Surface micelles of semifluorinated alkanes in Langmuir–Blodgett monolayers

Zhang, Guifang; Maaloum, Mounir; Muller, Pierre; Benoit, Nicole; Krafft, Marie Pierre

doi:10.1039/b314764a

Cited by 34 publications

(59 citation statements)

References 17 publications

(23 reference statements)

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“…[17,24,38] When spread on water, these compounds spontaneously self-assemble into surface hemimicelles. When reaching the first pressure liftoff recorded on their Langmuir isotherms, their monolayers consist of regular hexagonal arrays of such surface micelles, [29,30,33,39,40] as further confirmed by the AFM studies reported here. Therefore, the present study really concerns www.chemeurj.org the compression of monolayers of self-assembled objects rather than of independent molecules.…”

Section: Discussionsupporting

confidence: 85%

“…[29,30,33,37,40] These surface micelles are highly monodisperse, start forming at very low surface pressures, following a concentration-rather than pressure-dependent mechanism, [41] and, upon compression, organize in regular hexagonal arrays without significant change in micelle size and morphology. The aptitude to form monolayers patterned by surface micelles was shown to originate in the dipole moment of the diblocks [42] and already covers a wide range of compounds (n = 8-14, m = 14-20).…”

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confidence: 99%

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Compression of Self‐Assembled Nano‐Objects: 2D/3D Transitions in Films of (Perfluoroalkyl)Alkanes—Persistence of an Organized Array of Surface Micelles

Lux

Gallani

Waton

et al. 2010

Chemistry A European J

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Understanding and controlling the molecular organization of amphiphilic molecules at interfaces is essential for materials and biological sciences. When spread on water, the model amphiphiles constituted by C(n)F(2n+1)C(m)H(2m+1) (FnHm) diblocks spontaneously self-assemble into surface hemimicelles. Therefore, compression of monolayers of FnHm diblocks is actually a compression of nanometric objects. Langmuir films of F8H16, F8H18, F8H20, and F10H16 can actually be compressed far beyond the "collapse" of their monolayers at approximately 30 A(2). For molecular areas A between 30 and 10 A(2), a partially reversible, 2D/3D transition occurs between a monolayer of surface micelles and a multilayer that coexist on a large plateau. For A<10 A(2), surface pressure increases again, reaching up to approximately 48 mN m(-1) before the film eventually collapses. Brewster angle microscopy and AFM indicate a several-fold increase in film thickness when scanning through the 2D/3D coexistence plateau. Compression beyond the plateau leads to a further increase in film thickness and, eventually, to film disruption. Reversibility was assessed by using compression-expansion cycles. AFM of F8H20 films shows that the initial monolayer of micelles is progressively covered by one (and eventually two) bilayers, which leads to a hitherto unknown organized composite arrangement. Compression of films of the more rigid F10H16 results in crystalline-like inflorescences. For both diblocks, a hexagonal array of surface micelles is consistently seen, even when the 3D structures eventually disrupt, which means that this monolayer persists throughout the compression experiments. Two examples of pressure-driven transformations of films of self-assembled objects are thus provided. These observations further illustrate the powerful self-assembling capacity of perfluoroalkyl chains.

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Section: Discussionsupporting

confidence: 85%

mentioning

confidence: 99%

Compression of Self‐Assembled Nano‐Objects: 2D/3D Transitions in Films of (Perfluoroalkyl)Alkanes—Persistence of an Organized Array of Surface Micelles

Lux

Gallani

Waton

et al. 2010

Chemistry A European J

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“…Since the emergence of microscopy, especially AFM, it has become possible to investigate surface micelles directly. The formation of surfactant hemimicelles adsorbed onto hydrophobic solid surfaces in aqueous solutions observed by AFM, or transferred onto silicon wafers by the LB technique studied by AFM and X-ray reflectivity, has been reported [10,11]. Surface micelles at the air/water interface formed by nonionic diblock copolymers have been found [12,13].…”

Section: Introductionmentioning

confidence: 96%

Cationic Gemini surfactant at the air/water interface

Chen

Liang

Wang

et al. 2007

Journal of Colloid and Interface Science

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“…Previous studies have demonstrated that the ratio between Fn and Hm segments influences the collapse pressure of the FnHm monolayer [12][13][14] and modulates the domain size. [8,[23][24] However,i ts hould be noted that most of theses tudies are AFM studies that deal with monolayers transferred onto solid substrates, which may interferew ith the initial structure. Except the study by Bardin et al [23] ,there have been no studies shedding light on the impact of Hm segmentl ength on the surfacedomain structures at the air/waterinterface.…”

Section: Introductionmentioning

confidence: 99%

Size, Shape, and Lateral Correlation of Highly Uniform, Mesoscopic, Self‐Assembled Domains of Fluorocarbon–Hydrocarbon Diblocks at the Air/Water Interface: A GISAXS Study

et al. 2017

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The shape and size of self‐assembled mesoscopic surface domains of fluorocarbon–hydrocarbon (FnHm) diblocks and the lateral correlation between these domains were quantitatively determined from grazing incidence small‐angle X‐ray scattering (GISAXS). The full calculation of structure and form factors unravels the influence of fluorocarbon and hydrocarbon block lengths on the diameter and height of the domains, and provides the inter‐domain correlation length. The diameter of the domains, as determined from the form factor analysis, exhibits a monotonic increase in response to the systematic lengthening of each block, which can be attributed to the increase in van der Waals attraction between molecules. The pair correlation function in real space calculated from the structure factor implies that the inter‐domain correlation can reach a distance that is over 25 times larger than the domain's size. The full calculation of the GISAXS signals introduced here opens a potential towards the hierarchical design of mesoscale domains of self‐assembled small organic molecules, covering several orders of magnitude in space.

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Surface micelles of semifluorinated alkanes in Langmuir–Blodgett monolayers

Cited by 34 publications

References 17 publications

Compression of Self‐Assembled Nano‐Objects: 2D/3D Transitions in Films of (Perfluoroalkyl)Alkanes—Persistence of an Organized Array of Surface Micelles

Compression of Self‐Assembled Nano‐Objects: 2D/3D Transitions in Films of (Perfluoroalkyl)Alkanes—Persistence of an Organized Array of Surface Micelles

Cationic Gemini surfactant at the air/water interface

Size, Shape, and Lateral Correlation of Highly Uniform, Mesoscopic, Self‐Assembled Domains of Fluorocarbon–Hydrocarbon Diblocks at the Air/Water Interface: A GISAXS Study

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