Laboratory of Structural & Supramolecular Chemistry

Research Projects


 

A. Cyclodextrin Inclusion Complexes: crystalline state and solution structures and properties

                                                 CD               guest                CD dimer complex       layer organisation

CD-packing

                                    CH packing                IN packing                 CB packing                   SC packing

 

 

Figure 1. Schematic view of the βCD (pink) dimer formation upon inclusion of a guest molecule (blue). Organisation of the dimers into 2-D layers. Packing of the layers into four distinct modes: (a) Channel (CH), the guest in the cavity is shielded from the aqueous environment. (b) Chessboard (CB), the guest end-groups emerging from the primary sides of the dimer are exposed to the aqueous environment. (c)  Intermediate (IN) a case in-between the CH and CB modes, adjacent layers are parallel, but the dimer’s 7-fold axis forms an angle of about 20o with the stacking axis. Consequently, dimers are far from exactly aligned, thus a breaking of the channel is observed that leaves parts of the guests free to interact with hydroxy groups of adjacent hosts, as well as with water molecules. (d) Screw Channel (SC), where although the lateral displacement between two consecutive βCD dimers along the channel is only 2.7Å, as in the CH mode, the dimer’s 7-fold axis forms an approximately angle of 10o with the stacking axis but the 2-D layers are related by a 2-fold screw axis and they are not parallel therefore, the guests interact with water molecules and hydroxy groups of adjacent hosts channels.

 

 

References A. Cyclodextrin Inclusion Complexes: crystalline state and solution structures and properties

 

1. D. Mentzafos, I. M. Mavridis, G. Le Bas and G.Tsoucaris   The Crystal Structure of the 4-tert-Butylbenzyl Alkohol β -Cyclodextrin Complex. Common Features in the Geometry of the β-cyclodextrin Dimeric Complexes”  Acta Crystallogr. 1991, B47, 746-757.

2.  I. M. Mavridis, E. Hadjoudis and G. Tsoucaris  The Crystal Structure of the Inclusion Complex of Cyclomaltoheptaose (β -cyclodextrin) with 3,3-Dimethylbutylamine”  Carbohydr. Res. 1991 220, 11-21.

3.  I. M. Mavridis, E. Hadjoudis  “The Crystal Structure of the Inclusion Complex of Cyclomaltoheptaose (β -cyclodextrin) with 4-tert-Butyltoluene”  Carbohydr. Res. 1992 229, 1-15.

4. A. Rontoyanni, I. M. Mavridis, E. Hadjoudis, A. J. M. Duisenberg  The Crystal Structure of the Inclusion Complex of Cyclomaltoheptaose with 4-tert-Butylbenzoic acid” Carbohydr. Res. 1994, 252, 19-32.

5.       “Organization of Long Aliphatic Monocarboxylic Acids in β-Cyclodextrin Channels. Crystal Structures of the Inclusion Complexes of Tridecanoic Acid and (Z)-tetradecenoic Acid in β-Cyclodextrin”, S. Makedonopoulou, I. M. Mavridis, K. Yannakopoulou, J. Papaioannou, J. Chem. Soc. Chem. Commun. 1998, 2133-2134.

6. S. Makedonopoulou, A. Tulinsky, I. M. Mavridis  “The Dimeric Complex of β-cyclodextrin with 1,13-tridecanedioic acid” Supramol. Chem. 1999, 11, 73-81.

7. Α. Rontoyianni, I. M. Mavridis  Dimeric Complex of Alpha-cyclodextrin with 1,12-Diaminododecane. Comparison with other Alpha Cyclodextrin Dimeric Complexes” Supramol. Chem. 1999, 10, 213-218.

8. S. Makedonopoulou, I. M. Mavridis  “Structure of the Inclusion Complex of β-Cyclodextrin with 1,12-Dodecanodioic Acid using Synchrotron Radiation Data. A Detailed dimeric β-Cyclodextrin Structure” Acta Crystallogr. 2000, B56, 322-331.

9. S. Makedonopoulou, J. Papaioannou, I. Argyroglou, I. M. Mavridis  “Crystal Structure of the Inclusion Complex of β-Cyclodextrin with the Aliphatic monoacids Tridecanoic Acid and (Z)-Tetradecenoic Acid. Formation of [3]Pseudorotaxanes” J. Inclus. Phenom. Macrocycl. Chem. 2000, 36, 191-215.

10. S. Makedonopoulou, I. M. Mavridis “The dimeric complex of beta cyclodextrin with 1,14-tetradecanedioic acid. Comparison with related complexes” Carbohydr. Res. 2001, 335, 213-220.

11. I. M. Mavridis  “Influence of the Guest on the Packing of Dimeric β-Cyclodextrin Complexes”, in Current Challenges on Large Supramolecular Assemblies, Ed. G.Tsoucaris NATO ARW, Kluwer Acad. Publ., 1999 pp 393-403.

12.   “Molecular structures of the inclusion complexes β-Cyclodextrin/1,2-bis(4-aminophenyl)ethane and  β-Cyclodextrin/4,4΄-diaminobiphenyl. Packing of dimeric β-Cyclodextrin inclusion complexes”

13.  S. D. Chatziefthimiou, K. Yannakopoulou, I. M. Mavridis  β-Cyclodextrin trimers enclosing an unusual organization of guest: The inclusion complex β-Cyclodextrin/4-pyridinealdazine” Cryst. Eng. Comm. 2007, 9, 976-979.

14.  Κ. Eliadou, K. Yannakopoulou, A. Rontoyianni, I. M. Mavridis  NMR Detection of Simultaneous Formation of [2]- and [3]Pseudorotaxanes in Aqueous Solution between α-Cyclodextrin and Linear Aliphatic α,ω-Aminoacids, an α,ω-Diamine and an α,ω-Diacid of Similar Length, and Comparison with The Solid State Structures” J. Org. Chem. 1999, 64, 6217-6226.

15.  A. Tsortos, K. Yannakopoulou, K. Eliadou, I.M. Mavridis and G. Nounesis  “Partial Thermal Dethreading of [3]pseudorotaxanes of α-Cyclodextrin with Linear Aliphatic α,ω-Aminoacids in Aqueous Solution” J. Phys. Chem. 2001, B105, 2664-2667.

16.  N. Mourtzis, G. Cordoyiannis, G. Nounesis, K. Yannakopoulou Rotaxanation of Congo Red into γ-Cyclodextrin. Solution Structures and Thermodynamic Parameters of 1:1 and 2:2 Adducts, as Obtained from NMR Spectroscopy and Microcalorimetry”   Supramolecular Chem., 2003, 15, 639-649.

17. K. Yannakopoulou and I. M. Mavridis  “Threading of long end-functionalised organic molecules into cyclodextrins: Structural analysis in aqueous solution by NMR spectroscopy and in the solid state by X-ray crystallography” Current Org. Chem. 2004, 8, 25-34.

18.  K. Yannakopoulou, and I. M. Mavridis  Rotaxane and Catenane Structures Involving Cyclodextrins  invited chapter in the Handbook "Cyclodextrins and their Complexes. Chemistry, Analytical Methods and Applications", H. Dodziuk, Ed., p. 356-369, ISBN 3-527-31280-3 - Wiley-VCH, Weinheim, 2006.

19. K. Fotiadou, A. Thanassoulas, G. Nounesis, K. Yannakopoulou “Cooperative Heterodimer Formation Between Per-Guadinylated and Carboxylated or Phoshporylated Cyclodextrins in DMSO and DMSO-Water Studied by NMR Spectroscopy and Microcalorimetry” Supramol. Chem., 2011, 23, 493-500.

20.   A. Botsi, K. Yannakopoulou, E. Hadjoudis and B. Perly “NMR Differentiation of Enantiomeric (+)- and (-)-α-Pinene via Complexation with Cyclodextrins in Water" J. Chem. Soc. Chem. Commun. 1993, 1085.

21. A. Botsi, K. Yannakopoulou, E. Hadjoudis  “Inclusion Complexes of Cyclomaltoheptaose  and its Methylated Derivatives with the Main Components of the Pheromone of the Olive Fruit Fly" Carbohydr. Res. 1993, 241, 37.

22. I. M. Mavridis, D. Mentzafos and H. Schenk "Crystal Structure of the Heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin Complex with Ethyldodecanoate Ester" Carbohydr. Res. 1994, 253, 39-50.

23.  A. Botsi, K. Yannakopoulou, B. Perly and E. Hadjoudis  “Positive or Adverse Effects of Methylation on the Inclusion Behaviour of Cyclodextrins. A Comparative  NMR Study Using Pheromone Constituents of the Olive Fruit Fly" J. Org. Chem., 1995, 60, 4017.

24.  A. Botsi, K. Yannakopoulou, B. Perly and E. Hadjoudis  “Structural Aspects of Permethylated Cyclodextrins and Comparison to their Parent Oligosaccharides as Derived from Unequivocally Assigned 1H and 13C NMR Spectra in Aqueous Solutions" Magn. Reson. Chem. 1996, 34, 419-423.

25.   A. Botsi, K. Yannakopoulou, E. Hadjoudis, and J. Waite “AM1 Calculations on Inclusion Complexes of Cyclomaltoheptaose with 1,7-Dioxaspiro[5.5]undecane and Nonanal, and Comparison with Experimental Results" Carbohydr. Res., 1996, 283, 1-16.

26. K. Yannakopoulou, J. A. Ripmeester, I. M. Mavridis Controlled Release of the Prays Oleae Pheromone, as a Consequence of Supramolecular Structure: Study of the Z-7-Tetradecenal/β-Cyclodextrin Complex in the Solid state and in Solution.” J. Chem. Soc. Perkin 2, 2002, 1639-1644

27.   D. Mentzafos, I. M. Mavridis  β -Cyclodextrin (Z)-9-Dodecen-1-ol 2:1 Complex” Acta Crystallogr. 1996, C52, 1220-1223.

28.  A. Kokkinou, K. Yannakopoulou, I.M. Mavridis, D. Mentzafos  “Inclusion Compounds of Plant Growth Regulators in Cyclodextrins. Part II. Structure of the Complex of β-Cyclodextrin with β-Naphthyloxyacetic acid in solid state and in aqueous solution” Carbohydr.Res. 2001,332, 85-94.

29.   V. Mazomenos, I M. Mavridis Eur. Patent No 92 401 709.8, 1992; US Pat. No  US00650160A, 1997.

30.  K. Yannakopoulou, D. Mentzafos, I. M. Mavridis and K. Dandika  “Chiral Recognition of (R)-(_)-1,7-Dioxaspiro[5.5]undecane by Hexakis(2,3,6-tri-O-methyl)-α-Cyclodextrin” Angew. Chem. Int. Ed. Engl. 1996 35, 2480-2482.

31.   S. Makedonopoulou, K. Yannakopoulou, D. Mentzafos, V. Lamzin,  A. Popov, and I. M. Mavridis “Non-covalent interactions in the crystallization of enantiomers of 1,7-dioxaspiro[5.5]undecane (olive fly sex pheromone) by enantiospecific cyclodextrin hosts, hexakis(2,3,6-tri-O-methyl)-α-cyclodextrin and heptakis(2,36-tri-O-methyl)-β-cyclodextrin”, Acta Crystallogr. 2001, B57, 399-409.

32.  D. Zouvelekis, K.  Yannakopoulou, A. Antoniadou-Vyza, I.M. Mavridis "The Self-Association of the Drug Acemetacin and its Intermolecular Interactions and Stability with β-Cyclodextrin in Aqueous Solution. An NMR and HPLC Study", Carbohydr. Res.,  2002, 337, 1387-1395.

33.   D. Maffeo, L. Leondiadis, I. M. Mavridis, K. Yannakopoulou “Positive Effect of Natural and Negatively Charged Cyclodextrins on the Stabilization of Penicillins towards β-Lactamase Degradation due to Inclusion and External Guest-Host Association. An NMR and MS Study” , Org. Biomol. Chem. 2006, 4, 1297 – 1304.

34.  A. Paulidou, D. Maffeo, K. Yannakopoulou, I M. Mavridis “Crystal structure of the inclusion complex of the antibacterial agent triclosan in β-cyclodextrin and NMR study of its molecular encapsulation in positively and negatively charged cyclodextrins” Carbohydr. Res. 2008 343, 2634-2640.

35. A. Paulidou, D. Maffeo, K. Yannakopoulou, I.M. Mavridis Similar modes of inclusion in complexes of β-cyclodextrin with sulfonylurea hypoglycemic drugs” Cryst. Eng. Comm. 2010,12, 517-525.

36. C. Aggelidou,  I. M. Mavridis, K. Yannakopoulou “Binding of nucleotides and nucleosides to per(6-guanidino-6-deoxy)-cyclodextrins in solution”, Eur. J. Org. Chem. 2009, 2299-2305.

 

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