Amphiphilic cyclodextrins

Selective inclusion of naphthalene derivatives by monolayers of amphiphilic cyclodextrins at the air/water interface [23]. 

Figure 11. Amphiphilic cyclodextrins (Host molecules) and naphthalene derivatives (Guests).

Ferro, S., Jori, G., Sortino, S., Stancanelli, R., Nikolov, P., Tongon, G., Ricchelli, F., and Mazzaglia, A. (2009). Inclusion of 5-[4-(l-dodecanoylpyridinium)-10,15,20-triphenylpor-phine in supramolecular aggregates of cationic amphiphilic cyclodextrines Physic-chemical characterization of the complexes and strengthening of the antimicrobial photosensitizing activity. Biomacromolecules 10(9), 2592-2600. 

The incorporation of such compounds into mixed Langmuir-Blodgett films built from a fatty acid (see 97) [8.92] or from an amphiphilic cyclodextrin [8.93] produces oriented arrangfements presenting marked NLO features. 

The same push-pull carotenoid can also be introduced into LB multilayers built from 1/1 mixtures with an amphiphilic cyclodextrin. The polyenic chains are again perpendicular to the substrate and some carotenoid molecules do not aggregate, but are isolated by the host substance (21). 

Amphiphilic Cyclodextrins Nanoparticles have been obtained spontaneously from modified CDs of amphiphilic structure since the last decade. This approach differs from the previously discussed approaches in that amphiphilic CDs do not require the presence of another polymer or macromolecule or even surfactants. 

Nonionic Amphiphilic Cyclodextrins Nonionic amphiphilic CDs are obtained by grafting aliphatic chains of different length on the primary and/or secondary face of the CD glucopyranose unit. Different derivatives depicted in Figure 5 are named after their structure ... 

Anionic Amphiphilic Cyclodextrins Anionic amphiphilic CDs possess a sulfate group in their structure to render an anionic nature to the molecule. An efficient regiospecific synthetic route to obtain acyl-sulfated P-CDs was introduced in which the upper rim is functionalized with sulfates and the lower rim with fatty acid esters [69], These derivatives were able to form aggregates in aqueous medium. 

The authors wish to thank the TUBITAKThrkish Council of Scientific and Technical Research, projects SBAG-CNRS-3 and SBAG-CD-66, and the Hacettepe University Research Fund, project 0202301005, for financial support of the amphiphilic cyclodextrin research carried out by our group at Hacettepe University, Faculty of Pharmacy, Department of Pharmaceutical Technology. 

Munoz, M., Deschenaux, R., and Coleman, A. W. (1999), Observation of microscopic patterning at the air/water interface by mixtures of amphiphilic cyclodextrins—A comparison isotherm and Brewster angle microscopy study, /. Phys. Org. Chem., 12, 364-369. 

Zhang, P, Ling, C. C., Coleman, A. W., Parrot-Lopez, H., and Galons, H. (1991), Formation of amphiphilic cyclodextrins via hydrophobic esterification at the secondary hydroxyl face, Tetrahedron Lett., 32, 2769-2770. 

Memisoglu, E., Charon, D., Duchene, D., and Hmcal, A. A. (1999), Synthesis of per(2,3-di-0-hexanoyl)-P-cyclodextrin and characterization amphiphilic cyclodextrins nanoparticles, in Torres-Labandeira, J., and Vila-Jato, J., Eds., Proceedings of the 9th International Symposium on Cyclodextrins, Kluwer Academic, Dordrecht, pp. 622-624. 

Lesieur, S., Charon, D., Lesieur, P., Ringerd-Lefebvre, C., Muguet, V., Duchene, D., and Wouessidjewe, D. (2000), Phase behaviour of fully-hydrated DMPC-amphiphilic cyclodextrin systems, Chem. Phys. Lip., 10,127-144. 

Alexandre, S., Coleman, A. W., Kasselouri, A., and Valleton, J. M. (1996), Scanning force microscopy investigation of amphiphilic cyclodextrin Langmuir-Blodgett films, Thin Solid Films, 284-285, 765-768. 

Mazzaglia, A., Angelini, N., Darcy, R., Donohue, R., Lombardo, D., Micali, N., Sciortino, M.T., Villari,V.,and Scolaro,L.M. (2003), Novel heterotropic colloids of anionic porphyrins entangled in cationic amphiphilic cyclodextrins Spectroscopic investigation and intracellular delivery, Chem. Eur. 1,9,5762-5769. 

Matsumoto, M., Matsuzawa, Y., Noguchi, S., Sakai, H., and Abe, M. (2004), Structure of Langmuir-Blodgett films of amphiphilic cyclodextrin and water-soluble benzophenone, Mol. Cryst. Liq. Cryst., 425,197-204. 

Lemos-Senna, E., Wouessidjewe, D., Lesieur, S., Puisieux,F., Couarrazze, G., and Duchene, D. (1998), Evaluation of the hydrophobic drug loading characteristics in nanoprecipitated amphiphilic cyclodextrins nanospheres, Pharm. Dev. Technol, 3,1-10. 

Memisoglu-Bilensoy, E., Dogan, A. L., and Hincal, A. A. (2006), Cytotoxic evaluation of injectable amphiphilic cyclodextrin nanoparticles on fibroblasts and polymorphonuclear cells Surfactant effect,/. Pharm. Pharmacol, 58(5), 585-589. 

Sortino, S., Mazzagha, A., Scolaro, L. M., Merlo, F. M., Volveri, V., and Sciortino, M. T. (2006), Nanoparticles of cationic amphiphilic cyclodextrins entangling anionic porphyrins as carrier-sensitizer system in photodynamic cancer therapy, Biomaterials, 27, 4256-4265. 

The self-assembly properties of amphiphillic cyclodextrins esteiified at the 2- and 3-positions with lipophillic groups were examined in py-rfs and thf-rfs with the aid of Eu(fod)3. In py-fi/s the cyclodextrin molecules dimerized as indicated in Figure 2a, and the europium ion caused shifts and broadening of the primary methylene resonances. In iM-di, the cyclodextrin associates had the alignment shown in Figure 2b, and the europium shifted the methyl and methylene resonances of the fatty acyl groups". ... 

Dubes, A. Parrot-Lopez, H. Abdelwahed, W. Degobert, G. Fessi, H. Shahgaldian, P. Coleman, A.W. Scanning electron microscopy and atomic force microscopy imaging of solid lipid nanoparticles derived from amphiphilic cyclodextrins. Eur. J. Pharm. Biopharm 2003, 55 (3), 279-282. 

Other Amphiphilic Cyclodextrins Other amphiphilic CyDs as well as cholesteryl-CyDs can form lipidic vesicles. These vesicles can be liposomes or vesicles delimited by the bilayer of amphiphilic molecules, sometimes incorrectly named liposomes . 

In this brief review we will describe some important encapsulation processes by vesicular aggregates. Encapsulation will be broadly interpreted. Apart from solubilization in the aqueous pool inside the vesicle, the term will also encompass binding of solubilizates to all binding sites available in the vesicular system. We will not discuss bilayer vesicles formed from amphiphiles further functionalized by receptor molecules, such as amphiphilic cyclodextrins. ... 

Novel amphiphilic cyclodextrins have been prepared by grafting a phospholipid on a modified cyclodextrin The detergent properties have been evaluated and the aggregation process in water characterised by light scattering, DSC and P NMR. A proton NMR study of an a-cyclodextrin inclusion of short chain surfactants and the study of C chemical shift surfaces in the study of carbohydrate conformation and application to cyclodextrins in the solid state and in solution were reported. 

Amphiphilic cyclodextrins 56 have been synthesized in high yields in one step from the corresponding bromides 55. In a similar preparation of peracetylated heptakis [6-S-(2,3-dihydroxypropyl)-6-thio]-P-cyclodextrin (58), the heptakis iodide 57 was used as precursor. Oxidation with MCPBA furnished heptakis sulfone 59. Hemithiocyclodextrins (cyclodextrins in which half of the inter-glycosidic oxygen atoms are replaced by sulfur atoms) and hemithiocellodextrins have been obtained in yields of ca. 10 % by exposure of 4-thio-a-maltosyl fluoride to cyclodextringlycosyltransferases and 4-thio-P-cellobiosyl fluoride to cellu-lases, respectively. 

A common picture emerged from these studies the amphiphilic cyclodextrin acts as a host, wrapping the hydrophobic substrate and transferring it into the water phase, where the reaction occurs. The stability constant of the new host-guest complex is lower, and the product is then released into the organic phase (Fig. 5). 

Cyclodextrin polyplexes, which are called CDplexes, were prepared from polycationic thiolated amphiphilic cyclodextrin and DNA for gene delivery (see Figure ll.lC). CDplexes also can be functionalized for cellular targeting, nuclear localization and visualization purposes. ... 

Key words Spread monolayers amphiphilic cyclodextrin - poly (ethylene oxide) lipid - dynamic surface pressure - interfadal miscibility... 

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