RESUMO
A series of long-tail alkyl ethanolamine analogs containing amide-, urea-, and thiourea moieties was synthesized and the behavior of the corresponding monolayers was assessed on the Langmuir-Pockels trough combined with grazing incidence X-ray diffraction experiments and complemented by computer simulations. All compounds form stable monolayers at the soft air/water interface. The phase behavior is dominated by strong intermolecular headgroup hydrogen bond networks. While the amide analog forms well-defined monolayer structures, the stronger hydrogen bonds in the urea analogs lead to the formation of small three-dimensional crystallites already during spreading due to concentration fluctuations. The hydrogen bonds in the thiourea case form a two-dimensional network, which ruptures temporarily during compression and is recovered in a self-healing process, while in the urea clusters the hydrogen bonds form a more planar framework with gliding planes keeping the structure intact during compression. Because the thiourea analogs are able to self-heal after rupture, such compounds could have interesting properties as tight, ordered, and self-healing monolayers.
Assuntos
Etanolaminas/química , Compostos de Sulfidrila/química , Ureia/química , Simulação por Computador , Ligação de Hidrogênio , Espectrometria de Massas por Ionização por Electrospray , Difração de Raios XRESUMO
Bring it on: Organic chemistry on surfaces and in solution is not the same; this study offers a perfect example that small changes (from 27 to 35°; see graphic) can result in big consequences. Strained cyclic disulfides from asparagusic, but not lipoic acid, are ideal for growing functional architectures directly on surfaces; for the substrate-initiated synthesis of cell-penetrating poly(disulfide)s in solution, exactly the contrary is true.
