Introduction Synthesis of CarboxyFunctionalized Calixarenes as Templates for

Introduction Synthesis of Carboxy-Functionalized Calixarenes as Templates for Catalyst Deposition and Ligands for Quantum Dots Aubrey Jones, Frank De. Paula, Dr. Grigoriy A. Sereda • Calix-[8]-arene and calix-[4]-arene are being synthesized for the deposition of vanadia on metal oxide solid supports (Silica, Alumina, Titania) and carboxylated calixarenes are being used as ligands to produce water soluble quantum dots 1 • Calixarenes are cyclic oligomers characterized by having basket-like structures which entails that they have many tunable features. • Other than what calixarenes are used for in this particular field of research, they are also used as chiral recognition devices, optical sensors, and electrochemical sensors 2, 3, 4, 5 Synthetic Procedures Carboxy functionalized calixarenes are 6, 7 synthesized by a known sequence of procedures 1. Synthesis of calixarenes by hydroxymethylation of tert. butylphenol. 2. Alkoxycarbomethylation. 3. Hydrolysis. NPURC Conclusion • Different calixarene derivatives were synthesized and confirmed by 1 HNMR • For the firs time, water soluble Cd. Se/Zn. S QDs were prepared by coating with carboxylated tert. butylcalix[8]arene and their optical properties are being explored Future Work • Deposit carboxy functionalized calixarenes on metal oxide solid support and use as template to prepare vanadia catalysts 5 • To explore the properties of calix[4]arene coated water soluble quantum dots with tertiary and without the tertiary butyl group attached 6, 7, 8, 9, 10 Synthesis of carboxylated calix-[8]-arene 1 HNMR Quantum dots being coated by carboxy functionalized calix[4]arene 1 of Calix[8]arene References 1 HNMR of Alkylated Calix[4]arene 1 HNMR of Carboxy Functionalized Calix[8]arene Synthesis of carboxylated calix-[4]-arene 1 HNMR of Calix[4]arene 1. Jin, Takashi, Fujii, Yamada, Nodasaka, Kinjo; “Control of the Optical Properties of Quantum Dots by Surface Coating with Calix[n]arene Carboxylic Acids, ” 2. Diamond, D. ; Mc. Kervey, M. A. Chem. Soc. Rev. 1996, 15. 3. Forster, R. J. ; Cadogan, A. ; Diaz, M. T. ; Diamond, D. ; Harris, S. ; Mc. Kervey, M. A. , Calixarenes as active agents for chemical sensors, Sensors and Actuators B: Chemical 1991, 4(3 -4), 325 4. Diamond, D. ; Nolan, K. , Calixarenes: designer ligands for chemical sensors, Anal. Chem. 2001, 73(1), 22 -29 A. 5. Cadogan, F. ; Nolan, K. ; Diamond, D. In Calixarenes 2001 Asfari, Z. ; Bohmer, V. ; Harrowfield, J. ; Vicens, J. , Eds; Kluwer Academic Press: Dordrecht, The Netherlands, 2001; Ch. 34, pp 627 -641. 6. Tucker, D. S. Gamma-to Alpha Transformation in Spherical Aluminum Oxide Powders. J. Am. Ceram. Soc. 1985, 68, 7, C 163 -C 164. 7. Arduini, A. ; Pochini, A. ; Raverberi, S. ; Ungaro, R. J. Chem. Soc. Chem. Commun. 1984, 981 -982. 8. Chang, S. -K. ; Cho, I. J. Chem. Soc. Perkin Trans. 1. 1986, 211 -214. 9. Qu, L. ; Peng, X. J. Am. Chem. Soc. 2002, 124, 2049 -2055. 10. Hines, M. A. ; Guyot-Sionnest, P. J. Phys. Chem. 1996, 100, 468 -471. 11. Dabbousi, B. O. ; Rodriguez-Viejo, J. ; Mikulec, F. V. ; Heine, J. R. ; Mattoussi, H. ; Ober, R. ; Jensen, K. F. ; Bawendi, M. G. J. Phys. Chem. B. 1997, 101, 9463 -9475. 12. Percec et. al. J. Org. Chem. , 2001, 66, 2115