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Title: Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities

Abstract

electivity is a fundamental property of pervasive importance in chemistry and biology as reflected in phenomena as diverse as membrane transport, catalysis, sensing, adsorption, complexation, and crystallization. Although the key principles of complementarity and preorganization governing the binding interactions underlying such phenomena were delineated long ago, truly profound selectivity has proven elusive by design in part because synthetic molecular architectures are neither maximally complementary for binding target species nor sufficiently rigid. Even if a host molecule possesses a high degree of complementarity for a guest species, it all too often can distort its structure or even rearrange its conformation altogether to accommodate competing guests. One approach taken by researchers to overcome this challenge has been to devise extremely rigid molecules that bind species within complementary cavities. Although examples have been reported to demonstrate the principle, such cases are not generally of practical utility, because of inefficient synthesis and often poor kinetics. Alternatively, flexible building blocks can be employed, but then the challenge becomes one of locking them in place. Taking a cue from natural binding agents that derive their rigidity from a network of molecular interactions, especially hydrogen bonding, we present herein an example of a crystalline, self-assembled capsule thatmore » binds sulfate by a highly complementary array of rigidified hydrogen bonds (H-bonds). Although covalent or self-assembled capsules have been previously employed as anion hosts, they typically lack the strict combination of complementarity and rigidity required for high selectivity. Furthermore, the available structural data for these systems is either restricted to a limited number of anions of similar size and shape, or varies significantly from one anion to another, which hampers the rationalization of the observed selectivity. We have been employing crystalline host environments functionalized with anion-coordinating groups as a means to obtain maximal three-dimensional complementarity and rigidity. In the present study, we focused on the problem of sulfate recognition and separation, motivated by its high relevance to environmental remediation and nuclear waste cleanup.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. ORNL
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
931064
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition
Additional Journal Information:
Journal Volume: 47; Journal Issue: 10; Journal ID: ISSN 0570-0833
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; BONDING; CAVITIES; HYDROGEN; MEMBRANE TRANSPORT; RADIOACTIVE WASTES; SULFATES

Citation Formats

Custelcean, Radu, Remy, Priscilla, Jiang, Deen, Bonnesen, Peter V, and Moyer, Bruce A. Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities. United States: N. p., 2008. Web. doi:10.1002/anie.200704937.
Custelcean, Radu, Remy, Priscilla, Jiang, Deen, Bonnesen, Peter V, & Moyer, Bruce A. Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities. United States. doi:10.1002/anie.200704937.
Custelcean, Radu, Remy, Priscilla, Jiang, Deen, Bonnesen, Peter V, and Moyer, Bruce A. Tue . "Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities". United States. doi:10.1002/anie.200704937.
@article{osti_931064,
title = {Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities},
author = {Custelcean, Radu and Remy, Priscilla and Jiang, Deen and Bonnesen, Peter V and Moyer, Bruce A},
abstractNote = {electivity is a fundamental property of pervasive importance in chemistry and biology as reflected in phenomena as diverse as membrane transport, catalysis, sensing, adsorption, complexation, and crystallization. Although the key principles of complementarity and preorganization governing the binding interactions underlying such phenomena were delineated long ago, truly profound selectivity has proven elusive by design in part because synthetic molecular architectures are neither maximally complementary for binding target species nor sufficiently rigid. Even if a host molecule possesses a high degree of complementarity for a guest species, it all too often can distort its structure or even rearrange its conformation altogether to accommodate competing guests. One approach taken by researchers to overcome this challenge has been to devise extremely rigid molecules that bind species within complementary cavities. Although examples have been reported to demonstrate the principle, such cases are not generally of practical utility, because of inefficient synthesis and often poor kinetics. Alternatively, flexible building blocks can be employed, but then the challenge becomes one of locking them in place. Taking a cue from natural binding agents that derive their rigidity from a network of molecular interactions, especially hydrogen bonding, we present herein an example of a crystalline, self-assembled capsule that binds sulfate by a highly complementary array of rigidified hydrogen bonds (H-bonds). Although covalent or self-assembled capsules have been previously employed as anion hosts, they typically lack the strict combination of complementarity and rigidity required for high selectivity. Furthermore, the available structural data for these systems is either restricted to a limited number of anions of similar size and shape, or varies significantly from one anion to another, which hampers the rationalization of the observed selectivity. We have been employing crystalline host environments functionalized with anion-coordinating groups as a means to obtain maximal three-dimensional complementarity and rigidity. In the present study, we focused on the problem of sulfate recognition and separation, motivated by its high relevance to environmental remediation and nuclear waste cleanup.},
doi = {10.1002/anie.200704937},
journal = {Angewandte Chemie International Edition},
issn = {0570-0833},
number = 10,
volume = 47,
place = {United States},
year = {2008},
month = {1}
}