A variety of lariat ethers were employed to solubilize water-soluble cytochrome c in methanol, in which alcohol, ether, ester, amine, and amide functionalities were attached as cation-ligating side arms to 18-crown-6, 15-crown-5, and 12-crown-4 rings. Among these lariat ethers, the alcohol-armed 18-crown-6 derivative offered the highest solubilization efficiency for cytochrome c via supramolecular complexation. The resulting cytochrome c-lariat ether complexes were electrochemically and spectroscopically characterized and confirmed to have redox-active heme structures of 6-coordinate low-spin population in methanol. Some of them catalyzed the oxidation of pinacyanol chloride with hydrogen peroxide in methanol and exhibited higher activities than unmodified cytochrome c and its poly(ethylene glycolated) derivative. Since the supramolecular complexation between lariat ether and cytochrome c includes extremely simple procedures, it provides a facile preparation method of effective biocatalysts working in organic solvents from metalloproteins.
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http://dx.doi.org/10.1021/ic991286f | DOI Listing |
Antibiotics (Basel)
October 2023
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, St. Louis, MO 63121, USA.
Lariat ethers are macrocyclic polyethers-crown ethers-to which sidearms are appended. 4,13-Diaza-18-crown-6 having twin alkyl chains at the nitrogens show biological activity. They exhibit antibiotic activity, but when co-administered at with an FDA-approved antibiotic, the latter's potency is often strongly enhanced.
View Article and Find Full Text PDFChem Asian J
September 2022
Department of Chemistry, Shanghai University, 99 Shangda Rd., Shanghai, 200444, P. R. China.
Cyclic polyamine/ethers embedded with anthraquinone moieties and functional pendants, are structural analogues of crown ethers and (oxo-) cyclams, and could be utilized as sensitive and selective chemosensors towards metal cations. Those pseudo- (similar but geometrically distinct) crown and lariat ethers show various cation-binding patterns and stoichiometry, being modulated by donor type, cavity size and pendants' chelating ability. The luminescent and chromogenic properties also differ a lot along with the derivation of the parental macrocycle.
View Article and Find Full Text PDFAnal Bioanal Chem
October 2020
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
The potassium ion (K) plays significant roles in many biological processes. To date, great efforts have been devoted to the development of K sensors for colorimetric, fluorescent, and photoacoustic detection of K separately. However, the development of molecular K probes for colorimetric detection of urinary K, monitoring K fluxes in living cells by fluorescence imaging, and photoacoustic imaging of K dynamics in deep tissues still remains an open challenge.
View Article and Find Full Text PDFPhotochem Photobiol
November 2020
Department of Chemistry and Biochemistry, California State University, Los Angeles, CA, USA.
We investigated the effect of the cation-π interaction on the susceptibility of a tryptophan model system toward interaction with singlet oxygen, that is, type II photooxidation. The model system consists of two indole units linked to a lariat crown ether to measure the total rate of removal of singlet oxygen by the indole units in the presence of sodium cations (i.e.
View Article and Find Full Text PDFMolecules
December 2019
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, Marii Curie Skłodowskiej 34, 41800 Zabrze, Poland.
In the investigation presented here the synthesis of new lariat ether derivative obtained from the modification of tetrapyrrolidinyl-PNP-crown ether macrocycle is described. The polyheterotopic molecular coreceptor consisted of the replacement of chlorine atoms with an optically active (S)-(1-benzylpyrrolidin-2-yl) methanamine. The structure was confirmed by using elemental analysis, mass spectrometry, and NMR spectroscopy.
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