Abstract
Solid-phase PAMAM dendrimer was synthesized by the repetitive addition of a branching unit to silica gel. All synthesis steps were monitored by infrared spectroscopy to investigate the reaction rate. Based on the measurements of infrared spectra, which showed the ester group varied as a function of reaction time, a reaction kinetics model was proposed and simulated. FT-IR and TGA measurements suggested that a ‘cross-linking’ reaction occurred in amidation process and generated structural defects, which decreased the grafted amount of dendrimer on silica gel. In addition, the analysis of reaction rate constants indicated that due to the formation of an intermediate, Michael addition of methyl acrylate to diamine was probably hindered by steric crowding.
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Beezer, A. E., King, A. S.H., Martin, I.K., Mitchel, J.C., Twyman, L. J. and Wain, C. F., “Dendrimers as Potential Drug Carriers; Encapsulation of Acidic Hydrophobes Within Water Soluble PAMAM Derivatives,”Tetrahedron,59(22), 3873 (2003).
Bertorelle, F., Lavabre, D. and Fery-Forgues, S., “Dendrimer-tuned Formation of Luminescent Organic Microcrystals,”J. Am. Chem. Soc.,125(20), 6244 (2003).
Bourque, S. C., Alper, H., Manzer, L. E. and Arya, P., “Hydroformylation Reactions Using Recyclable Rhodium-complexed Dendrimers on Silica,”J. Am. Chem. Soc.,122(5), 956 (2000).
Bourque, S. C., Maltais, F., Xiao, W. J., Tardif, O., Alper, H., Arya, P. and Manzer, L. E., “Hydroformylation Reactions with Rhodiumcomplexed Dendrimers on Silica,”J. Am. Chem. Soc.,121(13), 3035 (1999).
Bu, J., Judeh, Z.M.A., Ching, C.B. and Kawi, S., “Epoxidation of Olefins Catalyzed by Mn(II) Salen Complex Anchored on PAMAMSiO2 Dendrimer,”Catal. Lett.,85(3-4), 183 (2003).
Choi, H. C., Kim, W., Wang, D.W. and Dai, H. J., “Delivery of Catalytic Metal Species onto Surfaces with Dendrimer Carriers for the Synthesis of Carbon Nanotubes with Narrow Diameter Distribution,”J. Phys. Chem. B,106(48), 12361 (2002).
Chung, Y. M. and Rhee, H.K., “Design of Silica-supported Dendritic Chiral Catalysts for the Improvement of Enantioselective Addition of Diethylzinc to Benzaldehyde,”Catal. Lett.,82(3-4), 249 (2002).
Chung, Y.M. and Rhee, H.K., “Pt-Pd Bimetallic Nanoparticles Encapsulated in Dendrimer Nanoreactor,”Catal. Lett.,85(3-4), 159 (2003).
Driffield, M., Goodall, D. M., Klute, A. S., Smith, D.K. and Wilson, K., “Synthesis and Characterization of Silica-supported L-Lysinebased Dendritic Branches,”Langmuir,18(22), 8660 (2002).
Hecht, S. and Frechet, J. M. J., “Dendritic Encapsulation of Function: Applying Nature’s Site Isolation Principle from Biomimetics to Materials Science,”Angew. Chem. Int. Edit,40(1), 74 (2001).
Jang, J.G., Park, H. B. and Lee, Y.M., “Molecular Thermodynamics Approach on Phase Equilibria of Dendritic Polymer Systems,”Korean J. Chem. Eng.,20, 375 (2003).
Luo, D., Haverstick, K., Belcheva, N., Han, E. and Saltzman, W.M., “Poly(ethylene glycol)-conjugated PAMAM Dendrimer for Biocompatible, High-efficiency DNA Delivery,”Macromolecules,35(9), 3456 (2002).
Marsh, I. R., Smith, H. and Bradley, M., “Solid Phase Polyamine Linkers — Their Utility in Synthesis and the Preparation of Directed Libraries Against Trypanothione Reductase,”Chem. Commun., (8), 941 (1996).
Oosterom, G. E., Reek, J. N. H., Kamer, P. C. J. and van Leeuwen, P., “Transition Metal Catalysis Using Functionalized Dendrimers,”Angew. Chem. Int. Edit,40(10), 1828 (2001).
Stiriba, S. E., Frey, H. and Haag, R., “Dendritic Polymers in Biomedical Applications: From Potential to Clinical Use in Diagnostics and Therapy,”Angew. Chem. Int. Edit,41(8), 1329 (2002).
Swali, V., Wells, N. J., Langley, G. J. and Bradley, M., “Solid-phase Dendrimer Synthesis and the Generation of Super-high-loading Resin Beads for Combinatorial Chemistry,”J. Org. Chem.,62(15), 4902 (1997).
Tsubokawa, N., Ichioka, H., Satoh, T., Hayashi, S. and Fujiki, K., “Grafting of ‘Dendrimer-like’ Highly Branched Polymer onto Ultrafine Silica Surface,”React. Funct. Polym.,37(1-3), 75 (1998).
van Heerbeek, R., Kamer, P. C. J., van Leeuwen, P. and Reek, J.N.H., “Dendrimers as Support for Recoverable Catalysts and Reagents,”Chem. Rev.,102(10), 3717 (2002).
Vogtle, F., Gestermann, S., Hesse, R., Schwierz, H. and Windisch, B., “Functional Dendrimers,”Prog. Polym. Sci.,25(7), 987 (2000).
Wells, M. and Crooks, R.M., “Interactions Between Organized, Surface-confined Monolayers and Vapor-phase Probe Molecules. 10. Preparation and Properties of Chemically Sensitive Dendrimer Surfaces,”J. Am. Chem. Soc.,118(16), 3988 (1996).
Zimmerman, S. C., Wendland, M. S., Rakow, N.A., Zharov, I. and Suslick, K. S., “Synthetic Hosts by Monomolecular Imprinting Inside Dendrimers,”Nature,418(6896), 399 (2002).
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This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.
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Li, R., Bu, J. A study on the reaction kinetics of dendrimerization by FT-IR spectroscopy: Propagation of PAMAM dendrimer on silica gel. Korean J. Chem. Eng. 21, 98–103 (2004). https://doi.org/10.1007/BF02705385
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DOI: https://doi.org/10.1007/BF02705385