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WO 93/13150 calixpyridinopyrrole, and calixpyridine macrocycles, having 7/1993 (WO) . 4, 5, 6, 7, or 8 heterocyclic rings, as Well as syntheses, OTHER PUBLICATIONS derivatives, conjugates, multimers, and solid supports Aoyama, et al., “Multi—Point Interaction of Phosphates With thereof. Such macrocycles have proved to be effective and Protonated Pyridylporphyrin Discrimination of Monoalkyl selective ion- and neutral molecule-binding agents forming and Dialkyl Phosphates,” Chemistry Letters, pp. 1241—1244, supramolecular ensembles, and ion- and neutral molecule 1991. separation agents. The macrocycles are fully meso-non Vogel, et al., “2,7,12,17—Tetraproplyporphycene—Counter hydrogen-substituted porphyrinogens, a feW molecules of part of Octaethylporphyrin in the Porphycene Series,” Which Were previously knoWn but not recognized as pos Angew. Chem. Int. Ed. Engl., 26, No. 9, pp. 928—931, 1987. sessing anion- or molecule-binding properties. The binding Vogel, et al., “NeW Porphycene Ligands: Octaethyl— and mode is noncovalent, primarily that of hydrogen-bonding, Etioporphycene (OEPc and EtioPc)—Tetra — and Pentaco thereby providing a neW mode for liquid chromatography, ordinated Zinc Complexes of OEPc,” Angew. Chem. Intl. that of Hydrogen Bonding Liquid Chromatography. Further Ed. EngL, 32, No. 11, pp. 1600—1604, 1993. useful applications of the macrocycles provided herein Pending Application in India; No. 708/MAS/97 to Gale et al. include environmental remediation by removal of undesired ?led Apr. 3, 1997. ions or neutral molecules, and removal of phosphate for Allen, et al., “Binding of Neutral Substrates by Calix[4] kidney dialysis. pyrroles,” J. Am. Chem. Soc., vol. 118, No. 49, pp. 12471—12472, Sep., 1996. 1 Claim, 30 Drawing Sheets US 6,262,257 B1 Page 2 OTHER PUBLICATIONS Fujimoto, et al., “Synthesis and Crystallographic Studies of a Calix[4]arene With a 1,3—Alternate Conformation,” J. 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Conformationally Rigid, Stereoisomeric Calix[4]arene DeAngelis, et al., “A Li2Ti2—substituted acetylene formed CroWn Ethers: A Quantitative Evaluation of PreorganiZa from ethylene by reaction With (meso— octaethyl porphy tion,” J. Am. Chem. Soc., 112:6979—6985, 1990. rinogen) titanium,” Angewante Chemie, International Edi Golder, et al., “5,10,15,20—meso—tetrakis(3, tion, English, 34:1092—1094, Jun., 1995. 5—di—t—butyl—4—quinomethide)porphyrinogen: a highly De Angelis, et al., “Solvent—dependent Forms of Lithiated puckered tetrapyrrolic macrocycle from the facile aerial 5,5,10,10,15,15,20,20—Octaethylporphyrinogen in Solution oxidation of a phenolic porphyrin,” J. Chem. Soc., Chemical and in the Solid State and Reaction With Tetrahydrofuran,” Communications, 1751—1753, 1989. J. Chem. Soc., Dalton Trans., 2467—2469, 1994. 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The redox chemistry Jacoby, et al., “Electrophilic activation of aliphatic C—H of iron (II)— and cobalt (II)—meso—octaethylporphyrinogen bonds mediated by Zirconium hydride entities and applied to complexes occurring With the formation and cleavage of tWo the functionaliZation of the porphyrinogen periphery,” J. cyclopropane units,” J. Am. Chem. Soc., 116:5702—5713, Amer. Chem. Soc., 117:2805—2816, Mar., 1995. 1994. Jacoby, et al., “Macrocyclic modi?cation using organome DeAngelis, et al., “Oxidation of metal—meso—octaethylpor tallic methodologies. Regiochemically controlled mono— phyrinogen complexes leading to novel oxidiZed forms of and bis—homologation reactions of porphyrinogen With car porphyrinogen other than porphyrins. 1. The redox chemis bon monoxide assisted by early