Characterization and Electroanalytical Application of ω‐Mercaptoalkanesulfonic Acid Monolayers on Gold

Turyan, Iva; Mandler, Daniel

doi:10.1002/ijch.199700026

Cited by 23 publications

(26 citation statements)

References 76 publications

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“…0.00 V (vs. SCE) as this was positive of the Nernst potential for bulk copper deposition [12,14]. Such ®lms were submonolayer in coverage, analogous to the behavior observed previously for MPS ®lms [27] and other mercaptoalkane sulfonate ®lms, including MES [24,25]. Broad reduction and oxidation peaks were observed for the deposition and stripping of the Cu monolayer.…”

Section: Resultssupporting

confidence: 78%

“…Taking the molecular brush approach of Mandler [25], we have been interested in the preparation of chemisorbed ®lms which are disorganized and therefore porous [27]. This characteristic can be built into the ®lms by use of short alkyl chains and highly charged end-groups, thereby minimizing attractive forces between adjacent alkyl chains and maximizing electrostatic repulsion between the end-groups.…”

Section: Introductionmentioning

confidence: 99%

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Underpotential Deposition of Copper at Mercaptoalkane Sulfonate-Coated Polycrystalline Gold

Arrigan

Iqbal²,

Pickup³

2001

Electroanalysis

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Underpotential deposition (UPD) of copper from aqueous sulfuric acid solution onto polycrystalline gold electrodes coated with 2‐mercaptoethane sulfonate (MES) or 3‐mercapto‐1‐propane sulfonate (MPS) films has been studied. On the basis of peak shape, the UPD reduction process was inhibited by the organosulfonate film, with the greater inhibition being observed for the MPS film. The inhibitory affects in the UPD can be overcome by deposition at a constant underpotential (0.00 V vs. SCE) for a set time. After this set time (≥60 s) the charge for stripping of the underpotential deposit was equivalent to the charge recorded for UPD stripping at the bare polycrystalline gold surface.

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Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Underpotential Deposition of Copper at Mercaptoalkane Sulfonate-Coated Polycrystalline Gold

Arrigan

Iqbal²,

Pickup³

2001

Electroanalysis

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“…179 Interestingly, a highly charged and hydrophilic SAM containing w-mercaptodecanesulfonic acid strongly blocks organic redox couples, regardless of their charge. 180 By extension, a bilayer of molecules on or near the electrode surface should provide even greater selectivity for analytes if ion transport agents are incorporated into the bilayer. 133,181 A phospholipid bilayer can be formed near but not on an electrode coated with a SAM whose constituent molecules possess a long hydrophilic body and a hydrophobic phytanyl tail.…”

Section: Selective Permeationmentioning

confidence: 99%

Self‐Assembled Monolayers on Electrodes

Finklea

2000

Encyclopedia of Analytical Chemistry

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Alkanethiols and related molecules spontaneously adsorb from solution or vapor phase onto oxide‐free metals, especially gold, to form close‐packed oriented monolayers. The ease and flexibility of the self‐assembly process provides a convenient method for altering the properties of the metal as an electrode. The close‐packed hydrocarbon layer blocks access of most solution species to the electrode surface. Consequently, interfacial capacitances are markedly reduced and most electron‐transfer reactions are strongly inhibited. The monolayers also provide a foundation for attachment of additional molecules or molecular layers to electrodes. Self‐assembled monolayers (SAMs) on electrodes have been used in voltammetric methods to improve the analytical sensitivity and to impart greater selectivity towards specific analytes. Redox molecules have been anchored at fixed and controllable distances from the electrode surface, thereby permitting the study of electron‐transfer kinetics over long distances and at large driving forces. The ability of SAMs to inhibit metal corrosion and to promote better adhesion of electroactive polymers has been demonstrated.

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“…Surveying the literature for Fe(II) complexation clearly indicates that very stable complexes of Fe(II) are formed with pyridine derivatives, in particular bidentate ligands, e.g., 2,2 H -bipyridine, where the two ligating sites form a ®ve member ring with the iron ion. Recently, we reported on SAMs of o-mercaptoalkanesulfonic acids [24]. While the ®rst approach resembles that of adsorptive stripping voltammetry, the second approach is more challenging due to the reduced degree of freedom of surface attached ligands.…”

Section: Self-assembled Monolayers (Sams) Of 10-mercaptodecanesulfonimentioning

confidence: 99%

“…Phen forms a strong, relatively selective and positively charged complex with Fe(II) ions [22±23] suggesting that it could be effectively attracted by a negatively charged SAM. Recently, we reported on SAMs of o-mercaptoalkanesulfonic acids [24]. We showed that these SAMs are negatively charged throughout a wide range of pH due to the strong acidity of the sulfonic acid moiety.…”

Section: Self-assembled Monolayers (Sams) Of 10-mercaptodecanesulfonimentioning

confidence: 99%

Comparing Different Approaches for Assembling Selective Electrodes for Heavy Metals

2001

Self Cite

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Different approaches for increasing the sensitivity and selectivity of voltammetric probes for heavy metals have been examined. These have involved adsorbed monolayers of host molecules, functionalized self‐assembled monolayers and thin polymeric films. Two systems are presented that focus on the selective analysis of Hg(II) and Fe(II). The electrode for Hg(II) is based on a macrocyclic ligand, i.e., Kryptofix‐222, while that for Fe(II) relies on the selective complexation by ferroin ligands, such as 1,10‐phenanthroline. The monomeric and polymeric approaches were examined and compared for both systems. The principal aim of this manuscript is to highlight the ability of fine‐tuning the selectivity characteristics of the solid‐liquid interface as a result of considering and optimizing analyte‐interface interactions. We find that basically, an interface comprising a monolayer, which is capable of forming a strong and selective complex with the analyte, is likely to exhibit sensitivity that is at least as good as a polymeric film. On the other hand, the stability and durability of the latter usually makes it a superior interface for repetitive analysis and will therefore be the preferred choice for flow analysis systems.

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Characterization and Electroanalytical Application of ω‐Mercaptoalkanesulfonic Acid Monolayers on Gold

Cited by 23 publications

References 76 publications

Underpotential Deposition of Copper at Mercaptoalkane Sulfonate-Coated Polycrystalline Gold

Underpotential Deposition of Copper at Mercaptoalkane Sulfonate-Coated Polycrystalline Gold

Self‐Assembled Monolayers on Electrodes

Comparing Different Approaches for Assembling Selective Electrodes for Heavy Metals

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