Inclusion compounds cyclodextrin

Immobilization. The abiUty of cyclodextrins to form inclusion complexes selectively with a wide variety of guest molecules or ions is well known (1,2) (see INCLUSION COMPOUNDS). Cyclodextrins immobilized on appropriate supports are used in high performance Hquid chromatography (hplc) to separate optical isomers. Immobilization of cyclodextrin on a soHd support offers several advantages over use as a mobile-phase modifier. For example, as a mobile-phase additive, P-cyclodextrin has a relatively low solubiUty. The cost of y- or a-cyclodextrin is high. Furthermore, when employed in thin-layer chromatography (tic) and hplc, cyclodextrin mobile phases usually produce relatively poor efficiencies. 

Cavilaics include crown rnacroring inclusion compounds (coronates), cryptates, podates. cytlophane host inclusion compnunds. calixarene inclusion compounds, cyclodextrin and amylose inclusion compounds, cucurbituril inclusion compounds, molecular deft inclusion compounds, and anionic guest inclusion compounds. 

Inclusion compounds of the Cg aromatic compounds with tris((9-phenylenedioxy)cyclotriphosphazene have been used to separate the individual isomers (43—47). The Schardinger dextrins, such as alpha-cyclodextrin, beta-dextrin, and gamma-dextrin are used for clathration alpha-dextrin is particularly useful for recovering PX from a Cg aromatic mixture (48,49). PyromeUitic dianhydride (50) and beryllium oxybenzoate (51) also form complexes, and procedures for separations were developed. 

Fig. 7. Schemes of crystalline cyclodextrin inclusion compounds (a) channel type (b) cage herringbone type (c) cage brick type (58).

Cyclodextrins 289, 294 Cyclophane-arene inclusion compounds 303 Cyclopolypeptides 289 f. Cyclopropanediazonium ion 126 Cyclosporin A 289 f. 

Cyclodextrins, toroidal molecules composed of 6, 7 and 8 D-glucose units, are now commercially available at reasonable cost. They form inclusion compounds with a variety of molecules and often differentially include sulfoxide enantiomers29,30. This property has been used to partially resolve some benzyl alkyl, phenyl alkyl and p-tolyl alkyl sulfoxides. The enantiomeric purities after one inclusion process ranged from 1.1 % for t-butyl p-tolyl sulfoxide to 14.5% for benzyl r-butyl sulfoxide. Repeating the process on methyl p-tolyl sulfoxide (10) increased its enantiomeric purity from 8.1% to 11.4% four recrystallizations raised the value to 71.5%. The use of cyclodextrins in asymmetric oxidations is discussed in Section II.C.l and in the resolution of sulfmate esters in Section II.B.l. 

Cyclodextrins (CDs) are inclusion compounds formed by enzymatic decomposition of starch to the cyclic oligosaccharides containing six to eight... 

As we saw in the previous sections, inclusion compounds have many structural properties which relate them to other systems based on the hierarchy of non-bound interactions, like enzymes or enzyme-substrate complexes. As a matter of fact, most of the so-called artificial enzymes are based on well-known host molecules (e.g. P-cyclodextrin) and are designed to act partly on such bases 108>109). Most of these models, however, take advantage of the inclusion (intra-host encapsulation) phenomena. Construction of proper covalently bound model molecules is a formidable task for the synthetic chemistuo>. Therefore, any kind of advance towards such a goal is welcomed. 

Thus, despite all the work carried out on starch-iodine, the exact nature of the guest iodine atoms is still not totally resolved. Teitelbaum, Ruby and Marks 156) have examined the compound using Raman and 129I Mossbauer spectroscopy and concluded that the pentaiodide ion 1 was the major chromophore present. However work based on iodine compounds of cyclodextrins 3-134 135) has shown that a variety of polyiodide species is possible, and the starch-iodine inclusion compound could conceivably involve I2 If, I2 I- I2, or I5 species 157). The anhydrous amylose-iodine compound has recently been found to exhibit semiconductor behaviour 158). 

Matsue et al. [43] attempted to study the molecular rocket reaction in a ruthenocene-/ -cyclodextrin inclusion compound using the I00Ru y, p) "raTc reaction. They noticed a parallel relationship between chemical processes and nuclear-recoil-induced processes in the non-included ruthenocene compound, as shown in Fig. 9. In the nuclear-recoil-induced processes no dimerization can be observed because of the extremely low concentration of the product, whereas in the chemical processes dimerization is possible, as demonstrated by Apostolidis et al. [48]. When ruthenocene included in /J-cyclodextrin is irradiated with y-rays, a part of the ruthenocene molecule is converted to [TcCp2-] which escapes from the jS-cyclodextrin cavity. The [TcCp2] rocket thus produced can attack neighboring inclusion compounds so as to extract the enclosed ruthenocene molecules and abstract H or Cp (Cp cyclopentadienyl radical). This process is shown schematically in Fig. 10. 

Direct insertion probe pyrolysis mass spectrometry (DPMS) utilises a device for introducing a single sample of a solid or liquid, usually contained in a quartz or other non-reactive sample holder, into a mass spectrometer ion source. A direct insertion probe consists of a shaft having a sample holder at one end [70] the probe is inserted through a vacuum lock to place the sample holder near to the ion source of the mass spectrometer. The sample is vaporized by heat from the ion source or by heat from a separate heater that surrounds the sample holder. Sample molecules are evaporated into the ion source where they are then ionized as gas-phase molecules. In a recent study, Uyar et al. [74] used such a device for studying the thermal stability of coalesced polymers of polycarbonate, PMMA and polylvinyl acetate) (PVAc) [75] and their binary and ternary blends [74] obtained from their preparation as inclusion compounds in cyclodextrins. 

Cyclobuxine-D, 2 104 P-Cyclocitral, 24 570 Cyclocitronellene acetate, 24 488 a-Cyclocitrylidenebutanone, 24 565 Cyclodehydrating agents, 20 276 Cyclodemol, 24 488 P-Cyclodextrin, 4 715 Cyclodextrin glucanotransferase, 24 48 Cyclodextrin glycosyltransferase, 4 715 Cyclodextrin inclusions, 74 183 Cyclodextrin inclusion compounds, 74 166-167... 

Inclusion complexation, 77 552-553 Inclusion compounds, 74 159-190, 170-182 amylose, 74 168 anionic guest, 74 170 cailixarene, 74 165-166 categories of, 74 160 crown macroring, 74 160-161 cucurbituril, 74 168-169 cyclodextrin, 74 166-167... 

Impulse response technique for measuring catalytic absorption, 19 243 Inactive additives and alloys, 32 190-191 Inclusion compounds, 32 418,420-426 cyclodextrin, 32 428-436, 462 unsubstituted compounds, 32 422-426... 

YC Guillaume, E Peyrin. Symmetry breaking during the formation of beta-cyclodextrin-imidazole inclusion compounds. Capillary electrophoresis study. Anal Chem 71 2046-2052, 1999. 

Reviews, 1998, 98, (5) covers several aspects of CDs chemistry while the books listed below mainly present their applications (b) Comprehensive Supramolecular Chemistry, v. 3, J. Szejtli, Ed., Kluwer Academic Publishers, Elsevier, Oxford, 1996 J. Szejtli, Cyclodextrin Technology, Kluwer, Dordrecht, 1988 (c) Cyclodextrins and Their Industrial Uses, D. Duchene, Ed., Edition du Sante, Paris, France, 1987 New Trends in Cyclodextrins and Derivatives, D. Duchene, Ed., Edition du Sante, Paris, France. 1991 (d) W. Saenger, Angew. Chem. Int. Ed. Engl., 1980, 19, 344 W. Saenger, in Inclusion Compounds, J. T. Atwood. J. E. D. Davies, D. D. MacNicol, Eds., v. 2, Academic Press. London, 1984, p. 231 K. Harata, ibid., v. 5, 1991, p. 311. 

A benzoyl benzoate substituent in 6-position of p-cyclodcxtrine can act as redox catalyst for the cathodic cleavage of a benzylester-cyclodextrine inclusion compound. Thus, a simple redox enzyme model was formed... 

Figure 7. Schematic representation of the packing arrangement in cyclodextrin complexes (a) channel type, (b) cage or herringbone type, and (c) brick type. (Reproduced with permission from W. Sanger in Inclusion Compounds, Vol. 2, J. L. Atwood, J. E. D. Davies, and D. D. MacNicol, Eds., Academic Press, New York, 1984, p. 231.)...

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