Fundamental studies of microscopic wetting on organic surfaces. 1. Formation and structural characterization of a self-consistent series of polyfunctional organic monolayers

Nuzzo, Ralph G.; Dubois, L. H.; Allara, David L.

doi:10.1021/ja00158a012

Cited by 1,566 publications

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“…In all cases of hydroxide-catalyzed exchange, the methylene asymmetric stretch is observed to increase in intensity by a factor of 2−3 and shift from ∼2919 to ∼2930 cm −1 , indicative of poor order in the resulting film. 57,84 Annealing the film in the same solution at an elevated temperature for 24 h and then repeating the spectroscopic analysis reveals a monolayer film indistinguishable from one deposited at room temperature, evidence of poor ordering after base-catalyzed displacement of thiolate by selenolate. Spectra and kinetic results are collected in the Supporting Information, Figure S3.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

et al. 2014

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When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate–gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

et al. 2014

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“…well-established techniques for forming and characterizing them, [231][232][233][234][235][236][237] and in principle, their chemistry should be less complex and therefore more amenable to obtaining detailed molecular level insights. SAMs formed by reaction of trichloroalkylsilanes on SiO x surfaces, for example on the thin oxide layer on silicon, may be particularly relevant to reactions of organic compounds on dust and on building materials for which silicates can be major components.…”

Section: This Journal Is C the Owner Societies 2009mentioning

confidence: 99%

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Finlayson-Pitts

2009

Phys. Chem. Chem. Phys.

231

272

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“…As discussed below, alcohols will be formed by addition of OH to the double bond, yet such a feature due to the O-H stretch was not present in our spectra, nor in those of previous studies of alcohol-SAMs. 53,54 For example, even in the infrared spectrum of a monolayer of 16-mercaptohexadecane-1-ol on Au in which all the chains have -OH terminal groups, only the -CH 2 -stretches and the C-O stretch at 1070 cm À1 were observed. 54 Thus, although alcohols are expected to be major products of the reaction, they are not necessarily readily observable by ATR-FTIR.…”

Section: Error Analysismentioning

confidence: 99%

Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations

Moussa

Finlayson-Pitts

2010

Phys. Chem. Chem. Phys.

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The kinetics and mechanisms of the reaction of gas phase OH radicals with organics on surfaces are of fundamental chemical interest, as well as relevant to understanding the degradation of organics on tropospheric surfaces or when they are components of airborne particles. We report here studies of the oxidation of a terminal alkene self-assembled monolayer (7-octenyltrichlorosilane, C8Q SAM) on a germanium attenuated total reflectance crystal by OH radicals at a concentration of 2.1 Â 10 5 cm À3 at 1 atm total pressure and 298 K in air. Loss of the reactant SAM and the formation of surface products were followed in real time using infrared spectroscopy. From the rate of loss of the CQC bond, a reaction probability within experimental error of unity was derived. The products formed on the surface include organic nitrates and carbonyl compounds, with yields of 10 AE 4% and r7 AE 4%, respectively, and there is evidence for the formation of organic products with C-O bonds such as alcohols, ethers and/or alkyl peroxides and possibly peroxynitrates. The yield of organic nitrates relative to carbonyl compounds is higher than expected based on analogous gas phase mechanisms, suggesting that the branching ratio for the RO 2 + NO reaction is shifted to favor the formation of organic nitrates when the reaction occurs on a surface. Water uptake onto the surface was only slightly enhanced upon oxidation, suggesting that oxidation per se cannot be taken as a predictor of increased hydrophilicity of atmospheric organics. These experiments indicate that the mechanisms for the surface reactions are different from gas phase reactions, but the OH oxidation of surface species will still be a significant contributor to determining their lifetimes in air.

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Fundamental studies of microscopic wetting on organic surfaces. 1. Formation and structural characterization of a self-consistent series of polyfunctional organic monolayers

Cited by 1,566 publications

References 0 publications

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations

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