Reclined trend of alkyl chain of sodium dodecylbenzenesulfonate molecules induced by friction

Surfactants tend to adsorb on the surface/interface mostly in a directional manner. The alkyl chain orientation and conformation order for molecular monolayers of sodium dodecylbenzenesulfonate (SDBS) at low concentrations are studied by using the sum frequency generation vibrational spectroscopy (SFG-VS). The molecular arrangement of the surfactants adsorbed at the solid/liquid interface is further investigated. It is found that the arrangement of the SDBS at the interface becomes relatively ordered with increasing bulk concentration. Meanwhile, the orientation angle reduces gradually, and the molecules tend to be upright state. In addition, the effect of friction on the conformation order and orientation angle are also analyzed. The intensity of the SDBS vibrational contraction peak becomes lower after friction, which indicates that the anion has a reorientation process at the interface. The arrangement of molecules becomes more disordered due to friction. The orientation angle increases slightly, which indicates the monolayer has an inclined trend relative to the lateral direction on the interface. A modified adsorption model considering friction effect is proposed. This work may provide a reference for the further study of adsorption mechanism and application of surfactants.

Converting non-Mesogenic to Mesogenic Stacking of Amino-s-Triazine-Based Dendrons with p-CN Phenyl Unit by Eliminating Peripheral Dipole

Three new amino-s-triazine-based dendrons, 1a, 1b, and 1c, containing an aryl-CN moiety in the dendritic skeleton were prepared in 72–81% yields (1a: R1 = − N(n-C8H17)2, R2 = n-OC8H17, 1b: R1 = R2 = − N(n-C8H17)2, 1c: R1 = − N(n-C8H17)2, R2 = − N(n-C4H9)2). Dendrons 1a with N(n-C8H17)2 and n-OC8H17 peripheral substituents, surprisingly, did not show any mesogenic phase during the thermal process. However, non-mesogenic 1a can be converted to mesogenic 1b or 1c by eliminating the peripheral dipole arising from the alkoxy substituent; dendron 1b only comprising the same N(n-C8H17)2 peripheral groups showed a ~25 °C mesogenic range on heating and ~108 °C mesogenic range on cooling. In contrast, dendron 1c possessing different N(n-CmH2m+1)2 (m = 8 versus m = 4) peripheral units, having similar stacking as 1b, exhibited a columnar phase on thermal treatment, but its mesogenic range (~9 and ~66 °C on heating and cooling, respectively) was much narrower than that of 1b, attributed to 1c’s less flexible alkyl chains in the peripheral part of dendron. Dendron 1a with the alkoxy substituent in the peripheral skeleton, creating additional dipole correspondingly, thus, leads to the dendritic molecules having a non-mesogenic stacking. Without the peripheral dipole for intermolecular side-by-side interaction, dendrons 1b and 1c exhibit a columnar phase on thermal treatment because of the vibration from the peripheral alkyl chain.

Molecular Recognition by Pillar[5]arenes: Evidence for Simultaneous Electrostatic and Hydrophobic Interactions

The formation of inclusion complexes between alkylsulfonate guests and a cationic pillar[5]arene receptor in water was investigated by NMR and ITC techniques. The results show the formation of host-guest complexes stabilized by electrostatic interactions and hydrophobic effects with binding constants of up to 107 M−1 for the guest with higher hydrophobic character. Structurally, the alkyl chain of the guest is included in the hydrophobic aromatic cavity of the macrocycle while the sulfonate groups are held in the multicationic portal by ionic interactions.