Packing Characteristics of Crystalline Monolayers of Fatty Acid Salts, at the Air-Solution Interface, Studied by Grazing Incidence X-ray Diffraction

Böhm, C.; Leveiller, F.; Jacquemain, D.; Möhwald, Helmuth; Kjaer, K.; Als‐Nielsen, J.; Weissbuch, W.; Leiserowitz, Leslie

doi:10.1021/la00015a038

Cited by 69 publications

(59 citation statements)

References 2 publications

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“…[15] In the high q range (q Ͼ 12 nm -1 ) the most intense event observed in all the diffractograms ( Figure S2) is a broad band centred at q = 15 nm -1 , associated with ordering within the siliceous domains, [27] amide-amide spacing [10c] and chainchain spacing. [28] Characteristic distances, d = 0.42-0.41 nm, were calculated by using the Bragg law. The coherence length, L, over which the structural unit survives was estimated by using the modified Sherrer equation L = Iλ/ (Acosθ) (where A, in radians, is the integrated area of the peaks and I is the corresponding maximum intensity).…”

Section: Structure and Thermal Behaviour Of The Monoamidosilsmentioning

confidence: 99%

Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

et al. 2010

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Registro de acceso restringido Este recurso no está disponible en acceso abierto por política de la editorial. No obstante, se puede acceder al texto completo desde la Universitat Jaume I o si el usuario cuenta con suscripción. Registre d'accés restringit Aquest recurs no està disponible en accés obert per política de l'editorial. No obstant això, es pot accedir al text complet des de la Universitat Jaume I o si l'usuari compta amb subscripció. Restricted access item This item isn't open access because of publisher's policy. The full--text version is only available from Jaume I University or if the user has a running suscription to the publisher's contents.

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Section: Structure and Thermal Behaviour Of The Monoamidosilsmentioning

confidence: 99%

Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

et al. 2010

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“…[72][73][74][75] Datta et al 72 use GIXD to consider pHdependent changes. [72][73][74][75] Datta et al 72 use GIXD to consider pHdependent changes.…”

Section: Analysis Of In Situ Titrationmentioning

confidence: 99%

Interfacial chemistry on carboxylate‐functionalized monolayer assemblies

Gershevitz

Osnis

Sukenik

2005

Israel Journal of Chemistry

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Deposition of trichlorosilanes with ester groups at their remote termini provides a convenient entry to carboxylic acid‐bearing siloxane‐anchored self‐assembled monolayers. The de‐esterification of these esters has been optimized to minimize monolayer damage, and their quantitative re‐esterification provides clear evidence for the stability of these systems. Both the structure of the ester‐terminated monolayer and its de‐esterification/esterification chemistry can be easily monitored by FTIR‐ATR measurements. This spectroscopic tool, together with a liquid cell that enables IR spectra to be measured in an aqueous environment, enables a detailed structural analysis of the carboxylic acid‐bearing siloxane‐anchored self‐assembled monolayers and an assessment of their acid/base behavior (by in situ titration). The use of D2O instead of H2O for the in situ titration experiments also improves the available IR window. Both monomeric and dimeric/oligomeric acid groups are seen, and the relative ease of deprotonation of these various species can be directly monitored. Monomers of alkyl carboxylic acids that are hydrogen bonded only to surrounding water molecules have a pKa = 4.9, while the pKa for the aggregated molecules is 9.3. Similar behavior is seen for surface‐bound benzoic acids, where the two pKa values are 4.7 and 9.0. The influence of temperature on these structures and their chemistry has been explored to a limited extent as well. When the alkylcarboxylic acid system is cooled to 10 °C, the pKa value for the acid monomers is reduced from 4.9 to 4.5 and increases from 9.3 to 10.3 for the aggregates.

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“…13, 18, 19 To gain a better understanding of the recognition at the nucleation stage we performed further analysis of the structure of the SAM/calcite interfaces. Previous studies20–22 of the carboxylic acid terminated Langmuir monolayers and SAMs in the presence of Ca 2+ and Cd 2+ ions have shown a considerable ordering of the surface that results in the fixation of the carboxylic groups in a specific orientation. In particular, it has been shown that the overlayer of Ca 2+ ions on a SAM of HS‐C 15 ‐COO − fixes the terminal groups in a preferred orientation, in which one CO bond is parallel to the substrate 23.…”

mentioning

confidence: 99%

Face‐Selective Nucleation of Calcite on Self‐Assembled Monolayers of Alkanethiols: Effect of the Parity of the Alkyl Chain

Han¹,

Aizenberg²

2003

Angew Chem Int Ed

112

111

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The use of self-assembled monolayers (SAMs) has provided an ideal platform to study the function of highly ordered organic surfaces for various applications, including nucleation of crystals. [1][2][3][4][5][6][7][8] In particular, SAMs of alkanethiols with a range of functionalities supported on gold and silver have been demonstrated to effectively nucleate calcium carbonate crystals, with a high degree of orientational specificity for each surface. [2,[9][10][11] It has been shown that the face-selective nucleation of calcite cannot be explained in terms of the lattice match between the SAM and the crystal face it nucleates. It has been suggested that a match may exist between the direction of the SAM terminal groups and that of anions in the nucleated crystal. [9] This situation would imply that the mechanism of the face-selective nucleation involves the translation of the orientation of the terminal groups on the SAM into the nucleating crystals. The validity of this hypothesis could not be explicitly tested in the previously reported systems, since the SAMs used differed in multiple parameters (for example, functional groups, metal support, chain length).Herein we verify the proposed mechanism by investigating the oriented growth of calcite on SAMs in which only one parameter-the orientation of the functional group-is varied. For this purpose, we utilized the so-called "odd-even effect" in the monolayers. [8,12,13] Detailed structural studies of SAMs [14,15] have shown that the orientation of long-chain alkanethiols (HS(CH 2 ) n CH 3 ) adsorbed from solution onto metal surfaces is determined by the cant (a, Figure 1 a) and twist (b) angles which the thiol molecules adopt in relation to the metal film during the formation of the monolayers. It has been demonstrated that when gold films are used to support SAMs, a and b have the same value and sign for all alkanethiol chains, while alkanethiol molecules assembled on silver show cant angles of opposite signs for alkyl chains of different parity. Therefore, the orientation of the terminal group X in SAMs on Ag is constant for both odd and even chains, and the terminal group X in SAMs on Au forms two different angles with the interface for odd and even chain lengths (Figure 1). SAMs with alkyl chains of different parity assembled on Au and Ag provide two ideal control systems to study the effect of terminal groups on the oriented growth of crystals. We anticipated that, if face-selective nucleation were controlled by the orientation of the functional groups in the templating surface, then all SAMs on Ag would induce the oriented crystal growth from the same crystal plane, while odd-and even-lengthed SAMs on Au should induce nucleation in two different crystallographic directions.Several sulfanylalkanoic acids with different methylene chain lengths were assembled on gold and silver to template the nucleation of calcite. Sulfanyloctanoic acid (HS-C 7 -COOH, denoted C 7 ), sulfanylundecanoic acid (HS-C 10 - Figure 1. Schematic representation of even and odd chain le...

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Packing Characteristics of Crystalline Monolayers of Fatty Acid Salts, at the Air-Solution Interface, Studied by Grazing Incidence X-ray Diffraction

Cited by 69 publications

References 2 publications

Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

Interfacial chemistry on carboxylate‐functionalized monolayer assemblies

Face‐Selective Nucleation of Calcite on Self‐Assembled Monolayers of Alkanethiols: Effect of the Parity of the Alkyl Chain

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Packing Characteristics of Crystalline Monolayers of Fatty Acid Salts, at the Air-Solution Interface, Studied by Grazing Incidence X-ray Diffraction

Cited by 69 publications

References 2 publications

EuIII‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

EuIII‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

Interfacial chemistry on carboxylate‐functionalized monolayer assemblies

Face‐Selective Nucleation of Calcite on Self‐Assembled Monolayers of Alkanethiols: Effect of the Parity of the Alkyl Chain

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Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids

Eu^III‐Doping of Lamellar Bilayer and Amorphous Mono‐Amide Cross‐Linked Alkyl/Siloxane Hybrids