Dataset Information

Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies.

ABSTRACT: Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Structures of complexes with Cl^- , Br^- , NO₃^- , SO₄^2- and AcO^- , supported by computational studies, show how the binding site can adapt to accommodate these anions. ¹ H?NMR binding studies revealed exceptionally high affinities for anions in DMSO, decreasing in the order SO₄^2- >H₂ PO₄^- ?HCO₃^- ?AcO^- ?HSO₄^- >Cl^- >Br^- >NO₃^- >I^- . Analysis of the binding results suggests that selectivity is determined mainly by the H-bond acceptor strength of different anions, but is also modulated by receptor geometry.

SUBMITTER: Jurcek O

PROVIDER: S-EPMC6055605 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Publications

Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies.

Jurček Ondřej O Valkenier Hennie H Puttreddy Rakesh R Novák Martin M Sparkes Hazel A HA Marek Radek R Rissanen Kari K Davis Anthony P AP

Chemistry (Weinheim an der Bergstrasse, Germany) 20180514 32

Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Struct ...[more]

PMID: 29603485

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Project description:The benzoylcyanoxime, NC-C(=N-OH)-C(O)-C6H5 (later H(BCO)), represents a new ampolydentate ligand that received attention in the light of useful biological properties of its coordination compounds. Colorless H(BCO), upon deprotonation, gains color that depends on the counter-cation and the system in general. Five derivatives of H(BCO), with colorless organic and inorganic mono-cations - Cs, Tl, Ag, N(CH3)4 and As(C6H5)4 - were synthesized and characterized by the X-ray analysis, vibrational and electronic spectroscopy. Compounds exhibited unexpected and significant differences in color, both in solid state and in solutions, that were challenging to explain, thereby warranting detailed investigation including high-level DFT/TDFT computations. It was found that the BCO- anion demonstrates negative solvatochromic in polar protic ROH (R = H, CH3, C2H5, C3H7, C4H9) solvents, and appears yellow in color, as tetraalkylammonium or alkali metal salts. In polar aprotic solvents, such as CH3CN, DMF, and DMSO, solutions of the BCO- anion are red. The color originates from n→π* transition in the anion. Solid state structures evidenced a considerable dependence on planarity of the BCO- anion on its color, as well as on the character of bonding in the C-N-O fragment: yellow color is associated with an oxime (bond length C-N is shorter than N-O), while red color is due to the nitroso character (bond length C-N is longer than the N-O). An addition of ethanol to red solutions of the BCO-containing salts leads to the color change to yellow, which is the result of the formation of an H-bond between the C-N-O fragment of cyanoxime and the solvent, also leading to the flattening of the structure. An explanation for this new color-changing effect was offered, based on experimental evidence and TD/DFT calculations. Glossary: H(BCO) is 1-cyano-1-oximino-acetophenone, or benzoylcyanoxime; BCO- is anion of the benzoylcyanoxime; AsPh4 + is tetraphenylarsonium cation; MMe4 + is tetramethyammonium cation; ROH - alcohols; DMF - dimethylformamide; DMSO - dimethylsulfoxide; AN - acetonitrile; DFT -Density Functional Theory; TDDFT - Time-Dependent Density Functional Theory.

Dataset Information

Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies.

Publications

Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies.

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