operated in the frequency range 10-3-105 Hz, was described
operatedin the boreof a 400-MHzNMR spectrometer (1123). in some detail (56). Schefold gave details of an instrument
The test system for this study was a 0.1 M Fe(CN)63-/4COUpk for intensity-modulated photocurrent spectroscopy that em-
in D20 solution. ployed a red LED as the light source ( J 7 ) . It was used in a
Several applications of ellipsometry to electrochemistry nice study of charge transfer at p-InP single crystal electrodes.
have been described by Hamnett (1124). Ellipsometric A simple impedance instrument was described for measure-
transients were followed during adsorption of thiols on gold, ment of double-layer capacities ( J 8 ) .
growth of metal oxide films, and growth and switching of Several experimental apparatuses designed for operation
polymer films. The time scale was relatively slow, on the under extreme conditions were noted. These include an
order of seconds, but the author predicted advances in automatic setup for impedance measurements on two-electrode
instrumentation that would allow measurements in the cells over a frequency range from to lo7 Hz and a
millisecond range, as well as spatial resolution of ca. 10" cm2. programmed temperature range from room temperature to
Chao et al. measured effective dielectric constants for the 1100 K ( J 9 ) . Pressure effects on electrochemical potentials
electrode/solution interface at single crystal electrodes using were measured with a cell that withstood pressures up to 10
an ellipsometry method (1125). kbar (J10). The Ag/AgCl reference electrode potential was
Electrochemical quartz microbalance methodology has found to be relatively pressure insensitive in this study. The
proved to be useful for the study of a variety of interfacial high-pressure cell of Sachinidis et al. operated at pressures up
processes as evidenced by the many applications to surface to 1.5 kbar ( J I 1 ) . Cyclic voltammograms of several metal/
electrochemistry and polymer film electrodes cited above. metal oxide couples were obtained at 700-900 OC in an yttria-
Several recent papers have addressed experimental artifacts stabilized zirconia oxygen ion conducting electrolyte (J12).
that can arise with this technique. The problem of nonuniform As noted above, low-temperature electrochemistry has been
mass sensitivity across a QCM electrode surface was treated performed at superconducting UMEs; details of a cell design
authoritatively by Hillier and Ward (1126). Bacskai et al. were given by Green et al. (E346).
have also considered the QCM response for uneven coatings Several cleverly designed flow cells have been described
of polymer films (1127). The effect of surface microstructure including a RVC spectroelectrochemical detector for LCEC
on the QCM response was analyzed, and the analysis applied ( J 1 3 ) ,a carbon fiber cell (514, and a flow reactor containing
to roughened Ag/AgCI surfaces (1128). Frequency shifts on mosaics of ion-exchange membranes and bipolar metal
the order of a few hertz (e20 Hz) were seen for EQCM electrodes (J15). In the latter device, electrons and ions were
experiments with nonadsorbing couples for 5-MHz AT-cut transported in the same or opposite directions by the driving
quartz crystals (1129). These shifts were assigned to changes forces of redox potential and concentration gradients.
in the density and viscosity of the depletion layer at the A technique called "current spike polarography" was used
electrode surface. to study aqueous/air interfaces and thin films of solution held
EQCM of poly(bithiophene) electrodes indicated that rigid in a silver ring (J16). In the latter situation, a small volume
films were electrodeposited from CH3CN up to 50 nmol/cm2 of solution (0.01 mL) was positioned just below a DME
electroactive sites and that the Sauerbrey equation was valid capillary and the i-E-t transients were measured as the Hg
(1130). For thicker films departure from rigidity was seen. drop touched and fell through the solution. Comparison of
The dependence of the superficial energy of a QCM the zero current potential with that of the bulk solution
oscillator on elastic strain and stress predicted by the Lippmann polarogram gave an estimate of the surface potential of the
equation was experimentally verified (1131). By use of a dual electrolyte solution.
QCM oscillator, connected to the EQCM via a pressure Reference electrodes recommended for nonaqueous solvents
chamber, the effects of mass and surface energy could be included the 13-/1- couple in CH3CN (J17), a cross-linked
separated. poly(ethy1eneimine) film electrode loaded with Fe(CN)63-/4
410R Analytical Chemistty, Vol. 66, No. 12, June 15, 1994
(JZ8), and Mg(Hg) amalgam in D M F (J19). An electrode, Koryta, J. Ions, Electrodes andMembranes, 2nd ed.;J. Wiley & Sons:
New York, 1991.
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J. OM., Eds.; Plenum: New York, 1993; Vol. 24.
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screen printing Pt onto a ceramic substrate (J24),and a very StructureofEfectrifled Interfaces;Lipkowskl, J., Ross, P. N., Eds.; VCH
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Saveant, J.-M. Acc. Chem. Res. 1993, 25, 455-461.
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