Order and disorder in alkyl stationary phases

Covalently modified surfaces represent a unique state of matter that is not well described by liquid or solid phase models. The chemical bond in tethered alkanes imparts order to the surface in the form of anisotropic properties that are evident in chromatographic and spectroscopic studies. An understanding of the structure, conformation, and organization of alkyl-modified surfaces is requisite to the design of improved materials and the optimal utilization of existing materials. In recent years, the study of alkyl-modified surfaces has benefited from advances in modern analytical instrumentation. Aspects of alkyl chain conformation and motion have been investigated through the use of nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, fluorescence spectroscopy, and neutron scattering studies. Chromatography provides complementary evidence of alkyl chain organization through interactions with solute probes. Computational simulations offer insights into the structure of covalently modified surfaces that may not be apparent through empirical observation. This manuscript reviews progress achieved in the study of the architecture of alkyl-modified surfaces.