NPURC

1. Synthesis of Carboxy-Functionalized Calixarenes as Templates for Catalyst Deposition and Ligands for Quantum Dots NPURC • Introduction • 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 dots1 • 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 sensors2,3,4,5 • Conclusion • Different calixarene derivatives were synthesized and confirmed by 1HNMR • For the firs time, water soluble CdSe/ZnS QDs were prepared by coating with carboxylated tert.butylcalix[8]arene and their optical properties are being explored Aubrey Jones, Frank DePaula, Dr. Grigoriy A. Sereda • Future Work • Deposit carboxy functionalized calixarenes on metal oxide solid support and use as template to prepare vanadia catalysts5 • To explore the properties of calix[4]arene coated water soluble quantum dots with tertiary and without the tertiary butyl group attached6,7,8,9,10 Synthetic Procedures Carboxy functionalized calixarenes are synthesized by a known sequence of procedures6,7 1.Synthesis of calixarenes by hydroxymethylation of tert.butylphenol. 2. Alkoxycarbomethylation. 3. Hydrolysis. Synthesis of carboxylated calix-[8]-arene Quantum dots being coated by carboxy functionalized calix[4]arene1 1HNMR of Calix[8]arene References 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.; McKervey, M.A. Chem. Soc. Rev. 1996, 15. 3. Forster, R.J.; Cadogan, A.; Diaz, M. T.; Diamond, D.; Harris, S.; McKervey, 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), 22-29A. 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, C163-C164. 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. Percecet.al. J. Org. Chem., 2001, 66, 2115 1HNMR of Alkylated Calix[4]arene Synthesis of carboxylated calix-[4]-arene 1HNMR of Calix[4]arene 1HNMR of Carboxy Functionalized Calix[8]arene