Hydrophilic interaction principles

Figure 1 Principles of reversed-phase high-performance liquid chromatography (RP-HPLC) and hydrophilic interaction liquid chromatography (HILIC).

Separation media, with bimodal chemistry, are generally designed for the complete separation of complex samples, such as blood plasma serum, that typically contain molecules differing in properties such as size, charge, and polarity. The major principle of bifunctional separation relies on the pore size and functional difference in the media. For example, a polymer bead with hydrophilic large pores and hydrophobic small pores will not interact with and retain large molecules such as proteins, but will interact with and retain small molecules such as drugs and metabolites. 

The restricted access principle is based on the concept of diffusion-based exclusion of matrix components and allows peptides, which are able to access the internal surface of the particle, to interact with a functionalized surface (Figure 9.2). The diffusion barrier can be accomplished in two ways (i) the porous adsorbent particles have a topochemically different surface functionalization between the outer particle surface and the internal surface. The diffusion barrier is then determined by an entropy controlled size exclusion mechanism of the particle depending on the pore size of adsorbent (Pinkerton, 1991) and (ii) the diffusion barrier is accomplished by a dense hydrophilic polymer layer with a given network size over the essentially functionalized surface. In other words, the diffusion barrier is moved as a layer to the interfacial... 

Different surfactants are usually characterised by the solubility behaviour of their hydrophilic and hydrophobic molecule fraction in polar solvents, expressed by the HLB-value (hydrophilic-lipophilic-balance) of the surfactant. The HLB-value of a specific surfactant is often listed by the producer or can be easily calculated from listed increments [67]. If the water in a microemulsion contains electrolytes, the solubility of the surfactant in the water changes. It can be increased or decreased, depending on the kind of electrolyte [68,69]. The effect of electrolytes is explained by the HSAB principle (hard-soft-acid-base). For example, salts of hard acids and hard bases reduce the solubility of the surfactant in water. The solubility is increased by salts of soft acids and hard bases or by salts of hard acids and soft bases. Correspondingly, the solubility of the surfactant in water is increased by sodium alkyl sulfonates and decreased by sodium chloride or sodium sulfate. In the meantime, the physical interactions of the surfactant molecules and other components in microemulsions is well understood and the HSAB-principle was verified. The salts in water mainly influence the curvature of the surfactant film in a microemulsion. The curvature of the surfactant film can be expressed, analogous to the HLB-value, by the packing parameter Sp. The packing parameter is the ratio between the hydrophilic and lipophilic surfactant molecule part [70] ... 

In principle, placing a hydrophilic residue in a non-aqueous environment is energetically unfavorable. In integral proteins with multiple a helices that span the membrane, hydrophilic side chains from different helical segments may interact and in some cases form a channel through which ions may diffuse. Portions of the helical segments exposed to the lipid will contain primarily hydrophobic amino acid residues. 

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