Monomolecular films on mercury

Smith, Tony

doi:10.1016/0001-8686(72)80003-4

Cited by 60 publications

(46 citation statements)

References 65 publications

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“…Langmuir troughs working with the mercury-air interface were first described a third of a century ago (34,35). The use of a mercury-conducting solvent interface at a well-defined electrochemical potential is appealing for electrochemical studies of layers adsorbed on mercury, but carries its own set of difficulties.…”

Section: Discussionmentioning

confidence: 99%

Self-assembly of a metal-ion-bound monolayer of trigonal connectors on mercury: An electrochemical Langmuir trough

Varaksa

Pospı́šil

Magnera

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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The adsorption of the trigonal connector, 1,3,5-tris[10-(3-ethylthiopropyl)dimethylsilyl-1,10-dicarba-closo-decaboran-1-yl]benzene (1), from acetonitrile͞0.1 M LiClO 4 on the surface of mercury at potentials ranging from ؉0.3 to ؊1.4 V (vs. aqueous AgͦAgClͦ1 M LiCl) was examined by voltammetry, Langmuir isotherms at controlled potentials, and impedance measurements. No adsorption is observed at potentials more negative than ϳ ؊0.85 V. Physisorption is seen between ϳ ؊0.85 and 0 V. At positive potentials, adsorbate-assisted anodic dissolution of mercury occurs and an organized surface layer is formed. Although the mercury cations are reduced at ؊0.10 V, the surface layer remains metastable to potentials as negative as ؊0.85 V. Its surface areas per molecule and per redox center are compatible with a regular structure with the connectors 1 woven into a hexagonal network by RRS3 Hg 2 2؉ 4SRR or RRS3 Hg 2؉ 4SRR bridges. The structure is simulated closely by geometry optimization in the semiempirical AM1 approximation. E lsewhere in this issue (1) we outline the motivation for our efforts to prepare extended regular grids on the surface of mercury by reversible self-assembly. Here, we describe an electrochemical Langmuir trough for the determination of a surface molecular area at the interface of mercury and an electrolyte solution at a controlled potential. We use it to shed light on the possible formation of a two-dimensional hexagonal grid by the binding of trigonal connectors to each other through a mutual coupling of their thioether-containing arm terminals by means of ligation to mercury cations.It has been long known (2) that anodic dissolution of mercury is facilitated by the presence of species with a large affinity for mercury ions. These can be anions, such as oxalate (3, 4), or neutral ligands, such as azaaromatics (5). Sulfur compounds, especially sulfide and thiols, have attracted particular attention (6-16). Often, the mercury-ion-containing salts adhere firmly to the mercury surface in the form of highly insoluble compact monolayers or multilayers. Although the mechanism of their formation has been much investigated (4,5,10,11,13,(17)(18)(19)(20)(21)(22)(23)(24), structural information for these layers on mercury is limited except for the simplest cases, such as Hg 2 Cl 2 (25, 26). The growth of two-dimensional crystals of salts of other metals on mercury surface is known (27, 28), and nucleation and growth phenomena in electrocrystallization have been reviewed recently (29). The mercury-adsorbed layers are compact, with lateral interactions among the adsorbed species essential for stability.We have reported (30) the formation of such an adsorbed layer on a dropping mercury electrode from acetonitrile and dichloromethane solutions of a trigonal connector with a thioether link in each of its three arms, and suggested an open hexagonal grid structure for it. We now examine in more detail the properties of a monolayer formed from a similar connector that differs only by substitution of 10-vertex for 12-v...

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Section: Discussionmentioning

confidence: 99%

Self-assembly of a metal-ion-bound monolayer of trigonal connectors on mercury: An electrochemical Langmuir trough

Varaksa

Pospı́šil

Magnera

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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“…Several attempts were made to give an explanation for the non-horizontal shape of Π-A isotherms in the 2D transition region [19][20][21][22][23][24][25][26][27]. In these studies, LE-LC transitions were treated in the framework of a quasi-chemical approach, where the mass action law was employed for the description of the monomer/aggregate equilibrium.…”

Section: Theorymentioning

confidence: 99%

Progress in characterization of Langmuir monolayers by consideration of compressibility

Vollhardt

Fainerman

2006

Advances in Colloid and Interface Science

101

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“…Mercury substrates have been used to crystallize proteins such as ferritin but its general applicability remains uncertain. [32][33][34][35][36][37] Finally, liquid/liquid interfaces have also been investigated to a limited extent. These systems offer good homogeneity and high lateral mobility; however, the liquid interfaces studied to date lack the strong interaction forces necessary to sufficiently concentrate most proteins at the interface.…”

Section: Two-dimensional Crystallization Of Proteins At Interfacesmentioning

confidence: 99%

Engineering Two-Dimensional Protein Order at Surfaces

Koppenol¹,

Stayton²

1997

Journal of Pharmaceutical Sciences

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Monomolecular films on mercury

Cited by 60 publications

References 65 publications

Self-assembly of a metal-ion-bound monolayer of trigonal connectors on mercury: An electrochemical Langmuir trough

Self-assembly of a metal-ion-bound monolayer of trigonal connectors on mercury: An electrochemical Langmuir trough

Progress in characterization of Langmuir monolayers by consideration of compressibility

Engineering Two-Dimensional Protein Order at Surfaces

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