Dendritic beta-cyclodextrin (betaCD) derivatives bearing multivalent mannosyl ligands have been prepared and assessed for their binding efficiency toward the tetrameric plant lectin concanavalin A (Con A) and a mammalian mannose/fucose specific cell surface receptor from macrophages. The synthetic strategy exploits the reactivity between isothiocyanate and amine functionalities for the high-yielding assembly via thioureido links of the various building blocks, including host, spacer, branching, and carbohydrate ligand elements. The methodology has been applied to the preparation of a series of betaCD-polymannoside scaffolds differing in the ligand valency and geometry. This series allowed us to explore: (i) The effects of the glycodendritic architecture on the binding efficiency; (ii) the mutual influence between the cyclodextrin core and the glycodendritic moieties on the molecular inclusion and lectin-binding properties; and (iii) the consequence of inclusion complex formation, using the anticancer drug docetaxel (Taxotère) as a target guest, on biological recognition. Our results confirm the high drug solubilization capability of this new type of betaCD-dendrimer construct and indicate that subtle changes in the architecture of the conjugate may have important consequences on receptor affinity. Interestingly, the host-guest interaction can be monitored to build up supramolecular dynamic glycoclusters with increased lectin affinity. Alternatively, the information obtained from the structure-lectin-binding avidity-inclusion capability studies has been put forward in the design of very efficient molecular transporters for docetaxel based on glycodendritic CD dimers.

0 . 0 0.1 0 . 2 0 . 3 0 . 4 A ( t ) -Fig. 3. Absorption at time I + dr vs absorption at time I for the photoreaction from the open to the closed photochromic form in toluene (A, , , = 496 nrn; copolyacrylate 5a with 9.4 mol % fulgimide groups).microscope observations have already revealed that irradiation of the materials with UV light leads to a higher clearing point of the meso phase. This suggests that the dihydrobenzofuran side groups (colored form) distort the parallel arrangement of the molecules in the meso phase less that the fulgimide groups. 0.1 1 2'0 4'0 6 0 ' S O '-00 t Chl -Fig. 4. Thermal stability of the colored form of the fulgimide groups in a copolymethacrylate 5 b with 2.5 mol% fulgimide content at 22 "C and 60 "C. A UV-irradiated film was used.To test the possibility of recording optical information, a film of a photochromic polymer was covered with a standard photomask and irradiated with UV light (k = 366 nm). The optically stored image of the mask could be observed with the polarizing microscope. Moreover, preliminary experiments have already shown that holographic patterns can be stored in the materials described here. The exact contribution of amplitude and phase effects is currently being investigated. Experimental Procedure1 was prepared by reaction of (E)/(Z)-2-[1-(2,5-dimethyl-3-furyl)ethylidene]-3isopropylidenesuccinic anhydride with ammonia in acetone solution [6,7]. 6-Hydroxyhexylacrylate 2a (R = H) and 6-hydroxyhexylmethacrylate 2 b (R = CH,) were synthesized as described in reference [lo]. Typical example of the procedure for 3a and 3b: 0.115 g of 1, 0.157 g of triphenylphosphane and 0.108 g of 2a were dissolved in dry THF. To this a solution of azodicarboxylate (0.108 g) in dry THF was added. A trace ofp-benzoquinone was also added to inhibit polymerization. The mixture was stirred for 14 hours in the dark. Afterwards the solvent was removed under vacuum and the product purified by flash chromatography (petrol ether: ethyl acetate 12:l). Yields: 3a 40.4% 3 b 29.3% (based on 1); oily compounds. All compounds have been characterized by IR, I3C and 'H NMR spectroscopy. 3a: 'HNMR (CDCI,, 400MHz): 6 =6.33 (m; Z-H of CH,=), 6.06 (t; H,C=CH), 5.87 (s; furan-H), 5.78 (m; E-H of CH,=), 4.11 (t; H,C-OOC), 3.55 (ti CH,-N), 2.54 ( s ; CH3-C=), 2.28 (S; 2-CH, of (CH,),C=), 2.20 ( s ; furan-5-CH3), 1.94 (s; furan-2-CH3), 1.64, 1.37 (m; N-CHI-(CHJ-CHI-OOC), 1.28 (s; E-CH, of (CH,),)C=). 3b: 'HNMR (CDCI,. 400MHz): 6 = 6.06 (m; Z-H of CH,=), 5.88 (s; furan-H), 5.52 (m; E-H of CH,=), 4.10 (ti CH,-OOC), 3.55 (ti CHI-N), 2.54 (s; CH3-C=). 2.28 (s; Z-CH3 of (CH,),C=); 2.21 (s; furan-5-CH3); 1.95 (s; furan-2-CH3); 1.91 (t; H,C=CCH,). 1.64. 1.37 (m; N-CHI-(CH,),-CH,-OOC), 1.28 (s; E-CH, ofThe mesogenic monomers 4 were prepared by standard methods [ l l , 121. The copolymers 5 were prepared by polymerization of the monomer (20-30 percent in THF solution) with 1.2 mol % of 2,2'-azohis(isobutyronitrile) at 55°C. The polymers were precipitated in methanol, purified by reprecipitation and dried under vacuu...

Self-assembled cyclodextrin (CD)-DNA nanoparticles (CDplexes) exhibiting transfection efficiencies significantly higher than PEI-based polyplexes have been prepared from homogeneous seven-fold symmetric polyaminothiourea amphiphiles constructed on a beta-cyclodextrin scaffold.