bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis, Structure, and Reactivity of Novel Intramolecularly Coordinated Organolead(II) Compounds
Authors: Jurkschat Klaus , Peveling Katja , Schürmann Markus 
Published: September 2003

AbstractThe intramolecularly coordinated heteroleptic organolead(II) compounds {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}PbX (2, X = Cl; 3, X = SPh) have been synthesized. Single‐crystal X‐ray analyses reveal that both compounds adopt polymeric chain structures by intermolecular Pb−X···Pb bridges, a structural motif previously unknown for organolead(II) derivatives. Compound 2 reacts with lithium diisopropylamide, iPr2NLi, and lithium bis(trimethylsilyl)methane, (Me3Si)2CHLi, respectively, to provide in situ the corresponding organolead(II) compounds {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}PbX (4, X = iPr2N; 5, X = (Me3Si)2CH], which were identified by NMR spectroscopy but could not be obtained as analytically pure substances. Attempts to isolate the intramolecularly coordinated organolead(II) hexafluorophosphate {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}Pb+PF6− from the reaction of 2 with TlPF6 also failed. Instead, the unprecedented salt [{5‐tBu‐1,3‐[P(O)(OEt)2]2C6H3}4·(Pb2F)] [PF6]3·4THF (6) was obtained, in which the [(Pb−F−Pb)]3+ cation is stabilized by eight intermolecular P=O⇄Pb interactions. Compound 6 was characterized by single‐crystal X‐ray analysis and electrospray mass spectrometry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Preparation of Optically Active α‐Amino[3]ferrocenophanes − Building Blocks for Chelate Ligands in Asymmetric Catalysis
Authors: Liptau Patrick , Tebben Ludger , Kehr Gerald , Wibbeling Birgit , Fröhlich Roland , Erker Gerhard 
Published: September 2003

AbstractTreatment of 1,1′‐diacetylferrocene (4) with dimethylamine and TiCl4 yielded the unsaturated dimethylamino‐substituted [3]ferrocenophane product 5. Its catalytic hydrogenation gave the corresponding saturated [3]ferrocenophane system 6 (trans/cis ≈︁ 7:1). The rac‐[3]ferrocenophane amine 6 was partially resolved (to ca. 80% ee) by means of L‐ or D‐O,O′‐dibenzoyltartrate salt formation. Treatment of 4 with the pure (R)‐ or (S)‐methyl(1‐phenylethyl)amine (8)/TiCl4 gave the corresponding optically active unsaturated [3]ferrocenophane amines (R)‐(+)‐9 and (S)‐(−)‐9, respectively. Their catalytic hydrogenation again proceeded trans‐selectively, giving the corresponding saturated diastereomeric [3]ferrocenophane amines (1R,3R,5R)‐10a and (1S,3S,5R)‐10b [starting from (R)‐9], their enantiomers ent‐10a and ent‐10b were obtained from (S)‐9, but with a poor asymmetric induction (10a/10b < 2:1). Quaternization of 6 (CH3I) followed by amine exchange using (R)‐ or (S)‐methyl(1‐phenylethyl)amine (8), respectively, proceeded with overall retention. Subsequent chromatographic separation gave the pure diastereoisomers (1R,3R,5R)‐10a and (1S,3S,5R)‐10b [from (R)‐8, ent‐10a and ent‐10b from (S)‐8] in > 60% yield. Subsequently, the benzylic (1‐phenylethyl) auxiliary was removed from the nitrogen atom by catalytic hydrogenolysis to yield the enantiomerically pure (> 98%) ([3]ferrocenophanyl)methylamines (1R,3R)‐11 and (1S,3S)‐11, respectively, which were converted into the corresponding dimethylamino‐substituted [3]ferrocenophanes (1R,3R)‐6 and (1S,3S)‐6. Each enantiomer from the following enantiomeric pairs was isolated in its pure form and characterized by X‐ray diffraction: (R)‐9/(S)‐9; (1R,3R,5R)‐10a/(1S,3S,5S)‐10a; (1R,3R,5S)‐10b/(1S,3S,5R)‐10b; (1R,3R)‐11/(1S,3S)‐11. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Self‐Assembly of Three CdII‐ and CuII‐Containing Coordination Polymers from 4,4′‐Dipyridyl Disulfide
Authors: Luo Junhua , Hong Maochun , Wang Ruihu , Yuan Daqiang , Cao Rong , Han Lei , Xu Yanqing , Lin Zhengzhong 
Published: September 2003

AbstractThree new organic/inorganic coordination polymers, [{Cu(4‐DPDS)2(H2O)}·2NO3·3H2O]n (1), [{Cu(4‐DPDS)2(SO4)}· 1.5H2O·CH3OH]n (2), and [Cd(4‐DPDS)2Cl2]n (3), have been synthesized by using the flexible ligand 4,4′‐dipyridyl disulfide (4‐DPDS). Complex 1 crystallized in the Ibca space group: a = 10.5275(6), b = 20.2670(1), c = 27.235(1) Å, V = 5811.5(6) Å3, Z = 16. Complex 2 crystallized in the Pnna space group: a = 10.547(2), b = 14.201(2), c = 19.667(3) Å, V = 2945.8(8) Å3, Z = 8. Complex 3 crystallized in the P21/c space group: a = 7.6146(3), b = 18.2606(8), c = 9.3203(2) Å, β = 100.26(1)°, V = 1275.24(8) Å3, Z = 4. The three coordination polymers display a variety of structural architectures, ranging from double‐stranded chains (1) to two‐dimensional channels (2) and two‐dimensional, puckered, grid‐like arrays (3). Magnetic characterizations show that complex 1 exhibits antiferromagnetic interactions while 2 is ferromagnetic. Solid‐state fluorescence results reveal that 3 exhibits fluorescence emissions at 418 and 575 nm (λex = 314 nm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Palladium‐Catalyzed Cyanation of Aryl Halides: Recent Developments and Perspectives
Authors: Sundermeier Mark , Zapf Alexander , Beller Matthias 
Published: September 2003

AbstractThe palladium‐catalyzed cyanation of aryl halides is an elegant method for the preparation of benzonitriles. Since its discovery in 1973, this reaction has been the topic of several investigations. Nevertheless, the general methodology is still somewhat underdeveloped compared to other palladium‐catalyzed coupling reactions. Here, we summarize important developments from 1997 until 2003 in this area. Recent contributions from our group include the development of palladium/phosphane/amine catalyst systems for the cyanation of aryl chlorides, the successful cyanation of aryl halides with acetone cyanohydrin and trimethylsilyl cyanide as cyanation reagents, and a general improvement of catalyst efficiency by using a continuous dosage of cyanide sources. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Characterization, and DNA Binding Studies of a Chromium(III) Complex Containing a Tridentate Ligand
Authors: Vaidyanathan Vaidyanathan Ganesan , Nair Balachandran Unni 
Published: September 2003

Abstract[Cr(bzimpy)2]Cl, where bzimpy is 2,6‐bis(benzimidazol‐2‐yl)pyridine, has been synthesized and characterized by ESI‐MS, UV/Visible, and fluorescence spectra. Absorption titration and thermal denaturation experiments indicate that the complex binds to DNA with moderate strength, while viscosity measurements show that it may undergo surface binding. The fluorescence intensity of the complex increases with increasing DNA concentration, in contrast to [Cr(phen)3]3+ and [Cr(bpy)3]3+. The complex cleaves pBR322 DNA in the presence of H2O2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Template‐Interface Co‐Reduction Synthesis of Hollow Sphere‐like Carbides
Authors: Li Cun , Yang Xiaogang , Yang Baojun , Yan Yan , Qian Yitai 
Published: September 2003

AbstractHollow sphere‐like carbides MC (M = Ti, V) with diameters of between 70 and 170 nm were synthesized via a template‐interface co‐reduction (TICR) route, in which MCl4 and hexachlorobuta‐1,3‐diene (C4Cl6) were reacted with metallic sodium at 500 °C for 24 h. X‐ray powder diffraction (XRD) patterns indicated the samples were single‐phase NaCl‐type carbides. Transmission electron microscopy (TEM) photographs showed the hollow spheres consisted of nanocrystalline carbides. The possible formation mechanism of hollow sphere‐like carbides is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Preparation and Study of Bis(2‐quinolyl) and Bis(2‐[1,8]naphthyridyl) Derivatives of Pyrimidine and Pyrazine as Bridging Ligands for RuII
Authors: Brown Darren , Muranjan Seema , Thummel Randolph P. 
Published: September 2003

AbstractThe 2:1 Friedländer condensation of 2‐aminobenzaldehyde or 2‐aminonicotinaldehyde with either 4,6‐diacetylpyrimidine or 2,5‐diacetylpyrazine leads to a family of four new bis(bidentate) bridging ligands. Subsequent complexation of these ligands with [RuCl2(bpy)2] (bpy = 2,2′‐bipyridine) leads to the corresponding mononuclear and dinuclear mixed‐ligand RuII complexes. Analysis of the 1H NMR spectra of these systems affords some insight into their conformational properties. Electronic spectra of the complexes evidence two long‐wavelength absorption bands which correspond to typical metal‐to‐ligand charge transfer states. The energies of these states may be explained by electronegativities of the pendant rings on the bridging ligand as well as the substitution pattern on the central ring. For the dinuclear complexes the lowest energy absorption shows components associated with coordination to the pendant and the central rings. The appearance of two metal‐based oxidations gives good evidence for strong intermetalic interaction and Koopman’s theorem is obeyed for all systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Study of the D⇄Sb (D = O, S) Transannular Interaction in Sb‐Monohalogenated Dibenzostibocines − An Experimental and Theoretical Study
Authors: Alvarado‐Rodríguez José G. , Andrade‐López Noemí , González‐Montiel Simplicio , Merino Gabriel , Vela Alberto 
Published: September 2003

AbstractIn order to gain a greater insight in the nature of the D⇄Sb transannular interaction in dibenzostibocines, a series of D(C6H4S)2SbHal complexes (D = S; Hal = Cl 1, Br 2, I 3; D = O, Hal = Cl 4) has been synthesised. X‐ray structure determinations of complexes 1−4 reveal that the antimony atom is in a distorted ψ‐bipyramidal geometry, acting as an acceptor atom. The eight‐membered ring conformation in 1, 2 and 4 can be described as a twist‐boat, while in 3 it is approaching Cs symmetry. DFT calculations were carried out on 1 and 4. Topological analysis of the electron density in 1 and 4 showed the presence of critical points in the D⇄Sb direction (D = O, S). The electron localisation function showed the presence of a lone pair located in an equatorial position on the antimony, and a lone pair of the donor along the D⇄Sb direction, confirming the presence of a dative bond in the system. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Self‐Organization of Dipolar 4,4′‐Disubstituted 2,2′‐Bipyridine Metal Complexes into Luminescent Lamellar Liquid Crystals
Authors: Pucci Daniela , Barberio Giovanna , Crispini Alessandra , Francescangeli Oriano , Ghedini Mauro , La Deda Massimo 
Published: September 2003

AbstractMononuclearcis‐dichloro complexes, [LnMCl2], with different metal centres (PtII, NiII, and ZnII) and a series of palladium and platinum derivatives, [L2MX2], in which chloride groups are replaced with iodide, bromide, and azide ligands, have been synthesized from 4,4′‐disubstituted‐2,2′‐bipyridines. Upon complexation of these non‐mesogenic ligands, the peculiar structural arrangement, characterized by intermolecular associations of the new derivatives, induces mesomorphism in most [L2MX2] complexes, confirming the importance of coordination chemistry in metal‐mediated formation of liquid crystals. Single crystal X‐ray structures have been determined for dihexadecyl 2,2′‐bipyridyl‐4,4′‐dicarboxylatopalladium and ‐zinc dichloride derivatives. Both the metal centres and the ancillary ligands have been varied to use dipole coupling as a tool to control molecular architecture: thermal, as well as spectroscopic properties, depend strongly upon molecular dipolar interactions. Tunable red and blue emitters based on PdIIand PtII, both in solution and in the solid state, have been obtained. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Novel Mixed‐Valence CuI/CuII Coordination Polymer: Solvothermal Synthesis, Crystal Structure, and Magnetic Properties of CuICuII(2‐Pyrazinecarboxylate)2(H2O)(ClO4)
Authors: Liu Cai‐Ming , Zhang De‐Qing , Luo Jian‐Lin , Wang Nan‐Lin , Hu Huai‐Ming , Zhu Dao‐Ben 
Published: September 2003

AbstractThe solvothermal reaction between Cu(ClO4)2·6H2O and 2‐pyrazinecarboxylic acid in methanol yields a novel mixed‐valence CuI/CuII coordination polymer, CuICuII(2‐pyrazinecarboxylate)2(H2O)(ClO4) (1), in which a three‐dimensional supramolecular array with square channels (9.3 × 9.3 Å) is formed through crisscross arrangement of the one‐dimensional CuICuII(2‐pyrazinecarboxylate)2(H2O)+ coordination polymer cation chains in the adjacent layers. Complex 1 exhibits weak ferromagnetic interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis of Chiral Cationic (Diimino‐ and diaminodiphosphane)ruthenium Complexes and Their Applications in Catalytic Oxidation − Crystal Structures of cis‐[RuCl(py){κ4‐Ph2PC6H4CH=NC6H10N=CHC6H4PPh2}]BF4 and cis‐[RuCl(py){κ4‐Ph2PC6H4CH=NC6H10N(H)CH2C6H4PPh2}]BF4
Authors: Wong Wai‐Kwok , Chen Xiao‐Ping , Chik Tat‐Wai , Wong Wai‐Yeung , Guo Jian‐Ping , Lee Fu‐Wa 
Published: September 2003

AbstractHalide abstraction of trans‐[RuCl2{κ4‐(1R,2R)‐PNNP}] {(1R,2R)‐PNNP = (1R,2R)‐N,N′‐bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diiminocyclohexane} and trans‐[RuCl2{κ4‐(1R,2R)‐P(NH)(NH)P}] {(1R,2R)‐P(NH)(NH)P = (1R,2R)‐N,N′bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diaminocyclohexane} with AgBF4 in acetonitrile at ambient temperature gave cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐PNNP}][BF4] (1) and cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐P(NH)(NH)P}][BF4] (2), respectively. When 1 was refluxed in pyridine (py), the coordinated CH3CN was replaced by pyridine to form cis‐[RuCl(py){κ4‐(1R,2R)‐PNNP}][BF4] (3). However, when 2 was refluxed in pyridine, one of the amino moieties (−CH2−NH−)was oxidized to an imino moiety (−CH=N−) with concomitant displacement of the coordinated CH3CN by pyridine to produce cis‐[RuCl(py){κ4‐(1R,2R)‐P(N)(NH)P}][BF4] (4). The structures of 3 and 4 were ascertained by X‐ray crystallography. Compounds 1−4 are effective catalysts for the epoxidation of various olefins with air. A turnover frequency of up to 733 h−1 and an enantiomeric excess of up to 24% were obtained for the epoxidation of styrene catalysed by 2. Compound 2 can also catalyse the epoxidation, dehydrogenation and C−H activation of various olefins, alcohols and alkanes by tert‐butyl hydroperoxide with high chemical selectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Structural Elucidation of a “Free” Phosphinoamide Anion
Authors: Fei Zhaofu , Scopelliti Rosario , Dyson Paul J. 
Published: September 2003

AbstractThe reaction of the aminophosphane C6H4(o‐CN)NHPPh2 with elemental potassium in the presence of 18‐crown‐6 affords the phosphinoamide‐containing complex [C6H4(o‐CN)N‐PPh2(THF)(18‐Crown‐6)K] which has been fully characterised in solution and the solid state. The potassium cation interacts with the nitrile substituent group and crown, but does not interact with the P−N bond. The anion appears to be considerably more reactive than related anions in which the cation interacts with the P‐N unit, as demonstrated by the reaction with O2/H2O which affords [Ph2P(:O)OK(18‐Crown‐6)] and C6H4(o‐CN)NH2. A co‐crystal containing these two products was obtained and the structure has been elucidated by single‐crystal X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Structural Characterization of Potassium Salts of Phosphane‐Substituted (Cyclopentadienyl)iron Dicyanides, and Their Use as Bridging Ligands for Copper(I) Phosphane Derivatives
Authors: Darensbourg Donald J. , Adams M. Jason , Yarbrough Jason C. , Phelps Andrea L. 
Published: September 2003

AbstractPhosphane‐substituted CpFe(CN)2 anions have been synthesized by photochemical decarbonylation of KCpFe(CN)2CO in the presence of various mono‐ and diphosphanes. The synthesis and characterization of uniquely bridged diphosphane derivatives, [KCpFe(CN)2]2‐μ‐(Ph2P)2−(CH2)n (n = 2−4), are particularly noteworthy. These phosphane‐substituted CpFe(CN)2− units have afforded stable mixed‐metal complexes upon reaction with CuI in the presence of tricyclohexylphosphane in acetonitrile solution. X‐ray crystallography shows these derivatives to display two‐dimensional diamond‐shaped structures with copper(I) of the form [Fe(CN)2Cu]2, where the CuI centers exhibit both trigonal and tetrahedral geometries. Infrared data reveal that the withdrawal of electron density from the iron centers in these mixed metal cyanides via the cyanide ligands is enhanced upon replacing CO in CpFe(CN)2CO− with phosphanes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Water‐Exchange Rate in Neutral Heptadentate DO3A‐Like GdIII Complexes: Effect of the Basicity at the Macrocyclic Nitrogen Site
Authors: Terreno Enzo , Boniforte Patrizia , Botta Mauro , Fedeli Franco , Milone Luciano , Mortillaro Armando , Aime Silvio 
Published: September 2003

AbstractThe rate of exchange of the two water molecules coordinated to a GdIII centre in neutral complexes with heptadentate DO3A derivatives is modulated by the basicity of the macrocyclic nitrogen bearing the pendant group: a lower basicity results in a slower water‐exchange rate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cover Picture: Synthesis, Structure, and Reactivity of Novel Intramolecularly Coordinated Organolead(II) Compounds (Eur. J. Inorg. Chem. 19/2003)
Authors: Jurkschat Klaus , Peveling Katja , Schürmann Markus 
Published: September 2003

AbstractThe cover picture shows as one representative out of the carbene‐analogue family, a novel heteroleptic lead(II) compound containing an O,C,O‐coordinating pincer‐type ligand. Details are discussed in the article by K. Jurkschat et al. on p. 3563 ff.
Synthesis and Evaluation of a Broad Range of New Chiral (Aminoalkyl)phosphane Ligands for Asymmetric Hydrogen‐Transfer Reduction of Prochiral Ketones
Authors: Léautey Matthieu , Jubault Philippe , Pannecoucke Xavier , Quirion Jean‐Charles 
Published: September 2003

AbstractTwenty new chiral (aminoalkyl)phosphane ligands have been prepared from four enantiomerically pure advanced chiral compounds. We describe their use for asymmetric hydrogen‐transfer reduction of three prochiral ketones. Enantioselectivities up to 90% were obtained. We investigated the influence on the enantioselectivity of each part of these new (aminoalkyl)phosphane ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthetic Study on Campylobacter jejuni Lipopolysaccharides: An Improved Synthesis of a Branched, Heptose‐Containing Trisaccharide Core Structure and Its Conversion into Ganglioside GD3 Related Hexasaccharide
Authors: Hori Koji , Sawada Naoki , Ando Hiromune , Ishida Hideharu , Kiso Makoto 
Published: September 2003

AbstractThe first synthesis of the oligosaccharide skeleton of the Campylobacter jejuni lipooligosaccharide composed of a branched, heptose‐containing trisaccharide core structure and, including a substantially improved preparation of the core structure, the ganglioside GD3 related trisaccharide epitope is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Thiaporphyrins with One, Two and Four Unsubstituted meso‐Carbons: Synthesis and Functionalization
Authors: Agarwal Neeraj , Hung C.‐H. , Ravikanth M. 
Published: September 2003

AbstractThiaporphyrins with one, two and four unsubstituted meso carbons were synthesized from easily available thiophene diols. The reactivity at these carbons was demonstrated by carrying out series of reactions and some very useful functional groups were introduced. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Direct Estimation of Total Arsenic Using A Novel Metal Side Disk Rotating Electrode
Authors: Prakash Rajiv , Srivastava R. C. , Seth P. K. 
Published: September 2003

AbstractA special type of metal side disk rotating electrode has been demonstrated for the direct estimation of total arsenic [As(III) and As(V)] at low ppb (μg/L) level using anodic stripping differential pulse voltammetry (ASDPV). A conventional three electrodes cell is used equipped with side disk rotating gold electrode as working, graphite/platinum electrode as auxiliary and Ag/AgCl/3M KCl as reference electrodes. Arsenic is estimated in various acidified samples without any digestion, containing a trace amount of copper at low ppb level. The major problems associated with ASDPV of high acidic condition (acid hazards), irreproducible results due to the interference of hydrogen bubbles, evolved at the cathode during the deposition of arsenic in acidified samples and poor detection level are overcome with the help of the specially designed gold side disk rotating electrode and modified electrolyte. The presence of a trace amount of copper(II) salt in the electrolyte is found to enhance the sensitivity of the technique. The shape and position of the metal disk at the electrode, rotation speed of the electrode and electrolyte are optimized to have less hydrogen gas bubbles interference and high reproducibility in the detection of arsenic up to 2 ppb±15% level in various samples. The electrode has been found very stable and reproducible even for more than 200 estimations.
Simultaneous Determination of Aluminum and Iron in High Salt Content Matrices by Adsorptive Stripping Voltammetry. Application to Dialysis Fluids
Authors: Locatelli Clinio 
Published: September 2003

AbstractA new analytical procedure for the simultaneous determination of aluminum(III) and iron(II) in two kinds of dialysis fluids (peritoneal and hemodialysis fluids) by differential pulse adsorptive stripping voltammetry (DPAdSV) is described. The voltammetric measurements were performed using, as working electrode, a stationary mercury electrode, and a platinum electrode and a Ag|AgCl|KCl(sat.) electrode as auxiliary and reference electrodes, respectively, employing acetate buffer solutions at different pH as supporting electrolyte. As complexing agents, Solochrome Violet RS, Palatine Chrome Black 6BN, Chromazurol S and Eriochrome Black T were employed. For both elements, the accuracy, expressed as relative recovery R%, was very satisfactory being in the range 94–105%, the precision as repeatability, expressed as relative standard deviation sr%, was lower than 6%, while the limits of detection were of the order of a few units of μg/L. The analytical voltammetric procedure has been validated by comparison with spectroscopic (graphite furnace atomic absorption spectroscopy, GFAAS) measurements.
Preparation of Fluorine‐Doped Lead Dioxide Modified Electrodes for Electroanalytical Applications
Authors: Ai Shiyun , Gao Mengnan , Zhang Wen , Sun Zhengdong , Jin Litong 
Published: September 2003

AbstractThe effect of F− on the modified films of lead dioxide in morphology and structure was studied. The results obtained by cyclic voltammetry (CV), X‐diffractometer (XRD) and scanning electron microscope (SEM) techniques indicated that F− could change the magnitude of lead dioxide crystal grain and the preferred crystallizing orientation on the substrate surface, even though it didn't change the basic structure of PbO2. When the modified electrode was applied as an analytical sensor to determine phenolic compounds, the linearity was in the range of 2×10−5 – 1×10−3 mol/L and the detection limit was 2.5×10−6 mol/L. It was all found that the stability and reproducibility of the oxide‐modified electrodes were improved by additional F−.
Solid Microelectrodes for In Situ Voltammetric Measurements
Authors: Pižeta Ivanka , Billon Gabriel , Fischer Jean‐Claude , Wartel Michel 
Published: September 2003

AbstractSolid Au and Ag microelectrodes for both, model, and in situ voltammetric measurements, have been designed and tested. Amalgamation procedure and the parameters of measurement procedure are discussed. Differences between gold and silver electrodes were studied. Silver electrodes showed more stable behavior and were used prevalently for calibration and in situ measurements. Calibration of a 30‐μm diameter Ag electrode for Mn(II), Fe(II), I(−I) and S(−II) showed good linearity with reasonable confidence intervals, necessary for quantification of the signals obtained in situ, with average sensitivity of 0.05, 0.01, 0.16 and 1.10 nA/(μmol L−1) and minimal detection limit of 3.5, 28, 0.3 and 0.05 μmol L−1, respectively. Additional checking of the electrode sensitivity with the reduction peaks of oxygen is proposed.