The Influence of Rhodium(+3) onVoltammetry of Selenium(+4) in Perchloric Acid

In comparison with previously described voltammetric behavior of selenium(+4)–rhodium(+3) system in sulfuric or hydrochloric acid, results obtained in 0.1 mol/L perchloric acid differ significantly. The difference includes: a) number of signals and conditions under which they appear b) current‐concentration plots with nonzero intercepts c) unusual dependence of the peak characteristics on the speed of the applied technique and d) much more pronounced peak height enhancement. In square wave voltammetry the signal at ?0.75 V can be even 230 times higher with rhodium(+3) than without it. Most probably the peak at ?1.15 V corresponds to the catalytic reduction of hydrogen ions whereas the signal at ?0.75 V is additionally influenced by some other processes. Results are highly dependent on the form of rhodium(+3) in the initial solution and qualitatively similar to those previously obtained with sulfur compounds and dissolved metal catalysts.     

Voltammetry of Selenium(+4) in Atmospheric Precipitates

Using square‐wave cathodic stripping voltammetry on a hanging mercury drop electrode, selenium(+4) was measured in rainwater samples and snow melts. The ratio of peak currents, obtained from filtered and nonfiltered fractions of the same sample, could be even three, but standard addition method indicates the same initial concentration in both cases. The influence of filtration is explained in terms of decreased surfactant level. From one of the samples, double peaks of unknown origin were obtained. They reflect two irreversible processes which are not fully independent. Possible explanation includes two modifications of the same deposit, formed during accumulation step. The influence of surfactants and/or other organic compounds on the signal of interest could perhaps be useful in various studies of organic matter, dissolved in rainwater or snow melt.     

Voltammetric Behavior of Osmium‐Labeled DNA at Mercury Meniscus‐Modified Solid Amalgam Electrodes. Detecting DNA Hybridization

The complex of osmium tetroxide with 2,2′‐bipyridine has been utilized as a probe of DNA structure and an electroactive marker of DNA in DNA hybridization sensors. It produces several voltammetric signals, the most negative of them has been observed only at mercury electrodes. This signal is of catalytic nature affording a high sensitivity of DNA determination. The catalytic current due to evolution of hydrogen in voltammetry of DNA modified by complex of osmium tetroxide with 2,2′‐bipyridine (DNA‐Os,bipy) was studied. Solid amalgam electrodes (modified with mercury menisci) of silver (m‐AgSAE), copper (m‐CuSAE), gold, and of combined bismuth and silver, were used as possible substitutes for mercury electrodes. Besides the hanging mercury drop electrode (HMDE), the catalytic current was observed only on m‐AgSAE and m‐CuSAE. Electrodes of gold and bismuth amalgams did not give the catalytic current. The detection limit of DNA‐Os,bipy on HMDE was 0.1 ng mL^?1 (RSD=2.3 %, N=11), and on m‐AgSAE 0.2 ng mL^?1 (RSD=3.1%, N=11). The m‐AgSAE was successfully applied as a detection electrode in double‐surface DNA hybridization experiments offering highly specific discrimination between complementary (target) and nonspecific DNAs, as well as determination of the length of a repetitive DNA sequence. The m‐AgSAE has proved a convenient alternative to the HMDE or carbon electrodes used for similar purposes in previous work.     

Voltammetric Behavior of Antileukemia Drug Glivec. Part II – Redox Processes of Glivec Electrochemical Metabolite

Glivec is a newly developed drug that belongs to the class of 2‐phenylaminopyrimidine. It is a potent inhibitor of ABL‐kinase, the main clinical manifestation of chronic myelogenous leukemia (CML). Based on its activity on CML, glivec is undergoing extensive evaluation for its activity against other tumor types. Detection and quantitation of glivec in biological fluids or cells is thus very important. The antileukemia drug glivec undergoes oxidation at glassy carbon electrodes and involves the formation of an oxidation product, P_glivec. The adsorption of P_glivec at the GCE surface yields a compact monolayer allowing an electrochemical study of this compound adsorbed at the GCE surface. The reversible redox reaction of the adsorbed P_glivec is pH dependent and occurs with the transfer of 2 electrons and 2 protons. The surface standard potential and the rate constant of the heterogeneous electrochemical reaction were calculated using cyclic voltammetry to be E^θ′=+180 mV and k=15.5 s^?1, respectively. The total surface concentration of adsorbed P_glivec is 2.5×10^?12 mol cm^?2. The analytical determination of glivec was carried out by differential pulse voltammetric measurement of the anodic peak current corresponding to either the oxidation peak of glivec or the oxidation peak of P_glivec adsorbed on the GCE surface. The limits of detection of glivec and adsorbed P_glivec based on three times the noise level are 3.3×10^?8 M and 2.9×10^?10 M, respectively.     

Ni(II)cyclam Catalyzed Reduction of CO2 – Towards a Voltammetric Sensor for the Gas Phase

The detection of CO₂ in the gas phase is possible in presence of oxygen with an amalgamated Au‐poly(tetrafluoroethylene) gas diffusion electrode and an internal electrolyte solution containing Ni(II)cyclam. For concentrations between 0.1 to 1% the electrochemical cell has a sensitivity of 3.58 mA %^?1 and the detection limit is 500 ppm. In preliminary experiments at rotating disk electrodes the optimum pH‐range was found to be between 3.5 to 6 and a selectivity ratio of the catalyst for CO₂/H⁺ of 5 : 1 could be determined. The relationship between reduction current and the square root of the angular speed is linear, indicating that the electrochemical process is limited by diffusion of CO₂. Tl and Pb are presented as alternative electrode materials at which the Ni(II)cyclam catalyzed reduction of CO₂ can be observed. Problems arise from fouling effects at the sensing electrode and a non‐linearity of the calibration plot at higher concentrations.     

Voltammetric Analysis of Trace Levels of Platinum Group Metals – Principles and Applications

The compelling use of autocatalytic converters, containing platinum group metals (PGMs), has been the cause, in the environmental and biological matrices, of an increasing concentration of such metals. For this reason, in the last decade, the literature has reported several papers regarding analytical procedures for the determination of Pt(II), Pd(II) and Rh(III) in real samples, generally employing spectroscopic methods. The present review intends to highlight the contribution of the voltammetric techniques for the determination of these metals, including also those less investigated, i.e. Iridium, Osmium and Ruthenium.     

Voltammetric Behavior of Antileukemia Drug Glivec. Part I – Electrochemical Study of Glivec

The electrochemical behavior of the antileukemia drug glivec was investigated at a glassy carbon electrode (GCE). The oxidation is a complex, pH‐dependent, irreversible electrode process involving the transfer of 2 electrons and 2 protons and the formation of an electroactive product, P_glivec, which strongly adsorbs on the GCE surface and undergoes reversible oxidation. The adsorption of P_glivec at the GCE surface yields a compact monolayer that inhibits further oxidation of glivec. The electrochemical reduction is a simple pH dependent irreversible process involving the transfer of 2 electrons and 2 protons and occurs with the formation of a nonelectroactive product. The diffusion coefficient of glivec was calculated to be D_O=7.35×10^?6 cm² s^?1 in pH 4.5 0.1 M acetate buffer.     

Application of the Bismuth Film Electrode for Voltammetric Determination of Titanium Using Ti(IV)‐Oxalate‐Chlorate Catalytic System

The catalytic voltammetric protocol for the determination of titanium at a bismuth film electrode is presented. The method is based on the reduction of the Ti(IV)‐oxalate complex to Ti(III)‐oxalate in an acidic solution. It was proven that the addition of KClO₃ causes rapid oxidation of Ti(III)‐oxalate and, subsequently, an increase of the reduction peak current of Ti(IV) at the bismuth film electrode. Parameters that influence the Ti response, including the film preparation, solution pH, oxalate acid and chlorate concentrations, were optimized. The exploitation of the bismuth film electrode under the optimized conditions yielded a stable response for titanium, with high sensitivity (12.5 μA μM^?1), good precision (RSD=5.0%) and a low detection limit (1×10^?8 M).     

Rhodium(I) and Silver(I) Complexes of 4, 5‐Dicyano‐1, 3‐dimesityl‐ and 4, 5‐Dicyano‐1, 3‐dineopentylimidazol‐2‐ylidene

The new N‐heterocyclic carbene (NHC) precursors 4, ‐dicyano‐1, ‐dimesityl‐ ( 9 ) and 4, 5‐dicyano‐1, 3‐dineopentyl‐2‐(pentafluorophenyl)imidazoline ( 14 ) were synthesized. The structure of 9 could be determined by X‐ray crystallography. With the 2‐pentafluorophenyl‐substituted imidazolines 9 and 14 , the [AgCl(NHC)], [RhCl(COD)(NHC)], and [RhCl(CO)₂(NHC)] complexes [NHC = 4, 5‐dicyano‐1, 3‐dimesitylimidazol‐2‐ylidene ( 3 ) and 4, 5‐dicyano‐1, 3‐dineopentylimidazol‐2‐ylidene ( 4 )] were obtained. Crystal structures of [AgCl( 3 )] ( 15 ), [RhCl(COD)( 3 )] ( 17 ), [RhCl(COD)( 4 )] ( 18 ), and [RhCl(CO)₂( 3 )] ( 19 ) were solved and with the crystal data of 19 , the percent buried volume ( %V_bur) of 31.8(±0.1) % was determined for NHC 3 . Infrared spectra of the imidazolines 9 and 14 and of the complexes 15 – 20 were recorded and the CO stretching frequencies of complexes 19 and 20 were used to determine the Tolman electronic parameters of the newly obtained NHCs 3 (TEP: 2060 cm^–1) and 4 (TEP: 2061 cm^–1), thus proving that 1, 3‐substitution of maleonitrile‐NHCs does not have a significant effect for the high π‐acceptor strength of these carbenes.     

Voltammetric Characterization of 2‐Methoxy‐4‐Nitrophenyl Derivatized Carbon Powder

Carbon powder has been functionalized with 2‐methoxy‐4‐nitrophenyl groups by the reduction of 2‐methoxy‐4‐nitrobenzenediazonium‐1,5‐naphthalenedisulfonate salt in presence of hypophosporous acid as a reducing agent. This provides an easy and inexpensive methodology to modify the carbon particle surface. This derivatization is carried out in the presence of 2‐methoxy‐4‐nitrobenzenediazonium 1,5‐naphthalenedisulfonate salt along with the carbon powder and hypophosporous acid. The electrochemical behavior of the resulting 2‐methoxy‐4‐nitrophenyl functionalized carbon powder was characterized by immobilizing it onto basal plane pyrolytic graphite (bppg) electrode and studying its voltammetric behavior. The surface morphology of derivatized carbon powder has been examined by SEM studies which revealed that the size of the functionalized carbon particles are larger than bare carbon particles The effect of pH on peak potentials, scan rate and stability of the functionalized carbon particles has revealed that they are surface bound species.     

Mono‐ and Binuclear Rhodium and Platinum Complexes of 1, 3, 5‐Trimethyl‐1, 3, 5‐triaza‐2σ3λ3‐phosphorin‐4, 6‐dionyloxy‐substituted Calix[4]arenes

The reaction behaviour of 1, 3, 5‐triaza‐2σ³λ³‐phosphorin‐4, 6‐dionyloxy‐substituted calix[4]arenes towards mono‐ and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)‐substituted calix[4]arene ( 4 ) and its tert‐butyl‐derivative ( 1 ) with [(cod)RhCl]₂ yielded the mono‐ and disubstituted binuclear rhodium complexes 2 , 3 , and 5 . In all cases, a C₂‐symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1, 3‐alternating conformation. The X‐ray crystal structure determination of 5 confirmed [(calixarene)RhCl]₂‐coordination through two opposite phosphorus atoms with a P ⃜P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh₂Cl₂ core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)‐bis(methoxy)‐substituted tert‐butyl‐calix‐[4]arene ( 7 ) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF₄ led to the expected cationic monorhodium complexes 5 and 8 , involving 1, 3‐alternating P‐Rh‐P‐coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the ¹J(PRh) coupling constants in the ³¹P‐NMR‐spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after addition of HBF₄, to the corresponding mononuclear cationic complexes 9 and 10 . Only two of the four phosphorus atoms in 9 and 10 are coordinated to the central metal atom. Displacement of either cycloocta‐1, 5‐diene or norbornadiene was not observed. For both compounds, the cone conformation was proved by NMR spectroscopy. Reaction of 4 with (cod)PtCl₂ led to the PtCl₂‐complex ( 11 ). As for all compounds mentioned above, only two phosphorus atoms of the ligand coordinate to platinum, while two phosphorus atoms remain uncoordinated (proved by δ³¹P and characteristic values of ¹J(PPt)). NMR‐spectroscopic evidence was found for the existence of the cone conformation in the cis‐configuration of 11 .     

Halide Abstraction by Na[B{C6H3(CF3)2‐3,5}4]: Synthesis and Structural Characterization of the Rhodium(I) Cations [(η6‐arene)Rh(PPh3)2]+ (Arene = benzene,toluene)

Halide abstraction from [(Ph₃P)₂Rh(μ‐Cl)]₂ by the sodium salt of the weakly coordinating [BAr^f₄]^? anion [Ar^f = C₆H₃(CF₃)₂‐3,5] in the presence of excess arene offers a convenient, high‐yielding route to the half‐sandwich cations [(arene)Rh(PPh₃)₂]⁺[BAr^f₄]^? [arene = benzene ( 1 ), toluene ( 2 )]. Crystalline samples of 1 and 2 are isomorphous [a = 13.1270(2), b = 15.3030(2), c = 17.5760(3) Å, α = 74.620(1), β = 81.533(1), γ = 88.540(1)° for 1 ] and feature the arene ligand bound to the rhodium atom in η⁶ fashion.     

Voltammetric Determination of 4‐Nitrophenol and 5‐Nitrobenzimidazole Using Different Types of Silver Solid Amalgam Electrodes – A Comparative Study

The voltammetric behavior of two genotoxic nitro compounds (4‐nitrophenol and 5‐nitrobenzimidazole) has been investigated using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a polished silver solid amalgam electrode (p‐AgSAE), a mercury meniscus modified silver solid amalgam electrode (m‐AgSAE), and a mercury film modified silver solid amalgam electrode (MF‐AgSAE). The optimum conditions have been evaluated for their determination in Britton‐Robinson buffer solutions. The limit of quantification (L_Q) for 5‐nitrobenzimidazole at p‐AgSAE was 0.77 µmol L^?1 (DCV) and 0.47 µmol L^?1 (DPV), at m‐AgSAE it was 0.32 µmol L^?1 (DCV) and 0.16 µmol L^?1 (DPV), and at MF‐AgSAE it was 0.97 µmol L^?1 (DCV) and 0.70 µmol L^?1 (DPV). For 4‐nitrophenol at p‐AgSAE, L_Q was 0.37 µmol L^?1 (DCV) and 0.32 µmol L^?1 (DPV), at m‐AgSAE it was 0.14 µmol L^?1 (DCV) and 0.1 µmol L^?1 (DPV), and at MF‐AgSAE, it was 0.87 µmol L^?1 (DCV) and 0.37 µmol L^?1 (DPV). Thorough comparative studies have shown that m‐AgSAE is the best sensor for voltammetric determination of the two model genotoxic compounds because it gives the lowest L_Q, is easier to prepare, and its surface can be easily renewed both chemically (by new amalgamation) and/or electrochemically (by imposition of cleaning pulses). The practical applicability of the newly developed methods was verified on model samples of drinking water.