A Synthetic Allosteric System with High Cooperativity between Polar and Hydrophobia Binding Sites

Schneider, Hans‐Jörg; Ruf, D.

doi:10.1002/anie.199011591

Cited by 80 publications

(29 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Multivalency is not to be confused with cooperativity, which refers to mutual intensification or weakening of binding centers. [30,31] By contrast, even strongly cooperative enzymes generally show significant levels of affinity in the presence of a single partner alone. These include positively cooperative allosteric systems, in which occupation of one binding center increases the affinity at a second center through conformative coupling within the host molecule.…”

Section: The Chelate Effect-"multivalency" In Synthetic and Biologicamentioning

confidence: 99%

Binding Mechanisms in Supramolecular Complexes

2009

Self Cite

View full text Add to dashboard Cite

Supramolecular chemistry has expanded dramatically in recent years both in terms of potential applications and in its relevance to analogous biological systems. The formation and function of supramolecular complexes occur through a multiplicity of often difficult to differentiate noncovalent forces. The aim of this Review is to describe the crucial interaction mechanisms in context, and thus classify the entire subject. In most cases, organic host-guest complexes have been selected as examples, but biologically relevant problems are also considered. An understanding and quantification of intermolecular interactions is of importance both for the rational planning of new supramolecular systems, including intelligent materials, as well as for developing new biologically active agents.

show abstract

Section: The Chelate Effect-"multivalency" In Synthetic and Biologicamentioning

confidence: 99%

Binding Mechanisms in Supramolecular Complexes

2009

Self Cite

View full text Add to dashboard Cite

show abstract

“…Over the years, a large number of artificial receptors displaying positive (5)(6)(7)(8) and negative (9)(10)(11) homotropic and positive (12)(13)(14)(15)(16)(17)(18)(19)(20) and negative (21)(22)(23) heterotropic cooperative binding phenomena have been developed. Although in many cases the origins of the cooperative effects could be identified, few studies have dealt in detail with the kinetics and thermodynamics of such complicated multicomponent receptor-guest systems.…”

mentioning

confidence: 99%

Squaring cooperative binding circles

Deutman

Monnereau

Moalin

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

The cooperative binding effects of viologens and pyridines to a synthetic bivalent porphyrin receptor are used as a model system to study how the magnitudes of these effects relate to the experimentally obtained values. The full thermodynamic and kinetic circles concerning both activation and inhibition of the cage of the receptor for the binding of viologens were measured and evaluated. The results strongly emphasize the apparent character of measured binding and rate constants, in which the fractional saturation of receptors with other guests is linearly expressed in these constants. The presented method can be used as a simple tool to better analyze and comprehend the experimentally observed kinetics and thermodynamics of natural and artificial cooperative systems.kinetics ͉ slippage ͉ supramolecular chemistry ͉ thermodynamics C ooperative binding plays an important role in nature, where it is used to construct well-defined assemblies and is used as a tool to transfer information at the cellular level (1). The formation of the tobacco mosaic virus (2) and the binding of oxygen to hemoglobin (3) are 2 well-known examples of cooperative processes. Cooperative binding interactions can be homotropic or heterotropic, when the combined binding to a multivalent receptor involves the same or different types of guests. In additions, these interactions can be positive or negative, when the binding of a guest promotes or obstructs the binding of a second guest (4).One of the challenges in the field of supramolecular chemistry is to design artificial systems that display cooperative binding effects, not only to better understand the mechanisms involved in the natural processes but also to prepare functional materials and catalysts that benefit from such binding interactions. Over the years, a large number of artificial receptors displaying positive (5-8) and negative (9-11) homotropic and positive (12-20) and negative (21-23) heterotropic cooperative binding phenomena have been developed. Although in many cases the origins of the cooperative effects could be identified, few studies have dealt in detail with the kinetics and thermodynamics of such complicated multicomponent receptor-guest systems. This is surprising, because unlike the complex biological systems, the artificial receptor-guest systems can be easily studied, and the fine details of cooperative behavior can be uncovered. It is generally known that measured association constants are context dependent in the sense that apparent values that depend on, e.g., the solvent system, salt concentrations, pH, and in the worst case impurities, are obtained (4). As a consequence, the observed cooperative binding effects might often deviate from the intrinsic ones.To investigate how the measured cooperative binding effects as derived from the observed experimental binding constants are related to the intrinsic ones, we present a detailed study of the combined binding of viologens and pyridines to the bivalent zinc porphyrin receptor Zn1 (24, 25) (Scheme 1). Pyridine ligan...

show abstract

“…[1] The challenge becomes even greater when aiming to develop molecules that can bind two or more partners simultaneously. Developing such systems by rational design, although not without success, [4] is often an iterative and time-consuming process, prompting us to explore an alternative selection approach using dynamic combinatorial libraries (DCLs). Prime examples are allosteric receptors (i.e.…”

Section: Jianwei LI Piotr Nowak and Sijbren Otto*mentioning

confidence: 99%

An Allosteric Receptor by Simultaneous “Casting” and “Molding” in a Dynamic Combinatorial Library

Nowak

Otto

2014

Angew Chem Int Ed

View full text Add to dashboard Cite

Allosteric synthetic receptors are difficult to access by design. Herein we report a dynamic combinatorial strategy towards such systems based on the simultaneous use of two different templates. Through a process of simultaneous casting (the assembly of a library member around a template) and molding (the assembly of a library member inside the binding pocket of a template), a Russian-doll-like termolecular complex was obtained with remarkable selectivity. Analysis of the stepwise formation of the complex indicates that binding of the two partners by the central macrocycle exhibits significant positive cooperativity. Such allosteric systems represent hubs that may have considerable potential in systems chemistry.

show abstract

A Synthetic Allosteric System with High Cooperativity between Polar and Hydrophobia Binding Sites

Abstract: No Absract.

Cited by 80 publications

References 17 publications

Binding Mechanisms in Supramolecular Complexes

Binding Mechanisms in Supramolecular Complexes

Squaring cooperative binding circles

An Allosteric Receptor by Simultaneous “Casting” and “Molding” in a Dynamic Combinatorial Library

Contact Info

Product

Resources

About