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Molecular recognition in curved ?-systems: effects of ?-lengthening of tubular molecules on thermodynamics and structures.

ABSTRACT: The thermodynamics and molecular structure of a supramolecular complex between a tubular molecule, (P)-(12,8)-[4]cyclo-2,8-anthanthrenylene, and fullerene were investigated. The enthalpy-driven characteristics of the association were enhanced upon lengthening of the curved sp2-carbon networks in the tubular molecule as a result of an increase in the C-C contact areas in addition to the emergence of CH-? contacts with aliphatic chains. The involvement of CH-? interactions in the molecular recognition consequently increased the entropy cost for the association, and the importance of molecular structures at the edge of tubular molecules was revealed. An inflection-free, smooth surface inside the tubular molecule was revealed by crystallographic analysis, which allowed for dynamic motions of the encapsulated fullerene molecule in solution. This study provided a new example of a molecular peapod with a smoothly curved ?-interface to be examined in the structure-thermodynamics relationship study and led to an in-depth understanding of peapods in general.

SUBMITTER: Matsuno T

PROVIDER: S-EPMC5811110 | biostudies-literature | 2015 Feb

REPOSITORIES: biostudies-literature

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Molecular recognition in curved π-systems: effects of π-lengthening of tubular molecules on thermodynamics and structures.

Matsuno Taisuke T Sato Sota S Iizuka Ryosuke R Isobe Hiroyuki H

Chemical science 20141014 2

The thermodynamics and molecular structure of a supramolecular complex between a tubular molecule, (<i>P</i>)-(12,8)-[4]cyclo-2,8-anthanthrenylene, and fullerene were investigated. The enthalpy-driven characteristics of the association were enhanced upon lengthening of the curved sp<sup>2</sup>-carbon networks in the tubular molecule as a result of an increase in the C-C contact areas in addition to the emergence of CH-π contacts with aliphatic chains. The involvement of CH-π interactions in the ...[more]

PMID: 29560176

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Project description:Understanding the fine balance between changes of entropy and enthalpy and the competition between a guest and water molecules in molecular binding is crucial in fundamental studies and practical applications. Experiments provide measurements. However, illustrating the binding/unbinding processes gives a complete picture of molecular recognition not directly available from experiments, and computational methods bridge the gaps. Here, we investigated guest association/dissociation with β-cyclodextrin (β-CD) by using microsecond-time-scale molecular dynamics (MD) simulations, postanalysis and numerical calculations. We computed association and dissociation rate constants, enthalpy, and solvent and solute entropy of binding. All the computed values of kon, koff, ΔH, ΔS, and ΔG using GAFF-CD and q4MD-CD force fields for β-CD could be compared with experimental data directly and agreed reasonably with experiment findings. In addition, our study further interprets experiments. Both force fields resulted in similar computed ΔG from independently computed kinetics rates, ΔG = -RT ln(kon·C0/koff), and thermodynamics properties, ΔG = ΔH - TΔS. The water entropy calculations show that the entropy gain of desolvating water molecules are a major driving force, and both force fields have the same strength of nonpolar attractions between solutes and β-CD as well. Water molecules play a crucial role in guest binding to β-CD. However, collective water/β-CD motions could contribute to different computed kon and ΔH values by different force fields, mainly because the parameters of β-CD provide different motions of β-CD, hydrogen-bond networks of water molecules in the cavity of free β-CD, and strength of desolvation penalty. As a result, q4MD-CD suggests that guest binding is mostly driven by enthalpy, while GAFF-CD shows that gaining entropy is the major driving force of binding. The study deepens our understanding of ligand-receptor recognition and suggests strategies for force field parametrization for accurately modeling molecular systems.

Dataset Information

Molecular recognition in curved ?-systems: effects of ?-lengthening of tubular molecules on thermodynamics and structures.

Publications

Molecular recognition in curved π-systems: effects of π-lengthening of tubular molecules on thermodynamics and structures.

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