13C isotope enrichment of the central trityl carbon decreases fluid solution electron spin relaxation times

Abstract

Electron spin relaxation times for perdeuterated Finland trityl 99% enriched in 13C at the central carbon (13C1-dFT) were measured in phosphate buffered saline (pH = 7.2) (PBS) solution at X-band. The anisotropic 13C1 hyperfine (Ax = Ay = 18 ± 2, Az = 162 ± 1 MHz) and g values (2.0033, 2.0032, 2.00275) in a 9:1 trehalose:sucrose glass at 293 K and in 1:1 PBS:glycerol at 160 K were determined by simulation of spectra at X-band and Q-band. In PBS at room temperature the tumbling correlation time, τR, is 0.29 ± 0.02 ns. The linewidths are broadened by incomplete motional averaging of the hyperfine anisotropy and T2 is 0.13 ± 0.02 µs, which is shorter than the T2 ~ 3.8 µs for natural abundance dFT at low concentration in PBS. T1 for 13C1-dFT in deoxygenated PBS is 5.9 ± 0.5 µs, which is shorter than for natural abundance dFT in PBS (16 µs) but much longer than in air-saturated solution (0.48 ± 0.04 µs). The tumbling dependence of T1 in PBS, 3:1 PBS:glycerol (τR = 0.80 ± 0.05 ns, T1 = 9.7 ± 0.7 µs) and 1:1 PBS:glycerol (τR = 3.4 ± 0.3 ns, T1 = 12.0 ± 1.0 µs) was modeled with contributions to the relaxation predominantly from modulation of hyperfine anisotropy and a local mode. The 1/T1 rate for the 1% 12C1-dFT in the predominantly 13C labeled sample is about a factor of 6 more strongly concentration dependent than for natural abundance 12C1-trityl, which reflects the importance of Heisenberg exchange with molecules with different resonance frequencies and faster relaxation rates. In glassy matrices at 160 K, T1 and Tm for 13C1-dFT are in good agreement with previously reported values for 12C1-dFT consistent with the expectation that modulation of nuclear hyperfine does not contribute to electron spin relaxation in a rigid lattice.