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NPURC Synthesis of Carboxy- Functionalized Calixarenes as Templates for Catalyst Deposition and Ligands for Quantum Dots Aubrey Jones, Frank DePaula, Dr. Grigoriy A. Sereda 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 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 synthesized by a known sequence of procedures 6,7 1.Synthesis of calixarenes by hydroxymethylation of tert.butylphenol. 2. Alkoxycarbomethylation. 3. Hydrolysis. OH CH 3 CH 3 C H 3 O H H + NaOH OH OH O H O H CH 3 C H 3 CH 3 CH 3 C H 3 C H 3 C H 3 CH 3 C H 3 C H 3 CH 3 CH 3 Reflux N 2 CH 3 C H 3 CH 3 CH 3 C H 3 C H 3 C H 3 CH 3 C H 3 C H 3 CH 3 CH 3 OCH 2 COOC 2 H 5 OCH 2 COOC 2 H 5 OCH 2 COOC 2 H 5 OCH 2 COOC 2 H 5 CH 3 C H 3 CH 3 CH 3 C H 3 C H 3 C H 3 CH 3 C H 3 C H 3 CH 3 CH 3 OCH 2 COOH OCH 2 COOH OCH 2 COOH OCH 2 COOH OH C H 3 CH 3 CH 3 + O H H OH C H 3 CH 3 CH 3 Xylene 8 N aO H reflux C H 3 CH 3 CH 3 8 OCH 2 COOC 2 H 5 C H 3 CH 3 CH 3 8 OCH 2 COOH 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 Conclusion • Different calixarene derivatives were synthesized and confirmed by 1 HNMR • 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 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. Synthesis of carboxylated calix-[4]-arene Synthesis of carboxylated calix-[8]-arene C H 3 CH 3 CH 3 8 OCH 2 COOH C H 3 CH 3 CH 3 4 OCH 2 COOC 2 H 5 OH C H 3 CH 3 CH 3 8 1 HNMR of Calix[8]arene 1 HNMR of Alkylated Calix[4]arene 1 HNMR of Carboxy Functionalized Calix[8]arene 1 HNMR of Calix[4]arene Quantum dots being coated by carboxy functionali zed calix[4]are ne 1
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Synthesis of Carboxy-Functionalized Calixarenes as Templates for Catalyst Deposition and Ligands for Quantum Dots. NPURC. Introduction - PowerPoint PPT Presentation
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NPURC
Synthesis of Carboxy-Functionalized Calixarenes as Templates for Catalyst
Deposition and Ligands for Quantum DotsAubrey Jones, Frank DePaula, Dr. Grigoriy A. SeredaIntroduction
• 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
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.
OH
CH3
CH3CH3
O
H H+
NaOHOH
OHOH
OH
CH3
CH3 CH3
CH3
CH3
CH3
CH3
CH3CH3
CH3
CH3
CH3
Reflux N2
CH3
CH3 CH3
CH3
CH3
CH3
CH3
CH3CH3
CH3
CH3
CH3
OCH2COOC2H
5
OCH2COOC2H5
OCH2COOC2H5
OCH2COOC2H5
CH3
CH3 CH3
CH3
CH3
CH3
CH3
CH3CH3
CH3
CH3
CH3
OCH2COOH
OCH2COOH
OCH2COOH
OCH2COOH
OH
CH3 CH3
CH3
+
O
HH
OH
CH3 CH3
CH3
Xylene8NaOH
reflux
CH3 CH3
CH3
8
OCH2COOC2H5
CH3 CH3
CH3
8
OCH2COOH
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
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
References1. Jin, Takashi, Fujii, Yamada, Nodasaka, Kinjo; “Control of the Optical Properties of Quantum Dots by Surface Coating withCalix[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), 3254. 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. Percec et.al. J. Org. Chem., 2001, 66, 2115
Synthesis of carboxylated calix-[4]-arene
Synthesis of carboxylated calix-[8]-arene
CH3 CH3
CH3
8
OCH2COOH
CH3 CH3
CH3
4
OCH2COOC2H5
OH
CH3 CH3
CH3
8
1HNMR of Calix[8]arene
1HNMR of Alkylated Calix[4]arene
1HNMR of Carboxy Functionalized Calix[8]arene1HNMR of Calix[4]arene
Quantum dots being coated by carboxy functionalized calix[4]arene1
