13C-DNP hyperpolarization (HP) in MR allows for single shot detection of 13C-labeled metabolites in vivo. The dynamic acquisition of 13C MR signals after injection of a HP 13C-substrate results in a two-dimensional time-domain dataset. Often the 1D NMR time domain is fitted first and the results are fed into a kinetic model. We present a 2D method, in which all data points in both NMR and kinetic time dimensions are fitted simultaneously. This results in an improved accuracy for all determined kinetic parameters compared to the 1D method, in particular for low-SNR metabolites. CRBs are significantly smaller using 2D analysis.
Experimental: All experiments were approved by the Animal Ethical Committee. LNCaP and PC3 prostate tumor cells were injected subcutaneously at the right hind leg of Balb/c nude mice until a tumor of 0.5 - 1 cm diameter was grown. [1-13C]pyruvate was hyperpolarized using DNP. After the mice were anesthesized, HP pyruvate (final concentration 80 mM) is injected intravenously. The 1H/13C NMR measurements were performed on a 7T MR system (Bruker, Clinscan) with a dedicated 13C/1H RF probe. The conversion of pyruvate into lactate was followed by measuring a 13C-FID every 2s (FA=30°) from a slice covering the tumor (Fig.1).
Steps for 1D data analysis: (1) jMRUI AMARES1,4,5 based fitting of the single NMR signal, obtained by summing all NMR signals of the HP dataset. (2) Batch fitting of the zero-order phases and metabolite amplitudes of all individual NMR signals of the dataset (again with AMARES), using fixed values of the first-order phase, metabolite frequencies and damping factors, obtained in the previous step. (3) Making an educated guess for starting values of the parameters, describing the kinetics of the HP compound. (4) Calculating (the first time with the starting values) theoretical values of the metabolite amplitudes by applying the ODE solver of the Scilab open-source software system6. (5) Updating in an iterative way the kinetic parameters with the Levenberg-Marquardt based Scilab function lsqrsolve, using in each iteration updated values of the differences between the theoretical and AMARES-produced metabolite amplitudes. (6) Obtaining estimations for the parameter statistical errors by calculating the Cramér-Rao bounds (CRBs).
Steps for 2D data analysis: [1] As in steps (1), (2), (3) and (4) above. [2] In essence as in step (5), now however in each iteration with updated values of the differences between theoretical NMR data points and the experimental data points. [3] To realize the previous step, the theoretical metabolite amplitudes, mentioned in step (4), now are used as inputs for a new function NMRmodel, which calculates theoretical values of all data points of the dataset. In this function the fitted zero-order phases and the fixed values of the first-order phase, the metabolite frequencies and damping factors, mentioned in step (2), are used. [4] As in step (6).
[1]Brindle K e,a, Magn Res Med 66:505–519 (2011)
[2]Van
Heijster,F.,e.a.ISMRMBenelux2017-O005(2017)
[3]Van Ormondt,D,.e.a.,ISMRMBenelux2017-P015(2017)
[4]Stefan,D.,e.a.,Meas. Sci. Technol.,20(2009)
[5]Vanhamme,L.e.a.,J. Magn. Res.,129(1997)
[6]Scilab,http://www.scilab.org(2017)
Table 1: Kinetic parameters of two datasets. SNR1 > SNR2. Flip angle is calculated from corresponding RF term.