How Does Halogen Bonding Behave in Solution? A Theoretical Study Using Implicit Solvation Model

Lu, Yunxiang; Li, Haiying; Zhu, Xiang; Zhu, Weiliang; Liu, Honglai

doi:10.1021/jp111616x

Cited by 116 publications

(115 citation statements)

References 103 publications

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“…This substantially disagrees with solution data [2,43], and also with results of QM calculations [40], which predict that a water molecule is not a halogen bond acceptor. It could thus be concluded that the weak accepting properties of a water molecule result from the large entropic contribution upon formation of an eventual halogen bond.…”

Section: Discussioncontrasting

confidence: 81%

“…These potentials, when determined separately for Cl…Acc, Br…Acc and I…Acc, show that the maximal stabilization of an X…Acc halogen bond is in the range of 0.5 kcal/mol for Cl to 1.5 kcal/mol for I. These values are approximately ten-fold lower that those reported by Voth et al [6], but agree with ab initio derived results for various X…Acc systems [40].…”

Section: Analysis Of X…acc Distance Distributionsupporting

confidence: 87%

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Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Poznański

Shugar

2013

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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Halogenated ligands have been widely developed as potent, and frequently selective, inhibitors of protein kinases (PK). Herein, all structures of protein kinases complexed with a halogenated ligand, identified in the PDB, were analyzed in the context of eventual contribution of halogen bonding to protein-ligand interactions. Global inspection shows that two carbonyl groups of residues located in the hinge region are the most abundant halogen bond acceptors. In contrast to solution data, well-defined water molecules, located at sites conserved across most PK structures, are also involved in halogen bonding. Analysis of cumulative distributions of halogen-acceptor distances shows that structures displaying short contacts involving a halogen atom are overpopulated, contributing together to clearly defined maxima of 2.82, 2.91 and 2.94 Å for chlorine, bromine and iodine, respectively. The angular preference of a halogen bond favors ideal topology (180°, 120°) for iodine. For bromine the distribution is much more dispersed, and no such preference was found for chlorine.

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Section: Discussioncontrasting

confidence: 81%

Section: Analysis Of X…acc Distance Distributionsupporting

confidence: 87%

Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Poznański

Shugar

2013

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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“…Halogen bonds form between nucleophilic acceptors, such as anions, and highly localized positive-charge density on halogen atoms appearing on the side opposite to the covalent bond [13][14][15][16][17][18][19][20][21][22] . They are most prominent with iodine atoms but occur, to a lesser extent, also with the less polarizable bromine, chlorine, and even fluorine (Fig.…”

mentioning

confidence: 99%

Transmembrane anion transport mediated by halogen-bond donors

et al. 2012

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In biology and chemistry, the transport of anions across lipid bilayer membranes is usually achieved by sophisticated supramolecular architectures. significant size reduction of transporters is hampered by the intrinsically hydrophilic nature of typical anion-binding functionalities, hydrogen-bond donors or cations. To maximize the atom efficiency of anion transport, the hydrophobic nature, directionality, and strength of halogen bonds seem promising. unlike the ubiquitous, structurally similar hydrogen bonds, halogen bonds have not been explored for anion transport. Here we report that transport across lipid bilayers can be achieved with small perfluorinated molecules that are equipped with strong halogen-bond donors. Transport is observed with trifluoroiodomethane (boiling point = − 22 °C); that is, it acts as a 'single-carbon' transporter. Contrary to the destructive action of small-molecule detergents, transport with halogen bonds is leakage-free, cooperative, non-ohmic and highly selective, with anion/cation permeability ratios < 37.

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“…The SAPT calculations of small model complexes of the halogen bond also show that electrostatic interactions are mainly responsible for the attraction. [68,72,73] On the other hand, it has been stressed repeatedly that charge-transfer (orbital-orbital) interactions are an important source of the attraction in halogen bonds. [7,[69][70][71][72][73][74][75][76][77][78][79] The strong correlation between the electron-density transfer and the interaction energy suggests that charge-transfer interactions play important roles in the attraction.…”

mentioning

confidence: 99%

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

Tsuzuki

Wakisaka

Ono

et al. 2011

Chemistry A European J

123

118

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The geometries and interaction energies of complexes of pyridine with C6F5X, C6H5X (X=I, Br, Cl, F and H) and RFI (RF=CF3, C2F5 and C3F7) have been studied by ab initio molecular orbital calculations. The CCSD(T) interaction energies (Eint) for the C6F5X–pyridine (X=I, Br, Cl, F and H) complexes at the basis set limit were estimated to be −5.59, −4.06, −2.78, −0.19 and −4.37 kcal mol−1, respectively, whereas the Eint values for the C6H5X–pyridine (X=I, Br, Cl and H) complexes were estimated to be −3.27, −2.17, −1.23 and −1.78 kcal mol−1, respectively. Electrostatic interactions are the cause of the halogen dependence of the interaction energies and the enhancement of the attraction by the fluorine atoms in C6F5X. The values of Eint estimated for the RFI–pyridine (RF=CF3, C2F5 and C3F7) complexes (−5.14, −5.38 and −5.44 kcal mol−1, respectively) are close to that for the C6F5I–pyridine complex. Electrostatic interactions are the major source of the attraction in the strong halogen bond although induction and dispersion interactions also contribute to the attraction. Short‐range (charge‐transfer) interactions do not contribute significantly to the attraction. The magnitude of the directionality of the halogen bond correlates with the magnitude of the attraction. Electrostatic interactions are mainly responsible for the directionality of the halogen bond. The directionality of halogen bonds involving iodine and bromine is high, whereas that of chlorine is low and that of fluorine is negligible. The directionality of the halogen bonds in the C6F5I– and C2F5I–pyridine complexes is higher than that in the hydrogen bonds in the water dimer and water–formaldehyde complex. The calculations suggest that the CI and CBr halogen bonds play an important role in controlling the structures of molecular assemblies, that the CCl bonds play a less important role and that CF bonds have a negligible impact.

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How Does Halogen Bonding Behave in Solution? A Theoretical Study Using Implicit Solvation Model

Cited by 116 publications

References 103 publications

Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Transmembrane anion transport mediated by halogen-bond donors

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine

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How Does Halogen Bonding Behave in Solution? A Theoretical Study Using Implicit Solvation Model

Cited by 116 publications

References 103 publications

Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Halogen bonding at the ATP binding site of protein kinases: Preferred geometry and topology of ligand binding

Transmembrane anion transport mediated by halogen-bond donors

Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C6F5X and C6H5X (X=I, Br, Cl and F) with Pyridine

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Product

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Magnitude and Origin of the Attraction and Directionality of the Halogen Bonds of the Complexes of C₆F₅X and C₆H₅X (X=I, Br, Cl and F) with Pyridine