JSCSEN 74(10)1021–1153(2009) e v ersion lectronic VOLUME 74 Available on line at No 10 BELGRADE 2009 www.shd.org.rs/JSCS/ The full search of JSCS is available through www.doaj.org J. Serb. Chem. Soc. Vol. 74, No. 10 (2009) CONTENTS K. Vytřas, I. Švancara and R. Metelka: Carbon paste electrodes in electroanalytical che- mistry (Authors’ review) ............................................................................................. 1021 Organic Chemistry and Biochemistry V. Tešević, S. Milosavljević, V. Vajs, I. Đorđević, M. Soković, V. Lavadinović and M. No- vaković: Chemical composition and antifungal activity of the essential oil of Douglas fir (Pseudosuga menziesii Mirb. Franco) from Serbia .................................................. 1035 S. F. Barbuceanu, G. L. Almajan, I. Saramet, C. Draghici, R. Socoteanu and F. Barbuce- anu: New S-alkylated 1,2,4-triazoles incorporating diphenyl sulfone moieties with potential antibacterial activity ..................................................................................... 1041 M. V. Zlatović, V. V. Šukalović, G. M. Roglić, S. V. Kostić-Rajačić and D. B. Andrić: The influence of dispersive interactions on the binding affinities of ligands with an aryl- piperazine moiety to the dopamine D2 receptor ......................................................... 1051 M. A. Nasar, A. Jarrari, M. A. Naseer, T. F. Subhani, B. V. Shetty and F. Shakeel: Anti- oxidant status of atorvastatin in hypercholesterolemic patients .................................. 1063 Inorganic Chemistry L. Mitu, N. Raman, A. Kriza, N. Stănică and M. Dianu: Template synthesis, characteri- zation and antimicrobial activity of some new complexes with isonicotinoyl hydrazone ligands ....................................................................................................... 1075 G. N. Krishnamurthy and N. Shashikala: Synthesis of ruthenium(II) carbonyl complexes with 2-monosubstituted and 1,2-disubstituted benzimidazoles ................................... 1085 C. Zhuang, X. Tang, D. Wang, A. Xia, W. Lian, Y. Shi and T. Shi: An unsymmetrical por- phyrin and its metal complexes: synthesis, spectroscopy, thermal analysis and liquid crystal properties ......................................................................................................... 1097 R. Ghiasi: Theoretical insights into the properties of the borazine⋅⋅⋅X–complexes (X– = H, F, Cl, CN, NC or NCO) .............................................................................................. 1105 Physical Chemistry S. Mentus, Z. Mojović and V. Radmilović: The use of NaX zeolite as a template to obtain a mono-atomic Pt dispersion by impregnation with Pt(II) acetylacetonate/acetone solution ....................................................................................................................... 1113 D. R. Sekulić, B. M. Babić, Lj. M. Kljajević, J. M. Stašić and B. V. Kaludjerović: The ef- fect of gamma radiation on the properties of activated carbon cloth .......................... 1125 Analytical Chemistry Z. J. Huang, X. G. Wang and J. Zhang: Solid phase extraction and a spectrophotometric method for the determination of trace amounts of gold with 4-rhodanineazo benzoic acid .............................................................................................................................. 1133 Z. B. Todorović, M. L. Lazić, V. B. Veljković and D. M. Milenović: Validation of an HPLC–UV method for the determination of digoxin residues on the surface of ma- nufacturing equipment ................................................................................................ 1143 Published by the Serbian Chemical Society Karnegijeva 4/III, 11000 Belgrade, Serbia Printed by the Faculty of Technology and Metallurgy Karnegijeva 4, P.O. Box 35-03, 11120 Belgrade, Serbia Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS J. Serb. Chem. Soc. 74 (10) 1021–1033 (2009) UDC 541.135.5–039.26:543.55: JSCS–3896 681.586.000.57 Authors’ review AUTHORS’ REVIEW Carbon paste electrodes in electroanalytical chemistry# KAREL VYTŘAS*, IVAN ŠVANCARA and RADOVAN METELKA Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, CZ – 532 10 Pardubice, Czech Republic (Received 17 April 2009) Abstract: An overview is given dealing with the applications of carbon paste electrodes in equilibrium potentiometry as well as in electrochemical stripping analysis using both voltammetric and potentiometric modes. Various modifica- tions of carbon pastes and carbon paste-based biosensors are also mentioned. The main emphasis in this article is directed at summarizing recent results of the authors’ research group during the past few years. Keywords: carbon paste electrodes; potentiometry; electrochemical stripping analysis; flow injection analysis; electrode modification; heavy metals deter- mination; biosensors. CONTENT 1. INTRODUCTION 2. CONSTRUCTION OF CARBON PASTE ELECTRODES 3. POTENTIOMETRY 3.1. Electrochemical stripping analysis with unmodified paste electrodes 3.2. Modified carbon pastes in stripping analysis 4. CARBON PASTE AS A SUPPORT FOR METALLIC FILM ELECTRODES 5. AMPEROMETRIC (BIO)SENSORS 6. CONCLUSION 1. INTRODUCTION Carbon paste electrodes (CPEs) belong to promising electrochemical or bio- electrochemical sensors of wide applicability. In 2008, it was exactly a half cen- tury since Ralph Norman Adams from the University of Kansas published a short one-page report1 in which he introduced this kind of electrode, which was origi- nally designed as an alternative to the dropping mercury electrode. Although the concept of a dynamic renewable electrode surface was not successful, it turned * Corresponding author. E-mail: [email protected] # Presented as Invited Lecture at 47th Meeting of the Serbian Chemical Society, Belgrade, Serbia, 2009. doi: 10.2298/JSC0910021V 1021 Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1022 VYTŘAS, ŠVANCARA and METELKA out that the material with paste-like consistency could be practically employed in voltammetric analysis. After the pioneering work of Kuwana,2,3 who actually first modified a CPE by introducing an electrochemically active surface into the material and, after the first chemical modification of an electrode for electrosyn- thesis,4 the modification was soon applied to carbon paste electrodes.5,6 Finally, Baldwin described a simple method of direct mixing of a solid modifier to the paste,7 which was the commencement of explosive research activity in this field. Quite a few reviews are exclusively devoted to CPEs.8–14 Presently, CPEs repre- sent one of the most frequent types of working electrodes. The overwhelming number of CPEs used worldwide belongs to pastes with insulating liquids (paraf- fin oil, silicon oil, bromonaphthalene, tricresyl phosphate and others). The basic requirements for a pasting liquid are its practical insolubility in the solution under measurement, a low vapor pressure to ensure both mechanical stability and long lifetime, and further, in the case of voltammetric and amperometric applications, its electrochemical inactivity in the potential window of interest. In contrast to the relatively complicated modifications of solid substrates, carbon pastes can be modified simply to obtain quantitatively new sensors with desired, often prede- fined, properties.15 Very recently, a review with 333 references was published16 in the form of a retrospective compilation presenting the field by means of va- rious facts, notes, data, surveys, and summaries that illustrate individual achieve- ments and milestones. A brief overview based mainly on the authors’ group con- tributions is thus given in this paper. 2. CONSTRUCTION OF CARBON PASTE ELECTRODES Common types of carbon pastes are soft and non-compact, and have to be kept in special bodies. A holder for carbon pastes can be realized as a well drilled into a short Teflon rod,17 a glass tube18 or a polyethylene syringe19 filled with a paste, which is electrically contacted via a conducting wire. Such constructions are very simple; however, there is one aspect which makes them not very conve- nient for practical use and this is the necessity of refilling the carbon paste in ex- periments requiring a regular removal of the electrode surface layer. More so- phisticated constructions circumventing this time-consuming procedure were de- signed by Monien et al.20 and Lindquist,21 who proposed piston-driven electrode holders where the desired amount of the used paste could simply be extruded from the electrode body and smoothed away or cut off. Similar types of home- -made piston-driven carbon paste holders are used by our research team.15,22 Recently, our research group also devoted particular attention to the develop- ment of novel or innovated carbon paste electrode holders. Two typical examples of these activities are illustrated in Fig. 1. Image “1A” shows two variants of the so-called carbon paste groove electrode (CPGrE) as atypical construction of CPE, copying the planar design of some screen-printed electrodes.23 The CPGrE Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1023 CARBON PASTE ELECTRODES IN ELECTROANALYTICAL CHEMISTRY assembly comprises a miniature plastic prismatic bar with a horizontal channel for carbon paste filling, a metal contact and additional plastic insert(s) defining the electrode surface via its mechanical coverage/exposure. The whole construc- tion can be devised as an electrically heated electrode (left), applicable for batch measurements and allowing the sensitivity of measurements that have to be made in still solutions to be enhanced or as the working electrode for hydrodynamic amperometry, and as the detector in flowing streams (right). The usefulness of the latter was demonstrated in a very recent study concerning its intimate testing in the FIA mode.24 Fig. 1. Some novel construction types of electrode holders for carbon paste. Two assembled carbon paste groove electrodes; the electrically heated variant (A – left) and set-up for detection in the FIA-mode (A – right); two carbon paste mini-electrodes; with an uncut tip (B – left), cut-off variant offering a larger surface diameter (B – right). For further specification, see original reports.23-25 A new type of carbon paste mini-electrode (CPmE) which can be made from common plastic pipette tips, the vertical cutting of which provides the desired surface area,25 is depicted in photograph “1B”. The advantage of this small de- sign is the minimization of the consumption of carbon paste(s), which can be economic when using some mixtures from rather expensive carbon nanotubes, for example. 3. POTENTIOMETRY From the viewpoint of equilibrium potentiometry, the composition of carbon pastes enables the classification of CPEs as ion-selective liquid membrane type electrodes. The pasting liquid usually exhibits good extraction ability against ne- utral electroactive species of non-dissociated weak acids, neutral metal chelates or ion associates. Then, the potential of an electrode containing such an organic solvent extract is predominantly governed by ionic exchange at the interface be- tween the organic phase of the electrode and the sample solution, resulting in the Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1024 VYTŘAS, ŠVANCARA and METELKA so-called Donnan potential.26 Carbon paste-based ion-selective electrodes (CPISEs) were reported and applied for the determination of several ions (see Refs.14,26 and references therein). For example, four ion-exchangers were prepared for new perchlorate and fluoroborate CPISEs, which found their application in the direct potentiometric determinations of the two anions, as well as monitoring sensors for potentiometric ion-pair formation-based titrations.27 Similarly, the ion-pairing principle was used in titrations of complex anions of trivalent thallium28 or ele- ments forming heteropolyanions.29,30 An application of the CPGrE type cons- truction (see above) in potentiometric pH measurements31 is presented in Fig. 2. Fig. 2. Potentiometric responses of carbon paste groove electrodes with dispersed bismuth powder (17 % w/w) in Britton–Robinson buffer solution (three repeated measurements). The electrode surface was renewed after each set of measurements (A); all sets measured at the same surface (B). A distinct advantage of carbon paste-based electrodes is their very low ohm- ic resistance (less than 10 Ω instead of up to MΩ values for electrodes equipped with polymeric membranes). Thus, experimental work with CPISEs is more con- venient and simpler potentiometers allowing voltage measurements of potentio- metric cells with lower inner resistance may be applied. This fact accompanied with a very quick response time is especially appreciated in automatic titration procedures.32 Thus, all procedures elaborated for potentiometric indication of ion-pair formation-based titrations with polymeric membrane electrodes33 can simply be monitored using CPISEs; the determination of surfactants can serve as an excellent example.34 Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1025 CARBON PASTE ELECTRODES IN ELECTROANALYTICAL CHEMISTRY 3.1. Electrochemical stripping analysis with unmodified paste electrodes In voltammetric stripping analysis, the choice of the main constituents for the preparation of the carbon paste was rather conservative and, in fact, there were no attempts to seek new alternative materials. The properties of conve- ntional paste mixtures from spectroscopic graphite and paraffin oils were found satisfactory for the majority of applications. An example can be given dealing with application of such an electrode for trace iron(III) determination in com- pounds of pharmaceutical significance.35 In 1993, some new types of CPEs con- taining more polar organic liquids, often used as plasticizers of polymeric mem- brane-based ion-selective electrodes, were introduced.36 Consequently, it was shown that these pasting liquids act as anion exchangers in acidic media due to the presence of some protonizable functional groups. For example, a CPE con- taining tricresyl phosphate was found suitable for the accumulation of some lipo- philic anions, forming ion-pairs with the protonized pasting liquid. At that time, some interesting applications of these pastes in both stripping voltammetry37,38 and stripping chronopotentiometry39–42 were introduced. 3.2. Modified carbon pastes in stripping analysis Carbon pastes undoubtedly represent one of the most convenient materials for the preparation of modified electrodes. A modifier can be dissolved in a bin- der or admixed mechanically to the paste during its homogenization. For examp- le, a CPE modified with cobalt(II) phthalocyanine was used for voltammetric de- termination of ascorbic acid in foodstuffs.43 In situ modification of the electrode paste surface is often used as well; examples may be given dealing with appli- cations of an anionic surfactant for voltammetric determination of silver(I) at ul- tratrace levels.44 Recently, some procedures utilizing cationic surfactants for in situ modifications of CPEs were reported for determinations of chromium(VI),45 osmium(IV)46 and other platinum metals,47 whereby negatively charged complex anions were formed. 4. CARBON PASTE AS A SUPPORT FOR METALLIC FILM ELECTRODES In order to prepare electrodes plated with metallic films, numerous conduc- tive materials have been proposed for use; glassy carbon is probably the most fre- quently employed material. It was confirmed that carbon paste as a support for plating with metallic films is able to offer results similar to those of well estab- lished solid electrodes and, in addition, their easy and inexpensive preparation and no risk of mechanical damage of the electrode surface are very advan- tageous. Mercury film electrodes were very popular and mostly employed in electro- chemical stripping determinations of heavy metal ions instead of stationary mer- cury electrodes. For example, a CPE containing tricresyl phosphate was found to Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1026 VYTŘAS, ŠVANCARA and METELKA be especially suitable for this purpose; both voltammetric and chronopotentio- metric modes were applied.48,49 It was also confirmed that a mercury film with properties similar to those of a mercury film generated from solutions of mer- cury(II) salts may be obtained by reduction of mercury(II) oxide dispersed in a paste.50 Since 1996, investigations on gold film-plated CPEs represents a new sub- ject of our research because, hitherto, no report on such electrodes had been pub- lished. They were found useful for the determination of mercury51 and arsenic.52 Bismuth film electrodes (BiFEs) were first prepared by Schwabe53 and used in potentiometric pH measurements. Into electrochemical stripping analysis, they were introduced by Wang et al. in 2000.54 This whole topic has already achieved a relevant position within research activities devoted to the development and ap- plication of mercury-free electrodes. Their most significant advantage is that they are environmentally friendly, since the toxicity of bismuth and its salts is signi- ficantly lower than that of salts of other heavy metals. Furthermore, the advanta- geous analytical properties of BiFEs in electrochemical stripping analysis, rough- ly comparable to those of mercury film electrodes, are attributed to the property of bismuth to form alloys with various metals (which is analogous to the amal- gams formed by mercury). Many papers appearing since introduction of BiFEs are referred to in recent reviews.55–59 Unfortunately, numerous authors simply followed the original procedure;54 this means that BiFEs were prepared using either different substrates or different varieties in their constructions but they were only applied in the determinations of the same metal ions - lead(II) and cad- mium(II) – in the same medium – a pH 4.5 acetate buffer. However, it has been shown that bismuth film-plated CPEs may also be applied in alkaline media, such as ammonia buffers60 or even 0.10 M KOH solution.61 The role of the plating regime in the deposition of bismuth films onto a car- bon paste surface was also investigated. It should be noted that the term “film” does not correspond with the real situation as it is not compact: analogously to mercury “films” deposited in form of isolated droplets, bismuth is deposited in form of isolated crystals. The new observations performed by scanning electron microscopy were focused mainly on morphological transformations of the micro- structure of the bismuth film in dependence on the deposition process and its intensity during potentiostatic electrolysis.62 To overcome such electrolytic depo- sitions, bismuth powder-dispersed CPEs were introduced.63 The electrode paste was prepared as a mixture of finely powdered metallic bismuth together with gra- phite powder and silicon oil and was characterized in solutions containing Cd(II) and Pb(II) at the microgram/liter level in conjunction with square-wave anodic stripping voltammetry. The electrode exhibited well-defined and separated strip- ping signals for both metals accompanied with a low background contribution. Moreover, it exhibited superior performance in comparison to the bare CPE and, Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1027 CARBON PASTE ELECTRODES IN ELECTROANALYTICAL CHEMISTRY surprisingly, yielded a response higher than that of an in situ prepared bismuth film CPE. The introduction of bismuth(III) salts and bismuth films into electroanalysis also instigated the novel approach of potentiometric stripping analysis based on total substitution of mercury by bismuth. First, Bi(III) salts could be applied to form bismuth films. Secondly, bismuth(III) salts could substitute mercury(II) in its role as an oxidant. These facts offer quite new possibilities of an attractive use of “mercury-free”, environmentally friendly PSA procedures for the determina- tions of some heavy metals. The highest signals were observed when working in solutions containing anions forming complexes with bismuth(III), such as chlo- rides or bromides.64 Similarly to bismuth, antimony bulk electrodes are also well known from equilibrium potentiometry. Concerning voltammetry, attempts with modifications of screen-printed carbon electrodes using either Bi O or Sb O were also real- 2 3 2 3 ized,65 but the first antimony film electrode prepared in situ on a glassy carbon electrode substrate and employed in combination with either stripping voltam- metry or stripping potentiometry was reported very recently.66 Simultaneously, initial studies with antimony-modified CPEs, focusing on their performance in anodic stripping voltammetry, were performed; the investigations comprised the first experiments with Sb film-plated and Sb powder-dispersed CPEs.67,68 Again, antimony films generated in situ on CPEs with excess antimony(III) salts as che- mical oxidants were introduced as new procedures for potentiometric stripping analysis following previous electrolytic preconcentration of the to be determined metals.69 Moreover in acidic solutions containing halide ions, the oxidation abi- lity of Sb(III) is adequately limited because of the formation of its corresponding halide complexes. Compared with similar total substitution of traditionally used mercury(II) by bismuth(III), the use of antimony(III) offers a higher sensitivity in the detection of heavy metals. Typical stripping voltammetric responses of metallic film, metal powder, and metal oxide-modified CPEs obtained by analyzing an equimolar mixture of Cd(II) and Pb(II) ions in model water samples are depicted in Fig. 3. The figure shows a comparison of the individual electrode configurations in two sets of vol- tammograms (A and B), taken from previous studies,59,67,70 in which the res- pective experimental conditions and, especially, the supporting electrolyte were optimized for the antimony-modified variants. 5. AMPEROMETRIC (BIO)SENSORS In collaboration with Austrian colleagues, the first modifications of carbon pastes with manganese dioxide films in order to obtain sensors for the determi- nation of hydrogen peroxide commenced at the end of the nineties.71–73 How- ever, for application in procedures utilizing flow injection analysis, it seemed Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS 1028 VYTŘAS, ŠVANCARA and METELKA more effective to transfer all experience obtained with such CPE-based sensors to their analogous screen-printed configurations.74 Such sensors enabled the detec- tion of hydrogen peroxide by either mediated oxidation or mediated reduction (Fig. 4). A B Fig. 3. Anodic stripping voltammograms of Cd(II) + Pb(II) at different types of metal film-plated and metal or metal oxide powder-dispersed carbon paste electrodes. Mercury, bismuth or antimony film-plated carbon paste electrode (MF-CPE, BiF-CPE, or SbF-CPE) (A); HgO (5 %), Bi (20 %) or Sb (20 % w/w) powder-dispersed CPE (B); supporting electrolyte, 0.01 M HCl; c(Cd,Pb) = 50 ppb; c(Hg,Bi,Sb) = = 1×10-5 mol L-1 (for A); accumulation potential, −1.2 V vs. Ag/AgCl/3M KCl; accumulation time, 120 s; equilibrium time, 15 s; potential range from −1.1 to −0.30 V. Furthermore, in combination with a proper biocatalyst (glucose oxidase was used in the initial experiments), they served as basic units in the construction of the corresponding biosensors;75,76 a similar biosensor based on sarcosine oxidase was also reported.77 Modification with other metal oxides were also studied.78–80 Recently, biosensors possessing very good properties were obtained when elec- trocatalysts based on the oxides of platinum group metals were used as modi- fiers/mediators.81–85 Biosensors based on dehydrogenases were also studied.86 Available online at www.shd.org.rs/JSCS/ ___________________________________________________________________________________________________________________________ 2009 Copyright (CC) SCS