The complexation of Mg with adenosine 5'-triphosphate (ATP) is omnipresent in biochemical energy conversion, but is difficult to interrogate directly. Here we use the spin- β-emitter Mg to study Mg -ATP complexation in 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) solutions using β-radiation-detected nuclear magnetic resonance (β-NMR). We demonstrate that (nuclear) spin-polarized Mg, following ion-implantation from an accelerator beamline into EMIM-Ac, binds to ATP within its radioactive lifetime before depolarizing. The evolution of the spectra with solute concentration indicates that the implanted Mg initially bind to the solvent acetate anions, whereafter they undergo dynamic exchange and form either a mono- ( Mg-ATP) or di-nuclear ( MgMg-ATP) complex. The chemical shift of Mg-ATP is observed up-field of MgMg-ATP, in accord with quantum chemical calculations. These observations constitute a crucial advance towards using β-NMR to probe chemistry and biochemistry in solution.
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http://dx.doi.org/10.1002/anie.202207137 | DOI Listing |
ChemSusChem
January 2025
Bedimensional Spa, Lungotorrente Secca, 3d, 16163, Genova, ITALY.
The design of interfaces between nanostructured electrodes and advanced electrolytes is critical for realizing advanced electrochemical double-layer capacitors (EDLCs) that combine high charge-storage capacity, high-rate capability, and enhanced safety. Toward this goal, this work presents a novel and sustainable approach for fabricating ionogel-based electrodes using a renewed slurry casting method, in which the solvent is replaced by the ionic liquid (IL), namely 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI). This method avoids time-consuming and costly electrolyte-filling steps by integrating the IL directly into the electrode during slurry preparation, while improving the rate capability of EDLCs based on non-flammable ILs.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Kemerovo State University, Krasnaya 6, Kemerovo, 650000, Russia.
The compressibility of crystalline tetrabromophthalic anhydride (TBPA) and 1-ethyl-3-methylimidazolium nitrate (EMN) was studied based on density functional theory including dispersion interactions at pressures below 1 GPa. It is found for the first time that EMN demonstrates negative linear compressibility (NLC) up to ∼0.15 GPa, whereas TBPA shows significant NLC at pressures higher than ∼0.
View Article and Find Full Text PDFInorg Chem
January 2025
Institute of Inorganic Chemistry (IAC), Karlsruhe Institute of Technology (KIT), Engesserstraße 15, D-76131 Karlsruhe, Germany.
Crown-ether coordination compounds of europium(II/III) and the crown ether (CHO) (24-crown-8, 24c8) are prepared, aiming at novel compounds, structures, and coordination modes as well as potential luminescence properties. By reacting EuCl, EuI, or EuCl with 24c8 or its derivatives in ionic liquids, the novel compounds [BuMeN][Eu(II)(NTf)] (), [BMIm][EuI] (), [EuCl(dibenzo-18c6)] (), [EuI(dibenzo-24c8)] (), [(Eu(III)Cl)(CHO)](24c8) (), and [Eu(III)Cl(24c8)]I () are obtained (BMIm: 1-butyl-3-methylimidazolium; EMIm: 1-ethyl-3-methylimidazolium). Based on different reaction conditions, different coordinative modes including the absence of the crown ether in the product (, ), splitting of the crown ether (), and coordination of 24c8 via six of eight oxygen atoms () and, finally, via all oxygen atoms () are observed.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, 05513-970 São Paulo, SP, Brazil.
Molecular dynamics (MD) simulation is used to study the intermolecular dynamics in the THz frequency range of the ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, [C2C1im][FSI]. Non-polarizable and polarizable models for classical MD simulation are compared using as quality criteria ab initio molecular dynamics (AIMD) and experimental data from far-infrared (FIR) spectroscopy and previously published data of inelastic x-ray scattering (IXS). According to data from IXS spectroscopy, incorporating polarization in the classical MD simulation has relatively little effect on the dispersion curve (excitation frequency vs wavevector) for longitudinal acoustic modes.
View Article and Find Full Text PDFSoft Matter
December 2024
South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China.
Understanding the interplay among the mechanical behavior, ionic conductivity and chain dynamics of ionogels is essential for designing flexible conductors that exhibit both high conductivity and excellent mechanical properties. In this study, ionogels were synthesized the radical polymerization of ,'-dimethylacrylamide (DMAA) and methacrylic acid (MAAc) monomers in the presence of ionic liquid 1-ethyl-3-methylimidazolium trifluoromethane sulfonate ([EMIM][OTf]). By varying the mass content of ionic liquid within ionogels, we investigated the mechanical behavior and ionic conductivity at the macroscopic scale using tensile, rheological testing and electrochemical impedance spectroscopy, as well as the dynamic behavior of chain segments and ions within the network at the microscopic scale using broadband dielectric relaxation spectroscopy (BDS) over a broad temperature range.
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