Evidence for an intrinsic binding force between dodecaborate dianions and receptors with hydrophobic binding pockets

Warneke, Jonas; Jenne, Carsten; Bernarding, Johannes; Azov, Vladimir A.; Plaumann, Markus

doi:10.1039/c6cc01233g

Cited by 49 publications

(26 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[3,19,20] Thee ffect becomes particularly pronounced for superchaotropic ions that reach beyond the classical Hofmeister scale. [10,18] Thechaotropic effect extends to molecular recognition events with macrocyclic hosts, [10,12,[21][22][23][24][25][26][27] biologically relevant interactions with proteins and peptides, [13,[28][29][30][31][32] association to small organic molecules, [10,33] binding to membranes, [17,[34][35][36][37][38] polymers, [39] as well as colloids, [15,18,40] and it manifests itself in solid-state structures between superchaotropic ions and organic components. [10,12,26,41,42] Thet erms "chaotropic effect" and "superchaotropic ions" have been readily absorbed by the chemical literature in different contexts.…”

Section: Introductionmentioning

confidence: 99%

The Chaotropic Effect as an Assembly Motif in Chemistry

2018

View full text Add to dashboard Cite

Following up on scattered reports on interactions of conventional chaotropic ions (for example, I−, SCN−, ClO4 −) with macrocyclic host molecules, biomolecules, and hydrophobic neutral surfaces in aqueous solution, the chaotropic effect has recently emerged as a generic driving force for supramolecular assembly, orthogonal to the hydrophobic effect. The chaotropic effect becomes most effective for very large ions that extend beyond the classical Hofmeister scale and that can be referred to as superchaotropic ions (for example, borate clusters and polyoxometalates). In this Minireview, we present a continuous scale of water–solute interactions that includes the solvation of kosmotropic, chaotropic, and hydrophobic solutes, as well as the creation of void space (cavitation). Recent examples for the association of chaotropic anions to hydrophobic synthetic and biological binding sites, lipid bilayers, and surfaces are discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

The Chaotropic Effect as an Assembly Motif in Chemistry

2018

View full text Add to dashboard Cite

show abstract

“…[17] Mass spectrometry has been used to investigate the interaction between halogenated dodecaborate dianions (i. e. B 12 Cl 12 2À ) with non-polar aromatic organic host molecules. [18] Collision induced dissociation of these ions required excitation energies approaching those used to dissociate covalent bonds. The self-assembly of these complexes were explained to be driven by strong dispersion interactions.…”

Section: Introductionmentioning

confidence: 99%

Endo or Exo? Structures of Gas‐Phase Alkali Metal Cation/Aromatic Half‐Belt Complexes

et al. 2018

View full text Add to dashboard Cite

1,1,9,9-Tetramethyl[9](2,11)teropyrenophane (TM9TP), a belt-shaped molecule, has a sizable cavity that molecules or ions could occupy. In this study, the question of whether TM9TP forms gas-phase ion-molecule complexes with metal cations (K , Rb , Cs ) situated inside or outside the TM9TP cavity was addressed using both experimental and computational methods. Complexes were trapped in a Fourier transform ion cyclotron resonance mass spectrometer and their structures were explored by some novel physical chemistry/mass spectrometry methods. Blackbody infrared radiative dissociation kinetics reveal two populations of ions, a fast dissociating fraction and a persistent fraction. Infrared multiphoton dissociation spectra (vibrational spectra) provide very strong evidence that the most abundant population is a complex where the metal cation is inside the TM9TP cavity, endo-TM9TP. Red-shifted C-H stretching bands present in the gas-phase vibrational spectra of these ionic complexes show that there is an interaction between the metal cation and bridge C-H bonds due to the cation sitting inside the cavity of TM9TP. B3LYP/6-31+G(d,p) calculations showed the endo complexes to be the lowest in energy; about 60 kJ mol more thermodynamically stable and more than 120 kJ mol kinetically more stable than the exo complex.

show abstract

“…13 Additionally, the large polarizability of the clusters contributes to the high stability of the formed inclusion complexes. 13,14 The binding constant with γ-CD reaches its maximum for B 12 Br 12 2− , while B 12 I 12 2− already becomes too large and binds more weakly. 13 We reckoned that these globular clusters, and in particular the largest ones, could serve as ideal guests for LRCDs and now present our results on the binding of dodecaborate clusters with δ-, ε-, and ζ-CD, synthesized and purified as described previously.…”

Section: Introductionmentioning

confidence: 99%

High-affinity host–guest chemistry of large-ring cyclodextrins

et al. 2016

View full text Add to dashboard Cite

The host-guest chemistry of large-ring cyclodextrins (LRCDs) has been largely unexplored due to the lack of suitable guest molecules that bind with significant affinities to enable potential applications. Herein, we report their complexation with dodecaborate anions (B12X12(2-)), a novel class of guest molecules. The binding constants of the inorganic guests (10(4)-10(6) M(-1)) allow their classification as the first tight binders for LRCDs.

show abstract

Evidence for an intrinsic binding force between dodecaborate dianions and receptors with hydrophobic binding pockets

Cited by 49 publications

References 40 publications

The Chaotropic Effect as an Assembly Motif in Chemistry

The Chaotropic Effect as an Assembly Motif in Chemistry

Endo or Exo? Structures of Gas‐Phase Alkali Metal Cation/Aromatic Half‐Belt Complexes

High-affinity host–guest chemistry of large-ring cyclodextrins

Contact Info

Product

Resources

About