Predicting 1H NMR relaxation in Gd3+-aqua using molecular dynamics simulations

Philip M. Singer; Arjun Valiya Parambathu; Thiago J. Pinheiro Dos Santos; Yunke Liu; Lawrence B. Alemany; George J. Hirasaki; Walter G. Chapman; Dilip Asthagiri

doi:10.1039/d1cp03356e

Predicting ¹H NMR relaxation in Gd³⁺-aqua using molecular dynamics simulations

Philip M. Singer, Arjun Valiya Parambathu, Thiago J. Pinheiro Dos Santos, Yunke Liu, Lawrence B. Alemany, George J. Hirasaki, Walter G. Chapman, Dilip Asthagiri

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

Atomistic molecular dynamics simulations are used to predict 1H NMR T1 relaxation of water from paramagnetic Gd3+ ions in solution at 25 °C. Simulations of the T1 relaxivity dispersion function r1 computed from the Gd3+-1H dipole-dipole autocorrelation function agree within ≃8% of measurements in the range f0 ≃ 5 ↔ 500 MHz, without any adjustable parameters in the interpretation of the simulations, and without any relaxation models. The simulation results are discussed in the context of the Solomon-Bloembergen-Morgan inner-sphere relaxation model, and the Hwang-Freed outer-sphere relaxation model. Below f0 ≲ 5 MHz, the simulation overestimates r1 compared to measurements, which is used to estimate the zero-field electron-spin relaxation time. The simulations show potential for predicting r1 at high frequencies in chelated Gd3+ contrast-agents used for clinical MRI.

Original language	English
Pages (from-to)	20974-20984
Number of pages	11
Journal	Physical Chemistry Chemical Physics
Volume	23
Issue number	37
DOIs	https://doi.org/10.1039/d1cp03356e
State	Published - Oct 7 2021
Externally published	Yes

Funding

We thank Vinegar Technologies LLC, Chevron Energy Technology Company, and the Rice University Consortium on Processes in Porous Media for financial support. We gratefully acknowledge the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy (No. DE-AC02-05CH11231) and the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for high-performance computer time and support.

Funders	Funder number
Chevron Energy Technology Company
Texas Advanced Computing Center
Vinegar Technologies LLC
U.S. Department of Energy	DE-AC02-05CH11231
Office of Science
National Energy Research Scientific Computing Center

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title = "Predicting 1H NMR relaxation in Gd3+-aqua using molecular dynamics simulations",

abstract = "Atomistic molecular dynamics simulations are used to predict 1H NMR T1 relaxation of water from paramagnetic Gd3+ ions in solution at 25 °C. Simulations of the T1 relaxivity dispersion function r1 computed from the Gd3+-1H dipole-dipole autocorrelation function agree within ≃8% of measurements in the range f0 ≃ 5 ↔ 500 MHz, without any adjustable parameters in the interpretation of the simulations, and without any relaxation models. The simulation results are discussed in the context of the Solomon-Bloembergen-Morgan inner-sphere relaxation model, and the Hwang-Freed outer-sphere relaxation model. Below f0 ≲ 5 MHz, the simulation overestimates r1 compared to measurements, which is used to estimate the zero-field electron-spin relaxation time. The simulations show potential for predicting r1 at high frequencies in chelated Gd3+ contrast-agents used for clinical MRI.",

author = "Singer, {Philip M.} and Parambathu, {Arjun Valiya} and {Pinheiro Dos Santos}, {Thiago J.} and Yunke Liu and Alemany, {Lawrence B.} and Hirasaki, {George J.} and Chapman, {Walter G.} and Dilip Asthagiri",

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T1 - Predicting 1H NMR relaxation in Gd3+-aqua using molecular dynamics simulations

AU - Singer, Philip M.

AU - Parambathu, Arjun Valiya

AU - Pinheiro Dos Santos, Thiago J.

AU - Liu, Yunke

AU - Alemany, Lawrence B.

AU - Hirasaki, George J.

AU - Chapman, Walter G.

AU - Asthagiri, Dilip

PY - 2021/10/7

Y1 - 2021/10/7

N2 - Atomistic molecular dynamics simulations are used to predict 1H NMR T1 relaxation of water from paramagnetic Gd3+ ions in solution at 25 °C. Simulations of the T1 relaxivity dispersion function r1 computed from the Gd3+-1H dipole-dipole autocorrelation function agree within ≃8% of measurements in the range f0 ≃ 5 ↔ 500 MHz, without any adjustable parameters in the interpretation of the simulations, and without any relaxation models. The simulation results are discussed in the context of the Solomon-Bloembergen-Morgan inner-sphere relaxation model, and the Hwang-Freed outer-sphere relaxation model. Below f0 ≲ 5 MHz, the simulation overestimates r1 compared to measurements, which is used to estimate the zero-field electron-spin relaxation time. The simulations show potential for predicting r1 at high frequencies in chelated Gd3+ contrast-agents used for clinical MRI.

AB - Atomistic molecular dynamics simulations are used to predict 1H NMR T1 relaxation of water from paramagnetic Gd3+ ions in solution at 25 °C. Simulations of the T1 relaxivity dispersion function r1 computed from the Gd3+-1H dipole-dipole autocorrelation function agree within ≃8% of measurements in the range f0 ≃ 5 ↔ 500 MHz, without any adjustable parameters in the interpretation of the simulations, and without any relaxation models. The simulation results are discussed in the context of the Solomon-Bloembergen-Morgan inner-sphere relaxation model, and the Hwang-Freed outer-sphere relaxation model. Below f0 ≲ 5 MHz, the simulation overestimates r1 compared to measurements, which is used to estimate the zero-field electron-spin relaxation time. The simulations show potential for predicting r1 at high frequencies in chelated Gd3+ contrast-agents used for clinical MRI.

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DO - 10.1039/d1cp03356e

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VL - 23

SP - 20974

EP - 20984

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 37

ER -

Predicting ¹H NMR relaxation in Gd³⁺-aqua using molecular dynamics simulations

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