TY - JOUR
T1 - Effect of cosolvent on the lateral order of spontaneously formed amphiphilic amide 2-dimensional crystallites at the air solution interface
AU - Weinbach, S.P.
AU - Jacquemain, D.
AU - Leveiller, F.
AU - Kjær, K.
AU - Als-Nielsen, J.
AU - Leiserowitz, L.
PY - 1993
Y1 - 1993
N2 - At low temperature (5–12 °C), uncompressed films of insoluble amphiphilic molecules C13H39X, where the head group X contains one (CONH2, 1) or two (CONHC2H4CONH2, 2) amide groups, spontaneously form two-dimensional (2D) crystalline clusters over aqueous subphases containing soluble amide or carboxylic acid molecules. These crystallites were detected and their structures were studied using grazing incidence X-ray diffraction (GID). In the presence of subphases containing carboxylic acid (RCO2H, R = H, CH2Cl) at sufficiently high concentrations, a loss of diffraction signal was observed for 1, while amide and less concentrated acid subphases did not show such a destructive effect. The effect of the subphase solute molecules was understood in terms of the different ways in which the solutes hydrogen bond to the amide head groups of the amphiphiles. Both amide and acid solute molecules can form hydrogen-bonded cyclic dimers with the amide head groups. With an amide subphase, such dimers lead to an extension of the hydrogen-bonding network of the crystallites, and thus enhance its stability, but acid molecules may also bind to the monolayer at low concentrations with less than full occupancy. At high acid concentration, and thus more extensive formation of cyclic dimers between carboxylic acid and amphiphilic amide molecules, repulsive interactions between lone pair electrons on oxygen atoms of bound acid molecules inhibit formation of ordered arrays of these dimers and lead to a lack of diffraction signal. In 2, the second amide group strengthens the crystallites to the extent that there is no decrease in crystallinity over a 1 M formic acid subphase. The shape of the intensity profiles of the Bragg rods and the specular X-ray reflectivity measurements of 2 indicate formation of molecular trilayers.
AB - At low temperature (5–12 °C), uncompressed films of insoluble amphiphilic molecules C13H39X, where the head group X contains one (CONH2, 1) or two (CONHC2H4CONH2, 2) amide groups, spontaneously form two-dimensional (2D) crystalline clusters over aqueous subphases containing soluble amide or carboxylic acid molecules. These crystallites were detected and their structures were studied using grazing incidence X-ray diffraction (GID). In the presence of subphases containing carboxylic acid (RCO2H, R = H, CH2Cl) at sufficiently high concentrations, a loss of diffraction signal was observed for 1, while amide and less concentrated acid subphases did not show such a destructive effect. The effect of the subphase solute molecules was understood in terms of the different ways in which the solutes hydrogen bond to the amide head groups of the amphiphiles. Both amide and acid solute molecules can form hydrogen-bonded cyclic dimers with the amide head groups. With an amide subphase, such dimers lead to an extension of the hydrogen-bonding network of the crystallites, and thus enhance its stability, but acid molecules may also bind to the monolayer at low concentrations with less than full occupancy. At high acid concentration, and thus more extensive formation of cyclic dimers between carboxylic acid and amphiphilic amide molecules, repulsive interactions between lone pair electrons on oxygen atoms of bound acid molecules inhibit formation of ordered arrays of these dimers and lead to a lack of diffraction signal. In 2, the second amide group strengthens the crystallites to the extent that there is no decrease in crystallinity over a 1 M formic acid subphase. The shape of the intensity profiles of the Bragg rods and the specular X-ray reflectivity measurements of 2 indicate formation of molecular trilayers.
KW - Materialer med særlige fysiske og kemiske egenskaber
U2 - 10.1021/ja00077a007
DO - 10.1021/ja00077a007
M3 - Journal article
SN - 0002-7863
VL - 115
SP - 11110
EP - 11118
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 24
ER -