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Site Directed Spin Labeling and EPR Spectroscopic Studies of Pentameric Ligand-Gated Ion Channels
Published on: July 4, 2016
Ligand Control of 59Co Nuclear Spin Relaxation Thermometry
Tyler M Ozvat1, Spencer H Johnson1, Anthony K Rappé1
1Department of Chemistry, Colorado State University, 1301 Center Ave., Fort Collins, CO 80523-1872, USA.
Abstract:
Studying the correlation between temperature-driven molecular structure and nuclear spin dynamics is essential to understanding fundamental design principles for thermometric nuclear magnetic resonance spin-based probes. Herein, we study the impact of progressively encapsulating ligands on temperature-dependent 59Co T 1 (spin-lattice) and T 2 (spin-spin) relaxation times in a set of Co(III) complexes: K3[Co(CN)6] (1); [Co(NH3)6]Cl3 (2); [Co(en)3]Cl3 (3), en = ethylenediamine); [Co(tn)3]Cl3 (4), tn = trimethylenediamine); [Co(tame)2]Cl3 (5), tame = triaminomethylethane); and [Co(dinosar)]Cl3 (6), dinosar = dinitrosarcophagine). Measurements indicate that 59Co T 1 and T 2 increase with temperature for 1-6 between 10 and 60 °C, with the greatest ΔT 1/ΔT and ΔT 2/ΔT temperature sensitivities found for 4 and 3, 5.3(3)%T 1/°C and 6(1)%T 2/°C, respectively. Temperature-dependent T 2* (dephasing time) analyses were also made, revealing the highest ΔT 2*/ΔT sensitivities in structures of greatest encapsulation, as high as 4.64%T 2*/°C for 6. Calculations of the temperature-dependent quadrupolar coupling parameter, Δe 2 qQ/ΔT, enable insight into the origins of the relative ΔT 1/ΔT values. These results suggest tunable quadrupolar coupling interactions as novel design principles for enhancing temperature sensitivity in nuclear spin-based probes.
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