10.1021/jo301911w.s004
Ling Chen
Ling
Chen
Heng-Yi Zhang
Heng-Yi
Zhang
Yu Liu
Yu
Liu
High Affinity Crown Ether
Complexes in Water: Thermodynamic
Analysis, Evidence of Crystallography and Binding of NAD<sup>+</sup>
American Chemical Society
2012
monocationic pyridinium moiety
NAD
microcalorimetric titration
crown ethers
NMR experiments
dinaphtho
UV
NADH
equilibrium association constants
tetrasulfonated
High Affinity Crown Ether Complexes
binding ability host molecule
dicationic bipyridiniums
2012-11-02 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/High_Affinity_Crown_Ether_Complexes_in_Water_Thermodynamic_Analysis_Evidence_of_Crystallography_and_Binding_of_NAD_sup_sup_/2473135
Improving traditional crown ether to the water-soluble
and high
binding ability host molecule is critical to our efforts to model
or mimic biological supramolecular systems. In this paper, we converted
two traditional crown ethers, 1,5-dinaphtho-32-crown-8 and 1,5-dinaphtho-38-crown-10,
into the water-soluble tetrasulfonated 1,5-dinaphtho-32-crown-8 and
tetrasulfonated 1,5-dinaphtho-38-crown-10, evaluated their complexation
with three dicationic bipyridiniums in aqueous solution by microcalorimetric
titration, UV–vis, and NMR experiments, and then determined
the crystal structures of three tetrasulfonatocrown ether-bipyridinium
complexes. The equilibrium association constants of tetrasulfonated
1,5-dinaphtho-32-crown-8 with these bipyridiniums reach up to 10<sup>7</sup> M<sup>–1</sup>, while those of tetrasulfonated 1,5-dinaphtho-38-crown-10
are just in the range of 10<sup>5</sup> M<sup>–1</sup> order
of magnitude. The thermodynamic data obtained show that the complexation
of two tetrasulfonatocrown ethers with dicationic bipyridiniums is
absolutely enthalpy-driven in water with an accompanying little entropic
gain, and each monocationic pyridinium moiety in guest molecules can
provide about −10 to −15 kJ·mol<sup>–1</sup> enthalpy contribution irrespective of the size of ether crowns.
Moreover, we also investigated the recognition capability of the two
water-soluble crown ethers with NAD<sup>+</sup> and NADH by microcalorimetric
titration and NMR experiments, indicating that tetrasulfonated 1,5-dinaphtho-32-crown-8
shows exclusive selectivity to NAD<sup>+</sup>. The water-solubility
and high affinity of this system as well as the flexible and non-preorganized
characteristic of these crown ethers make it suitable to serve as
a model for mimicking biological systems.