Cyclodextrin hydrophobic, types

There are three main types of CDs a-cyclodextrin (a-CD), -cyclodexlrin (p-CD), and y-cyclodextrin (y-CD), which are macrocycles formed by six, seven, and eight sugar ring molecules, respectively. The spatial structure of p-CD is shown on Fig. 3. Review [19] generalizes data on the synthesis, modification, physicochemical and theoretical investigations of CDs, and certain applications particularly for enantio-separation and pharmaceutical applications. CDs are able to form host-guest complexes (pseudorotaxanes) with hydrophobic molecules such as aza-dyes... 

The PO mode is a specific elution condition in HPLC enantiomer separation, which has received remarkable popularity especially for macrocyclic antibiotics CSPs and cyclodextrin-based CSPs. It is also applicable and often preferred over RP and NP modes for the separation of chiral acids on the cinchonan carbamate-type CSPs. The beneficial characteristics of the PO mode may arise from (i) the offset of nonspecific hydrophobic interactions, (ii) the faster elution speed, (iii) sometimes enhanced enan-tioselectivities, (iv) favorable peak shapes due to improved diffusive mass transfer in the intraparticulate pores, and last but not least, (v) less stress to the column, which may extend the column lifetime. Hence, it is rational to start separation attempts with such elution conditions. Typical eluents are composed of methanol, acetonitrile (ACN), or methanol-acetonitrile mixtures and to account for the ion-exchange retention mechanism the addition of a competitor acid that acts also as counterion (e.g., 0.5-2% glacial acetic acid or 0.1% formic acid) is required. A good choice for initial tests turned out to be a mobile phase being composed of methanol-glacial acetic acid-ammonium acetate (98 2 0.5 v/v/w). 

It was pointed ouF that while ionomer-modified electrodes have greater selectivity than naked electrodes, ionomers provide only a general form of selectivity (charge type and mass or hydrophobicity selectivity), and special methods were suggested to improve specific selectivity. For example, it was thought that applying an additional cellulose acetate layer over the Nafion film would make the electrode selective with respect to dopamine specifically (in contrast to other neurotransmitters). To make the electrode system specifically selective to o-nitrophenol (in contrast to /(-isomer), a complexation with cyclodextrin was performed, which increased the selectivity ratio one order of magnitude with respect to the o-isomer. ... 

Thus, it seems that both the hydrophobic interactions and the van der Waals interactions undoubtedly play a part in inclusion-complex formation, although the relative contribution of each type of interaction may vary with the chemical properties of the guest this would account for the ability of the cyclodextrins to form complexes with a wide variety of guest molecules. The existence of a close spatial fit between the guest and the cyclodextrin cavity is, however, a necessary requirement for the formation of a stable inclusion-complex. 

There are several types of natural and synthetic molecular hosts, such as cyclodextrin and cyclophane, that are shaped to accommodate neutral and charged organic molecules in the three-dimensional cavity. The inclusion complexation by molecular hosts is driven by various weak forces like van der Waals, hydrophobic, hydrogen bonding, ion-dipole, and dipole-dipole interactions, and therefore the molecular recognition process seems much more complicated. In expanding the scope of the present theory, it is intriguing and inevitable to perform the extrather-... 

This technique is a variant of CZE. A cationic or anionic surfactant compound, such as sodium dodecylsulphate, is added to the mobile phase to form charged micelles. These small spherical species, whose core is essentially immiscible with the solution, trap neutral compounds efficiently by hydrophylic/hydrophobic affinity interactions (Fig. 8.7). Using this type of electrophoresis, optical purity analysis can be conducted by adding cyclodextrins instead of micelles to the electrolyte. This is useful for separating molecules that are not otherwise separable. Under such conditions, the enantiomers form inclusion complexes of different stability with cyclodextrin (cf. 3.6). 

The adsorption isotherms of acid azo dyes onto water soluble and insoluble polymers containing cyclodextrin were measured in aqueous solution. The adsorption of dyes on both types of polymers increased with increase in the ratio of hydrophobic components in the dyes [38], Dyes derivative of dialkylaminobenzene were used for the dyeing of nylon 6 and 6,6 in the presence of interacting / -CD [39], / -CD showed good levelling properties in the dyeing of polyamide fibers. The observed effect can be due to the formation of complexes between /Acyclodcxtri n and dyes. 

Inclusion complexing partners are classified as hosts and guests [46]. There are two types of hosts that were successfully employed in the chromatographic separation of enantiomers hosts that have a hydrophobic interior and hosts with a hydrophilic interior. The hydrophilic interior means that the cavity contains heteroatoms such as oxygen, where lone-pair electrons are able to participate in bonding to electron acceptors such as an organic cation (e.g., chiral crown ethers). In contrast, a host with a hydrophobic interior cavity is able to include hydrocarbon-rich parts of a molecule [47]. This type of host is found in the cyclodextrins. 

Pseudorotaxanes can also be obtained as a consequence of simple hydrophobic/ hydrophilic interactions. This is the case for the since long known species in which a wire-type component (9 +) threads the cavity of a-cyclodextrin 10 (Figure 3b) [9]. 

The selection of a stationary phase is extremely important in GC since it is the major controllable variable of selectivity in the separation process. Stationary phases can be non-polar, polar, or of intermediate polarity. Cyclodextrins, cyclic oligosaccharides composed of varying numbers of glucopyranose units, were found recently to be extremely useful for the separation of chiral compounds. Three types of derivatives, 5-hydroxypropyl (hydrophilic), dialkyl (hydrophobic), and trifiuoroacetyl (intermediate) have been used, each of these phases having a selected area of specificity. 

Cyclodextrins are bucketlike or conelike toroid molecules, with a rigid structure and a central cavity, the size of which varies according to the cyclodextrin type see Section 8. The internal surface of the cavity is hydrophobic and the outside of the torus is hydrophilic this is due to the arrangement of hydroxyl groups within the molecule. This arrangement permits the cyclodextrin to accommodate a guest molecule within the cavity, forming an inclusion complex. 

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