On the formation and structure of self-assembling monolayers. I. A comparative atr-wettability study of Langmuir—Blodgett and adsorbed films on flat substrates and glass microbeads

Maoz, Rivka; Sagiv, Jacob

doi:10.1016/0021-9797(84)90452-1

Cited by 595 publications

(404 citation statements)

References 65 publications

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“…The morphology of hydrocarbon chain monolayers has been studied theoretically in several molecular-dynamics (MD) calculations in which the head group was either free to move in the plane of the surface, as is the case for Langmuir films on water, [18][19][20][21] or fixed at specific lattice sites, as found for alkanethiol monolayers on gold. 22 These calculations provide explicit predictions of the atomic positions, from which scattering cross sections have been calculated.…”

Section: J Introductionmentioning

confidence: 99%

X-ray grazing incidence diffraction from alkylsiloxane monolayers on silicon wafers

Tidswell

Rabedeau

Pershan

et al. 1991

The Journal of Chemical Physics

136

103

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X-ray reflection (both specular and off-specular) and grazing incidence diffraction (GID) have been used to study the structure of alkylsiloxane monolayers (n-C18H37SiO1.5) formed by self-assembly from solution on silicon wafers. GID studies of complete monolayers reveal a single ring of scattering associated with the monolayer. The Lorentzian line shape of this ring indicates that the film is characterized by liquidlike order, with a typical translational correlation length of about 45 Å. The thermal coefficient of expansion of the monolayer, as determined from the GID peak position, is approximately equal to the value for liquid n-alkanes. Upon either heating or cooling, the monolayer correlation lengths decrease, suggesting that the differential thermal-expansion coefficients of the film and substrate figure prominently in thermal changes of the molecular ordering. GID data for incomplete monolayers also reveal a single ring of scattering associated with the monolayer. While both the translational correlation lengths and integrated peak areas are significantly reduced relative to complete monolayers, the peak positions of the incomplete monolayers are comparable to those of complete monolayers. Given the lower average areal density of incomplete monolayers, this finding implies that incomplete monolayers are inhomogeneous.

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Section: J Introductionmentioning

confidence: 99%

X-ray grazing incidence diffraction from alkylsiloxane monolayers on silicon wafers

Tidswell

Rabedeau

Pershan

et al. 1991

The Journal of Chemical Physics

136

103

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“…249 More recently, the ozonolysis of the 8-carbon alkene SAM has been revisited using ZnSe and SiO x -coated ZnSe ATR crystals. 250 SAMs on ZnSe are not nearly as well characterized as those on silicon, [251][252][253] but have the advantage that ZnSe transmits down to B650 cm À1 , well beyond the B1500 cm À1 cut-off for the silicon ATR crystal. This allows one to probe for additional products that absorb below 1500 cm À1 .…”

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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“…This may be due to the greater instability of the oxide layer on Ge. 36,37 Fig . 3 shows typical spectra as a function of reaction time during exposure to OH.…”

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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On the formation and structure of self-assembling monolayers. I. A comparative atr-wettability study of Langmuir—Blodgett and adsorbed films on flat substrates and glass microbeads

Cited by 595 publications

References 65 publications

X-ray grazing incidence diffraction from alkylsiloxane monolayers on silicon wafers

X-ray grazing incidence diffraction from alkylsiloxane monolayers on silicon wafers

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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