Surface-Confined Monomers on Electrode Surfaces. 4. Electrochemical and Spectroscopic Characterization of Undec-10-ene-1-thiol Self-Assembled Monolayers on Au

Peanasky, John; McCarley, Robin L.

doi:10.1021/la970823a

Cited by 54 publications

(83 citation statements)

References 73 publications

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“…Octadecanethiol (98%, C 18 H 38 S, ODT) was purchased from Sigma‐Aldrich and used without further purification. Undec‐10‐ene‐1‐thiol (C 11 H 22 S, UDT) was synthesized according to the procedure described by Peanasky and McCarley [1998]. NO 2 (99.5%) was purchased from Matheson, N 2 (99.999%), O 2 (99.993%) and He (99.999%) were purchased from Praxair.…”

Section: Methodsmentioning

confidence: 99%

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals

Gross¹,

Bertram²

2009

J. Geophys. Res.

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[1] The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO 3 radicals (in the presence of NO 2 and O 2 ) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO 2 ). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO 3 radicals. The reactive uptake coefficient (g) of NO 3 on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the g value determined in our studies, we show that under conditions where NO 3 is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO 3 . The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.Citation: Gross, S., and A. K. Bertram (2009), Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO 3 radicals,

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Section: Methodsmentioning

confidence: 99%

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals

Gross¹,

Bertram²

2009

J. Geophys. Res.

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“…109 Internal polymerizations of SAMs include conversion of diacetylenes to a conjugated ene -yne structure, 110,111 cross-linking of a terminal vinyl group, 112 hydrolysis and cross-linking of a trimethoxysilane, 113 dehydration of a boronic acid to a borate glass, 114 and electrochemical polymerization of a terminal pyrrole. 115,116 The polymerized SAMs exhibit increased stability towards thermal desorption and greater resistance to exchange with solution thiols.…”

Section: Nonelectrochemical Characterization Of Self-assembled Monolamentioning

confidence: 99%

“…110 However, polymerization of a terminal vinyl group has the opposite effect. 112 Nonaqueous electrolytes tend to increase the permeability of SAMs, presumably because of increased solvent interactions with the pendant chains. Some redox couples (e.g.…”

Section: Blocking Behaviormentioning

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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“…Undec-10-ene-thiol was synthesized by following the procedure described elsewhere. 31,32 Fabrication of the Composite Membrane. Functionalization of the Alumina Membrane.…”

Section: ■ Introductionmentioning

confidence: 99%

Composite Fluorocarbon Membranes by Surface-Initiated Polymerization from Nanoporous Gold-Coated Alumina

Escobar

Zulkifli

Faulkner

et al. 2012

ACS Appl. Mater. Interfaces

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This manuscript describes the versatile fabrication and characterization of a novel composite membrane that consists of a porous alumina support, a 100 nm thick nanoporous gold coating, and a selective poly(5-(perfluorohexyl)norbornene) (pNBF6) polymer that can be grown exclusively from the nanoporous gold or throughout the membrane. Integration of the three materials is achieved by means of silane and thiol chemistry, and the use of surface-initiated ring-opening metathesis polymerization (SI-ROMP) to grow the pNBF6. The use of SI-ROMP allows tailoring of the extent of polymerization of pNBF6 throughout the structure by varying polymerization time. Scanning electron microscopy (SEM) images indicate that the thin polymer films cover the structure entirely. Cross-sectional SEM images of the membrane not only corroborate growth of the pNBF6 polymer within both the porous alumina and the nanoporous gold coating but also show the growth of a pNBF6 layer between these porous substrates that lifts the nanoporous gold coating away from the alumina. Advancing contact angle (θ(A)) measurements show that the surfaces of these composite membranes exhibit both hydrophobic (θ(A) = 121-129)° and oleophobic (θ(A) = 69-74)° behavior due to the fluorocarbon side chains of the pNBF6 polymer that dominate the surface. Results from electrochemical impedance spectroscopy (EIS) confirm that the membranes provide effective barriers to aqueous ions, as evidenced by a resistive impedance on the order of 1 × 10(7) Ω cm(2). Sulfonation of the polymer backbone substantially enhances ion transport through the composite membrane, as indicated by a 40-60 fold reduction in resistive impedance. Ion transport and selectivity of the membrane change by regulating the polymerization time. The fluorinated nature of the sulfonated polymer renders the membrane selective toward molecules with similar chemical characteristics.

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Surface-Confined Monomers on Electrode Surfaces. 4. Electrochemical and Spectroscopic Characterization of Undec-10-ene-1-thiol Self-Assembled Monolayers on Au

Cited by 54 publications

References 73 publications

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals

Self‐Assembled Monolayers on Electrodes

Composite Fluorocarbon Membranes by Surface-Initiated Polymerization from Nanoporous Gold-Coated Alumina

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Surface-Confined Monomers on Electrode Surfaces. 4. Electrochemical and Spectroscopic Characterization of Undec-10-ene-1-thiol Self-Assembled Monolayers on Au

Cited by 54 publications

References 73 publications

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals

Self‐Assembled Monolayers on Electrodes

Composite Fluorocarbon Membranes by Surface-Initiated Polymerization from Nanoporous Gold-Coated Alumina

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Product

Resources

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Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO₃ radicals