Molecular imprinting inside dendrimers.
Synthetic hosts capable of binding porphyrins have been produced by a mixed-covalent-noncovalent imprinting process wherein a single binding site is created within cross-linked dendrimers. Two synthetic hosts were prepared, using as templates 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin and 5,10,15,20-tetrakis(3,5-dihydroxyphenyl)porphyrin. These two templates were esterified with, respectively, fourth- and third-generation Fréchet-type dendrons containing homoallyl end-groups. The resulting tetra- and octadendron macromolecules underwent the ring-closing metathesis reaction using Grubbs' Type I catalyst, RuCl(2)(P(C(6)H(5))(3))(2)(CHCH(2)C(6)H(5)), to give extensive interdendron cross-linking. Hydrolytic removal of the porphyrin cores afforded imprinted hosts whose ability to bind porphyrins with various peripheral substituents was investigated by UV-visible spectrophotometric titrations and size exclusion chromatography. The results indicate a high yield of imprinted sites that show high selectivity for binding of porphyrins capable of making at least four hydrogen bonds, but only a moderate degree of shape selectivity.
Zimmerman
Steven C
SC
Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA. sczimmer@uiuc.edu
Zharov
Ilya
I
Wendland
Michael S
MS
Rakow
Neal A
NA
Suslick
Kenneth S
KS
D001665:Binding Sites; D003432:Cross-Linking Reagents / Q000737:chemistry; D007700:Kinetics; D011108:Polymers / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013056:Spectrophotometry, Ultraviolet; D013379:Substrate Specificity
D003432:Cross-Linking Reagents; D011108:Polymers; D011166:Porphyrins