Lithium-7 nuclear magnetic resonance and calorimetric study of lithium crown complexes in various solvents

Smetana, Alfred J.; Popov, Alexander I.

doi:10.1007/bf00648325

Cited by 116 publications

(57 citation statements)

References 27 publications

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“…These observations can be explained as follows. Due to its small size and high desolvation energy, Li þ does not form a very stable complex with 18c6 (42). Thus, the slightly deeper current blockage of the AP-18c6 adduct observed in LiCl electrolyte compared to unmodified DNA is likely due to the added steric bulk of the uncomplexed crown ether in an elliptical conformation.…”

Section: Resultsmentioning

confidence: 99%

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Fleming

White

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

129

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DNA abasic (AP) sites are one of the most frequent lesions in the genome and have a high mutagenic potential if unrepaired. After selective attachment of 2-aminomethyl-18-crown-6 (18c6), individual AP lesions are detected during electrophoretic translocation through the bacterial protein ion channel α-hemolysin (α-HL) embedded in a lipid bilayer. Interactions between 18c6 and Na þ produce characteristic pulse-like current amplitude signatures that allow the identification of individual AP sites in single molecules of homopolymeric or heteropolymeric DNA sequences. The bulky 18c6-cation complexes also dramatically slow the DNA motion to more easily recordable levels. Further, the behaviors of the AP-18c6 adduct are different with respect to the directionalities of DNA entering the protein channel, and they can be precisely manipulated by altering the cation (Li þ , Na þ or K þ ) of the electrolyte. This method permits detection of multiple AP lesions per strand, which is unprecedented in other work. Additionally, insights into the thermodynamics and kinetics of 18c6-cation interactions at a singlemolecule level are provided by the nanopore measurement.alpha-hemolysin | crown ethers | single-molecule detection | DNA damage

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Section: Resultsmentioning

confidence: 99%

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Fleming

White

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

129

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“…However, most authors consider that, analogous to H 2 O, DMSO, and PC, ion pairing does not take place in solvents like MeOH, AN, and DMF for which 32 < ε r < 40, at least with diluted solutions (concentrations lower than 0.05 M) [95DL]. The situation should be different in AC and EtOH [80SP].…”

Section: Thermodynamic Origin Of the Complex Stabilitymentioning

confidence: 99%

Critical evaluation of stability constants and thermodynamic functions of metal complexes of crown ethers (IUPAC Technical Report)

Arnaud‐Neu¹,

Delgado²,

Chaves³

2003

Pure and Applied Chemistry

118

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“…Crown ethers and cryptands are good macrocyclic ligands for alkali-metal cations (22)(23)(24). It has also been reported that charge transport of a lithium salt in a solid electrolyte is enhanced by addition of crown ethers (25,26).…”

Section: The Addition Of Crown Ethersmentioning

confidence: 99%

A Raman spectral study of solvation and ion association in the systems LiAsF₆/CH₃CO₂CH₃ and LiAsF₆/HCO₂CH₃

Deng¹,

Irish²

1991

Can. J. Chem.

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ZHONGYI DENG and DONALD E. IRISH. Can. J. Chem. 69, 1766 (1991).The structure of the solvated lithium cation in methyl acetate (MA) solutions has been investigated using Raman spectroscopy. Two bands at 844 and 864 cm-' have been assigned to two different types of MA: the former is from the bulk solvent and the latter arises from MA molecules solvating the lithium cation. From measurement of changes in intensity of these bands with increasing salt concentration a solvation number of four for Li+ in MA has been inferred. Changes in the Raman bands at ca. 1740 cm-' suggest that solvation occurs through the carbonyl group. Evidence for contact ion pairing between Li'and AsF; is also presented. An equilibrium between solvent-shared ion pairs and contact ion pairs is proposed for which an equilibrium constant is estimated. The system LiAsF,Imethyl formate (MF) is similar in structure.Key words: Raman, ion pair formation, lithium and hexafluoroarsenate ions, methyl acetate and formate, lithium ion solvation. IntroductionThe search for new electrolyte-solvent systems capable of providing improved performance of both primary and secondary lithium cells and batteries is ongoing. Aprotic solvents, such as ethers, esters, amides carbonates, nitriles, and dimethyl sulfoxide, either alone or mixed, have received extensive study (1). Effort has been focused on overcoming the inferior conductivity of the electrolyte, relative to aqueous systems. Recently methyl formate (MF) and methyl acetate (MA) were identified as possible solvents (2-5). Conductance measurements (3-5) and, for MAILiAsF, and MALiClO,, microwave relaxation spectroscopy and some infrared spectra (5) have been reported. Solutions of MA have a surprisingly high conductance over a wide temperature range. Despite evidence for ion pairing, strong ion-solvent interactions were also suggested in these studies.Raman spectroscopy has proved to be a powerful technique for probing ion-ion and ion-solvent interactions. Recently Hyodo and Okabayashi studied local structure in LiClO,/EC (ethylene carbonate) and mixed solvent systems (6). We have reported Li' solvation in CH,CN solutions, and adsorption of the species at silver electrode surfaces (7). In anticipation of surface

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Lithium-7 nuclear magnetic resonance and calorimetric study of lithium crown complexes in various solvents

Cited by 116 publications

References 27 publications

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Critical evaluation of stability constants and thermodynamic functions of metal complexes of crown ethers (IUPAC Technical Report)

A Raman spectral study of solvation and ion association in the systems LiAsF₆/CH₃CO₂CH₃ and LiAsF₆/HCO₂CH₃

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Lithium-7 nuclear magnetic resonance and calorimetric study of lithium crown complexes in various solvents

Cited by 116 publications

References 27 publications

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Crown ether–electrolyte interactions permit nanopore detection of individual DNA abasic sites in single molecules

Critical evaluation of stability constants and thermodynamic functions of metal complexes of crown ethers (IUPAC Technical Report)

A Raman spectral study of solvation and ion association in the systems LiAsF6/CH3CO2CH3 and LiAsF6/HCO2CH3

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A Raman spectral study of solvation and ion association in the systems LiAsF₆/CH₃CO₂CH₃ and LiAsF₆/HCO₂CH₃