Spectroscopic and Thermal Characterization of the Host-Guest Interactions between α-, β-, and γ-cyclodextrins and vanadocene dichloride.

Host-guest interactions between α-, β-, and γ-cyclodextrins and vanadocene dichloride (Cp(2)VCl(2)) have been investigated by a combination of thermogravimetric analysis, differential scanning calorimeters, PXRD and solid state and solution EPR spectroscopy. The solid state results demonstrated that only β- and γ-cyclodextrins form 1:1 inclusion complexes, while α-cyclodextrin does not form an inclusion complex with Cp(2)VCl(2). The β- and γ-CD-Cp(2)VCl(2) inclusion complexes exhibited anisotropic electron-(51)V (I = 7/2) hyperfine coupling constants whereas the α-CD- Cp(2)VCl(2) system showed only an asymmetric peak with no anisotropic hyperfine constant. On the other hand, solution EPR spectroscopy showed that α-CD may be involved in weak host-guest interactions in equilibrium with free vanadocene species.

[1]  S. Braga,et al.  A Combined Theoretical−Experimental Study of the Inclusion of Niobocene Dichloride in Native and Permethylated β-Cyclodextrins , 2007 .

[2]  E. Monflier,et al.  Cyclodextrins as supramolecular hosts for organometallic complexes. , 2006, Chemical reviews.

[3]  J. Teixeira-Dias,et al.  Inclusion of molybdenocene dichloride (Cp2MoCl2) in 2-hydroxypropyl- and trimethyl-β-cyclodextrin: Structural and biological properties , 2005 .

[4]  J. Holubová,et al.  Inclusion compounds of cystostatic active (C5H5)2VCl2 and (CH3C5H4)2VCl2 with α-, β- and γ-cyclodextrines: Synthesis, EPR study and microbiological behavior toward Escherichia coli , 2005 .

[5]  W. Lo,et al.  Structure and Bonding , 2005 .

[6]  E. D. Valle,et al.  Cyclodextrins and their uses: a review , 2004 .

[7]  H. Köpf,et al.  Tumor inhibition by titanocene dichloride: First clues to the mechanism of action , 1980, Naturwissenschaften.

[8]  P. Köpf-Maier,et al.  Tumorhemmung durch Metallocene: Wirkung von Titanocen-, Zirconocen- und Hafnocen-dichlorid gegenüber Ehrlich-Aszites-Tumor der Maus , 2004, Journal of Cancer Research and Clinical Oncology.

[9]  P. Köpf-Maier,et al.  Complexes of metals other than platinum as antitumour agents , 2004, European Journal of Clinical Pharmacology.

[10]  E. Meléndez Titanium complexes in cancer treatment. , 2002, Critical reviews in oncology/hematology.

[11]  J. Teixeira-Dias,et al.  Experimental and theoretical study of the interaction of molybdenocene dichloride (Cp2MoCl2) with β-cyclodextrin , 2001 .

[12]  J. Teixeira-Dias,et al.  Interactions of Cationic and Neutral Molybdenum Complexes with β-Cyclodextrin Host Molecules , 2001 .

[13]  M. Harding,et al.  Antitumour metallocenes: structure-activity studies and interactions with biomolecules. , 2000, Current medicinal chemistry.

[14]  J. Teixeira-Dias,et al.  Modification of β-Cyclodextrin with Ferrocenyl Groups by Ring Opening of an Encapsulated [1]Ferrocenophane , 2000 .

[15]  J. Teixeira-Dias,et al.  Encapsulation of half-sandwich complexes of molybdenum with β-cyclodextrin , 2000 .

[16]  I. Turel,et al.  The Interactions of Titanocene Dihalides with α-, β- and γ-cyclodextrin Host Molecules , 1999 .

[17]  D. Kerr,et al.  Phase I trial of weekly scheduling and pharmacokinetics of titanocene dichloride in patients with advanced cancer. , 1998, Journal of clinical oncology : official journal of the American Society of Clinical Oncology.

[18]  C. Villena-Heinsen,et al.  Human ovarian cancer xenografts in nude mice: chemotherapy trials with paclitaxel, cisplatin, vinorelbine and titanocene dichloride , 1998, Anti-cancer drugs.

[19]  R. Rossetti,et al.  Vibrational Study of (η5-Cyclopentadienyl)metal Complexes , 1997 .

[20]  P. Andreotti,et al.  In vitro activity of titanocenedichloride versus cisplatin in four ovarian carcinoma cell lines evaluated by a microtiter plate ATP bioluminescence assay , 1995, Anti-cancer drugs.

[21]  S. Fricker Metal Compounds in Cancer Therapy , 1994, Springer Netherlands.

[22]  M. Kanatzidis,et al.  Metallocene Antitumor Agents. Solution and Solid-State Molybdenocene Coordination Chemistry of DNA Constituents , 1991 .

[23]  A. Harada,et al.  X-Ray structure of the α-cyclodextrin–ferrocene (2 : 1) inclusion compound , 1990 .

[24]  H. Köpf,et al.  Transition and main-group metal cyclopentadienyl complexes: Preclinical studies on a series of antitumor agents of different structural type , 1988 .

[25]  P. Koepf-Maier,et al.  Non-platinum group metal antitumor agents. History, current status, and perspectives , 1987 .

[26]  T. Marks,et al.  Aqueous coordination chemistry of vanadocene dichloride with nucleotides and phosphoesters. Mechanistic implications for a new class of antitumor agents , 1986 .

[27]  T. Marks,et al.  Hydrolysis chemistry of the metallocene dichlorides M(.eta.5-C5H5)2Cl2, M = titanium, vanadium, or zirconium. Aqueous kinetics, equilibria, and mechanistic implications for a new class of antitumor agents , 1985 .

[28]  T. Marks,et al.  Hydrolysis chemistry of the metallocene dichlorides M(η5-C5H5)2Cl2, M=Ti, V, Zr. Aqueous kinetics, equilibria, and mechanistic implications for a new class of antitumor agents , 1985 .

[29]  A. Harada,et al.  Preparation and properties of cyclodextrin inclusion compounds of organometallic complexes. Ferrocene inclusion compounds , 1984 .

[30]  H. Köpf,et al.  Tumor inhibition by metallocenes: Antitumor activity of niobocene and tungstocene dichlorides , 1980 .

[31]  P. Köpf-Maier,et al.  Molybdocen-dichlorid als Antitumor-Agens / Molybdocene Dichloride as an Antitumor Agent , 1979 .

[32]  H. Köpf,et al.  Titanocene dichloride--the first metallocene with cancerostatic activity. , 1979, Angewandte Chemie.

[33]  P. Köpf-Maier,et al.  Vanadocen-dichlorid - ein weiteres Antitumor-Agens aus der Metallocenreihe / Vanadocene Dichloride - Another Antitumor Agent from the Metallocene Series , 1979 .

[34]  G. Wilkinson,et al.  Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta , 1954 .