Polymerized Monomolecular Films: Microscopic Structure, Viscosity, and Photopolymerization Kinetics

Rolandi, R.; Dante, Silvia; Gussoni, A.; Leporatti, Stefano; Maga, L.; Tundo, Pietro

doi:10.1021/la00008a043

Cited by 11 publications

(11 citation statements)

References 3 publications

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“…Hence, in the model, one must also consider the time-dependent area variation in conjunction with the time-dependent change in the monomer concentration near the reaction centers. This concept was first introduced successfully by Rolandi et al (1995). These two effects can be considered by the combination of the independently measured data obtained from UV-vis spectra (Fig.…”

Section: Kinetic Modelsmentioning

confidence: 99%

“…In a special case, however, topochemical polymerization takes place, which means that the crystal structure remains unchanged and no area contraction occurs during the reaction (Wegner, 1969). The polymerization reaction can also be followed ex situ by various complementary techniques such as surface viscosity (Dubault et al, 1975;Rolandi et al, 1995), atomic force microscopy (Peltonen et al, 1993;Tillmann et al, 1994;Rolandi et al, 1995), fluorescence microscopy (Warta and Sixl, 1988;Meller et al, 1989;Rolandi et al, 1995), UV-vis (Tieke et al, 1979;Laschewsky et al, 1988;Mino et al, 1991;Viitala et al, 1997), and IR spectroscopy (Letts et al, 1976;Lindén et al, 1995).…”

Section: Introductionmentioning

confidence: 99%

“…The theoretical treatment of a reaction performed on a monolayer is not as straightforward as it seems to be, and models for three-dimensional reaction kinetics cannot be directly applied because of the peculiar features of a twodimensional system (Raudino, 1994;Rolandi et al, 1995). Successful attempts at modeling the reaction kinetics of a floating monolayer have been made by a few research groups (Bodalia and Duran, 1993;Rolandi et al, 1995;Viitala et al, 1997).…”

Section: Introductionmentioning

confidence: 99%

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UV-Induced Reaction Kinetics of Dilinoleoylphosphatidylethanolamine Monolayers

Peltonen

1999

Biophysical Journal

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The UV-induced reactivity of dilinoleoylphosphatidylethanolamine (DLiPE) Langmuir and Langmuir-Blodgett films has been studied by in situ measurements of the changes in the mean molecular area, UV-vis and Fourier transform infrared spectroscopy, and atomic force microscopy (AFM). Optimum orientation and packing density of the DLiPE molecules in the monolayer were achieved by adding uranyl acetate to the subphase. A first-order reaction kinetic model was successfully fitted to the experimental reaction kinetics data obtained at a surface pressure of 30 mN/m. Topographical studies of LB films by AFM were performed on bilayer structures as a function of subphase composition and UV irradiation time. The orientational effect of the uranyl ions on the monolayer molecules was observed as an enhanced homogeneity of the freshly prepared monomeric LB films. However, the long-term stability of these films proved to be bad; clear reorganization and loss of a true monolayer structure were evidenced by the AFM images. This instability was inhibited for the UV-irradiated films, indicating that the UV irradiation gave rise to a cross-linked structure.

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Section: Kinetic Modelsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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UV-Induced Reaction Kinetics of Dilinoleoylphosphatidylethanolamine Monolayers

Peltonen

1999

Biophysical Journal

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“…Besides the presence of isomer, the presence of isolated molecules of polymer may be also suggested in the unpolymerized AEEAm domains. Rolandi et al also observed by fluorescence microscopy such an uncomplete polymerization . They polymerized monolayers of surfactants functionalized with styrene groups by UV irradiation and studied the evolution of the structure of the film during the irradiation.…”

Section: Discussionmentioning

confidence: 99%

Polymerization of Aminoethyl Elaidamide in Langmuir and Langmuir−Blodgett Films Studied by SFM

1999

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The polymerization of aminoethyl elaidamide in Langmuir and Langmuir−Blodgett films has been studied. In Langmuir films, changes induced by the polymerization process were investigated by pressure/area isotherm measurements and after transfer of the irradiated film by scanning force microscopy and IR spectroscopy. The pressure/area isotherms showed a phase transition at 16 mN/m, vanishing when the irradiation time is increased. At low resolution, scanning force microscopy images revealed that the irradiation induced the formation of structured domains. The shapes of these domains and the area occupied by these domains are dependent on irradiation time. At intermediate resolution, these domains which correspond to the polymeric phase appeared to be constituted of fibrillar structures characteristic of a crystalline polymer. Besides these domains, the film has a similar structure to the monomer film. For the polymerization in LB films, the changes in the structure of the film were followed by scanning force microscopy and IR spectroscopy as a function of irradiation time. Few changes in surface topography were observed at the micrometer scale during the polymerization. However we observed an increase of tip/sample interactions with irradiation time; moreover the irradiated film was found to be unsoluble. These results are indirect proofs of the polymerization.

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“…The divergence of the surface viscosity is strong evidence for a cross-linking reaction and not just the formation of a linear polymer. [50] Additional chemical insight is provided assuming that the area change per chemical reaction is constant; the resulting inset scale then gives an approximation of the extent of reaction as the monomer converts to products, even though the exact chemical nature of the product is not completely known. The extrapolation of the gel point line corresponds to about 85% of the extent of reaction.…”

Section: Surface Viscositymentioning

confidence: 99%

Interfacial Behavior of a Reacting Alkoxysilane Monolayer System

Carino

Duran

2004

Macro Chemistry & Physics

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Summary: We report here the results on the investigations of the dynamic interfacial behavior of a trifunctional alkoxysilane, octadecyltrimethoxysilane (OTMS) as it is reacting at the air‐water interface. We have investigated both the Π‐A isotherms and A(t) isobars of OTMS at acidic subphases. An attempt to analyze the kinetics of the reaction in the monolayer was limited to the early stages of the reactions and only describes the kinetics of hydrolysis. We also confirmed by rheological measurements that this system does indeed form a network inefficiently and the resulting structure most likely consists of extensive linear segments as has been suggested in earlier reports. The general rheological characteristic indicates the product to have high molecular weight. The product also exhibited a 2D sol‐gel transition that has general features of a percolating network. However, the scaling behavior does not follow exactly that predicted; several reasons for this are discussed.A(t) isobars of OTMS at various subphase pHmagnified imageA(t) isobars of OTMS at various subphase pH

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Polymerized Monomolecular Films: Microscopic Structure, Viscosity, and Photopolymerization Kinetics

Cited by 11 publications

References 3 publications

UV-Induced Reaction Kinetics of Dilinoleoylphosphatidylethanolamine Monolayers

UV-Induced Reaction Kinetics of Dilinoleoylphosphatidylethanolamine Monolayers

Polymerization of Aminoethyl Elaidamide in Langmuir and Langmuir−Blodgett Films Studied by SFM

Interfacial Behavior of a Reacting Alkoxysilane Monolayer System

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