Sum frequency generation imaging microscopy (SFGIM) is used to image the chemically distinct regions of a microcontact-printed monolayer surface. The contrast in the images is based on the vibrational spectrum of each component in the monolayer. Mixtures of C16 thiols on gold with CH3 and phenyl termination are imaged with a resolution of approximately 10 microm. Microcontact printing produces films that are different compared to the immersion procedure of forming self-assembled monolayers. The SFGIM technique is able to obtain a vibrational spectrum at each point on the surface and demonstrate that the stamped area has significant mixing with the molecules deposited from the backfilling solution.
Friction converts kinetic energy at sliding interfaces into lattice vibrations, but the detailed mechanisms of this process remain unresolved. Atomic force microscopy measurements reveal that changing the mass of the terminating atoms on a surface, and thus their vibrational frequencies, affects nanoscale friction substantially. We compared hydrogen- and deuterium-terminated single-crystal diamond and silicon surfaces, and in all cases the hydrogenated surface exhibited higher friction. This result implies that the lower natural frequency of chemisorbed deuterium reduces the rate at which the tip's kinetic energy is dissipated. This discovery is consistent with a model describing energy transfer to adsorbates from a moving surface.
The molecular orientation of trimethylamine N-oxide (TMAO), a powerful protein stabilizer, was explored at aqueous/hydrophobic interfaces using vibrational sum frequency spectroscopy (VSFS). The systems studied included the octadecyltrichlorosilane (OTS)/water interface, which represents an aqueous solution in direct contact with a hydrophobic medium. Surprisingly, the measurements revealed that the methyl groups of TMAO pointed into the aqueous phase and away from the OTS. This orientation may arise from the more hydrophilic nature of methyl groups attached to a strongly electron-withdrawing atom such as a quaternary nitrogen. Additional studies were performed at the air/water interface. This interface showed a high degree of TMAO alignment, but the dangling OH from water was present even at 5 M TAMO. Moreover, the addition of this osmolyte modestly increased the surface tension of the interface. This meant that this species was somewhat depleted at the interface compared to the bulk solution. These findings may have implications for the stabilizing effect of TMAO on proteins. Specifically, the strong hydration required for the methyl groups as well as the oxide moiety should be responsible for the osmolyte's depletion from hydrophobic/aqueous interfaces. Such depletion effects should help stabilize proteins in their folded and native conformations on entropic grounds, although orientational effects may play an additional role.
Sum frequency generation imaging microscopy has been used to investigate a self-assembled monolayer of an alkanethiol (octadecanethiol, ODT) on a mild steel surface. The images are used to analyze the orientation of the alkanethiol monolayer and the distribution of orientational angles as well as defects in the film. The results show that, on average, ODT forms an ordered monolayer on mild steel when compared to the same monolayer on gold. However, the image analysis suggests that the distribution of tilt angles and conformational defects is greater for ODT on a mild steel surface compared to ODT/Au.
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