Cyclodextrin-solute complexation dependence

Aqueous a-cyclodextrin solutions seem to be generally applicable for TLC separation of a wide variety of substituted aromatics on polyamide thin-layer stationary sheet (13-14). In most cases, the compounds moved as distinct spots and their R, values were dependent on the concentration of the cyclodextrin in tne mobile phase. In a given family of compounds, (o-, m-, and p-nitrophenols, for example) the isomer with the largest stability constant for a-cyclodextrin complex formation had the larger value. In general, the para-substituted isomers have larger R values than the meta-isomers, which in turn have larger R values than the ortho substituted ones. 

The results reported in this work indicate that cyclodextrins chemically bonded to gel (PMHS) or incorporated in polymer matrix (PVC) appear as promising sensitive membrane for heavy ion sensors. The performances of ionic sensors are related to their aptitude to be used several times. The effect of the pH solution on the sensitivity of the sensors was also investigated for the P-CD/PMHS membrane towards Pb(Il) ions. The obtained results indicate a decrease of the membrane sensitivity going from neutral to acidified solutions. This indicate that the stabUily of the cyclodextrine complex depends on the acidity of the tested solution. 

An important advantage of the inclusion complexes of the cyclodextrins over those of other host compounds, particularly in regard to their use as models of enzyme-substrate complexes, is their ability to be formed in aqueous solution. In the case of clathrates, gas hydrates, and the inclusion complexes of such hosts as urea and deoxycholic acid, the cavity in which the guest molecule is situated is formed by the crystal lattice of the host. Thus, these inclusion complexes disintegrate when the crystal is dissolved. The cavity of the cyclodextrins, however, is a property of the size and shape of the molecule and hence it persists in solution. In fact, there is evidence that suggests that the ability of the cyclodextrins to form inclusion complexes is dependent on the presence of water. Once an inclusion complex has formed in solution, it can be crystallized however, in the solid state, additional cavities appear in the lattice, as in the case of the hosts previously mentioned, which enable the inclusion of further guest molecules. ... 

The distribution of a-, P- and y-CDs is highly dependent on the origin of biocatalyst used (See section on Cyclodextrin Glucanotransferases). Product distributions maybe altered by the addition of specific precipitants, such as aromatics and long chain alcohols 9, 20), Depending on molecular size, these precipitants preferentially complex with specific CD species and are removed from solution. 

The hetero-dimerization behavior of dye-modified -cyclodextrins with native CDs was investigated by means of absorption and induced circular dichroism spectroscopy in aqueous solution [43], Three types of azo dye-modified /i-CDs show different association behavior, depending on the positional difference and the electronic character of substituent connected to the CD unit in the dye moiety. p-Methyl Red-modified fi-CD (1), which has a 4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4 position by an amido linkage, forms an intramolecular self-complex, inserting the dye moiety in its / -CD cavity (Figure 13). 1 also associates with native a-CD by inserting the dye residue into the a-CD cavity. The association constants for such hetero-dimerization are 198 M"1 at pH 1.00 and 305 M 1 at pH 6.59, which are larger than the association constants of 1 for / -CD (43 M 1 at pH 1.00). 

Armstrong et al. developed a chromatographic technique which could be used to evaluate the stoichiometry and all relevant binding constants for most substrate-CD systems (8). This method was not dependent on a solute s spectroscopic properties, conductivity, electrochemical behavior, or solubility. This work presented theory and chromatographic evidence for multiple cyclodextrin complex formation. Previous theoretical work considered only 1 1 complex formation (9-12). A two to one complexation equation was derived by expanding on the equation first used in 1981 to describe the 1 1 complexation behavior of a solute in a pseudophase system (13.14). Using this method, it was demonstrated that closely related compounds such as structural isomers of nitroaniline could exhibit different binding behaviors (8). 

There are a variety of organic acids and bases that have protonated and unprotonated forms at different pH s. Each form of the solute can have a distinct binding constant to a cyclodextrin or micelle. Coupling these pH effects with multiple complexation behavior results in a somewhat complicated system. Solutes which have geometric cis-trans isomers as well as are pH dependent have been previously reported for 1 1 complexes (11). Sybilska et al. derived an equation which related the absorption of both neutral and anionic species on a reversed stationary phase (10) as shown in Equation 6. 

Cyclodextrins can form inclusion complexes with some drugs, modifying their physical and chemical properties. Because cyclodextrins are mainly used to increase the solubility of poorly soluble drugs, most investigations in this field focus on photostability of drugs in solution. Here, the positive effect of cyclodextrins on the photostability of colchicine (36), emetine and cephaeline (37) could be shown. However, these results show that the photoprotective effect depends on the particular cyclodextrin used. For some forms of cyclodextrin, an increase of the photodegradation rate can be obtained, as the example of molsidomine shows (13). 

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