Selective Anion Binding by a Cofacial Binuclear Zinc Complex of a Schiff-Base Pyrrole Macrocycle

Devoille, Aline M. J.; Richardson, Patricia; Bill, Nathan L.; Sessler, Jonathan L.; Love, Jason B.

doi:10.1021/ic200082r

Cited by 34 publications

(23 citation statements)

References 50 publications

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“…Control experiments using ZnL 2-4 showed little change in the UV/Vis and emission spectra after titration with Hg 2+ ions under identical conditions (see the Supporting Information, Figures S2-S4). Similar changes in the UV/Vis and emission spectra have been observed previously in the anion-and pyridine-derivative-induced disassemblies of Znsalen or Zn-salophen aggregates, [8] thus suggesting that metal ions such as Hg 2+ ion may similarly induce the efficient disassembly of ZnL 1 aggregates.…”

Section: Resultssupporting

confidence: 80%

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Cai

Zhan

Yan

et al. 2012

Chemistry A European J

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There is widespread interest in non-covalent bonding and weak interactions, such as electrostatic interactions, hydrogen bonding, solvophobic/hydrophobic interactions, metal-metal interactions, and π-π stacking, to tune the molecular assembly of planar π-conjugated organic and inorganic molecules. Inspired by the roles of metal-aromatic interaction in biological systems, such as in ion channels and metalloproteins, herein, we report the first example of the use of Hg(2+) -aromatic interactions to selectively control the assembly and disassembly of zinc-salen complexes in aqueous media; moreover, this process exhibited significant "turn on" fluorescent properties. UV/Vis and fluorescence spectroscopic analysis of the titration of Hg(2+) ions versus complex ZnL(1) revealed that the higher binding affinity of Hg(2+) ions (compared to 13 other metal ions) was ascribed to specific interactions between the Hg(2+) ions and the phenyl rings of ZnL(1); this result was also confirmed by (1)H NMR spectroscopy and HRMS (ESI). Further evidence for this type of interaction was obtained from the reaction of small-molecule analogue L(1) with Hg(2+) ions, which demonstrates the proximity of the N-alkyl group to the aromatic protons during Hg(2+)-ion binding, which led to the consequential H/D exchange reaction with D(2) O. DFT modeling of such interactions between the Hg(2+) ions and the phenyl rings afforded calculated distances between the C and Hg atoms (2.29 Å) that were indicative of C-Hg bond-formation, under the direction of the N atom of the morpholine ring. The unusual coordination of Hg(2+) ions to the phenyl ring of the metallosalen complexes not only strengthened the binding ability but also increased the steric effect to promote the disassembly of ZnL(1) in aqueous media.

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Section: Resultssupporting

confidence: 80%

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Cai

Zhan

Yan

et al. 2012

Chemistry A European J

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“…have performed calculations on Cu 2+ ‐Aβ 1–16 complex using M06, M06L and M06‐2X functionals and found that there is not much structural differences among the three functionals . So we have performed quantum chemical calculations for Histidine complex (Zn(His6‐His13‐His14), Cu(His6‐His13‐His14) , Fe(His6‐His13‐His14) using M06‐2X functional with GENECP basis set, where the 6–311++G(2df, 2pd) basis set has been employed for the C, H, O and N atoms and the effective pseudo potential basis set LANL2DZ , being used for Zn, Cu and Fe atoms. Force constants for the metals (Zn, Cu, Fe) along with co‐ordination sphere in Aβ structure were generated from the hessian matrix obtained from the vibrational frequency analysis has been added to the OPLSAA force field for the molecular dynamics simulation.…”

Section: Methodsmentioning

confidence: 99%

Fe²⁺binding on amyloid β-peptide promotes aggregation

Boopathi

Kolandaivel

2016

Proteins

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The metal ions Zn(2+) , Cu(2+) , and Fe(2+) play a significant role in the aggregation mechanism of Aβ peptides. However, the nature of binding between metal and peptide has remained elusive; the detailed information on this from the experimental study is very difficult. Density functional theory (dft) (M06-2X/6-311++G (2df,2pd) +LANL2DZ) has employed to determine the force field resulting due to metal and histidine interaction. We performed 200 ns molecular dynamics (MD) simulation on Aβ1-42 -Zn(2+) , Aβ1-42 -Cu(2+) , and Aβ1-42 -Fe(2+) systems in explicit water with different combination of coordinating residues including the three Histidine residues in the N-terminal. The present investigation, the Aβ1-42 -Zn(2+) system possess three turn conformations separated by coil structure. Zn(2+) binding caused the loss of the helical structure of N-terminal residues which transformed into the S-shaped conformation. Zn(2+) has reduced the coil and increases the turn content of the peptide compared with experimental study. On the other hand, the Cu(2+) binds with peptide, β sheet formation is observed at the N-terminal residues of the peptide. Fe(2+) binding is to promote the formation of Glu22-Lys28 salt-bridge which stabilized the turn conformation in the Phe19-Gly25 residues, subsequently β sheets were observed at His13-Lys18 and Gly29-Gly37 residues. The turn conformation facilitates the β sheets are arranged in parallel by enhancing the hydrophobic contact between Gly25 and Met35, Lys16 and Met35, Leu17 and Leu34, Val18 and Leu34 residues. The Fe(2+) binding reduced the helix structure and increases the β sheet content in the peptide, which suggested, Fe(2+) promotes the oligomerization by enhancing the peptide-peptide interaction. Proteins 2016; 84:1257-1274. © 2016 Wiley Periodicals, Inc.

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“…A, Fig. 1) that promote a diversity of chemistry within the dinuclear molecular cleft, including dioxygen reduction catalysis, [38][39][40][41] halide sensing, 42 and uranyl reduction and oxo-group functionalisation. [43][44][45][46][47][48][49][50] We have also exploited a steric variation of the meso-substituent (H instead of alkyl, L 1 and L 2 , Fig.…”

Section: Introductionmentioning

confidence: 99%

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO₂

et al. 2019

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Selective Anion Binding by a Cofacial Binuclear Zinc Complex of a Schiff-Base Pyrrole Macrocycle

Cited by 34 publications

References 50 publications

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Fe²⁺binding on amyloid β-peptide promotes aggregation

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO₂

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Selective Anion Binding by a Cofacial Binuclear Zinc Complex of a Schiff-Base Pyrrole Macrocycle

Cited by 34 publications

References 50 publications

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Molecular Assembly Directed by Metal–Aromatic Interactions: Control of the Aggregation and Photophysical Properties of Zn–Salen Complexes by Aromatic Mercuration

Fe2+binding on amyloid β-peptide promotes aggregation

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

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Product

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Fe²⁺binding on amyloid β-peptide promotes aggregation

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO₂