Quantitative H-2 NMR analysis at the natural abundance represents a well-recognized and efficient method for the identification of the origin of ethanol from different sources. An intrinsic limitation of the protocol used is the long time required, about 8 h, because of the long T, values of the H-2 resonances. In this work we propose the use a paramagnetic relaxation agent that significantly catalyzes the relaxation times and reduces the total time of the analysis. This agent is the macrocyclic Schiff base complex [Gd(H2L)(H2O)(3)(EtOH)](Cl)(3) (.) 2 EtOH (H2L is the [1 + 1] macrocycle derived from the condensation of 3,3'-(3-oxapentane-1,5diyldioxy)bis(2-hydroxybenzaldehyde) with 1,5-diamino-3-azamethylpentane), which is highly stable and soluble in the alcoholic solution used. Elemental analysis, IR and mass spectrometry have characterized this complex. The homogeneity of the complex and the correct Gd:CI = 1:3 ratio was established by SEM-EDS measurements. Further characterization of the paramagnetic complex has been achieved by measuring the magnetic field dependence of the H-1 longitudinal nuclear magnetic relaxation time of a 1 mM solution in CH3OD with a field-cycling relaxometer. The Gd-111 ion accommodates up to four methanol molecules in its inner coordination sphere, whose rapid exchange with the bulk provides an efficient relaxation mechanism. The addition of about 37 mg of the complex to a solution of ethanol (3.0 g) and tetramethylurea (TMU) (1.5 g) results in the reduction of the experimental time of more than 50% with a S/N ratio compatible with that required for this application. (C) 2003 Elsevier B.V. All rights reserved.
Synthesis and characterization of a macrocyclic Schiff base Gd-III complex as a relaxation agent for a faster acquisition of H-2 NMR spectra of ethanol
AIME, Silvio;BOTTA, Mauro;
2004-01-01
Abstract
Quantitative H-2 NMR analysis at the natural abundance represents a well-recognized and efficient method for the identification of the origin of ethanol from different sources. An intrinsic limitation of the protocol used is the long time required, about 8 h, because of the long T, values of the H-2 resonances. In this work we propose the use a paramagnetic relaxation agent that significantly catalyzes the relaxation times and reduces the total time of the analysis. This agent is the macrocyclic Schiff base complex [Gd(H2L)(H2O)(3)(EtOH)](Cl)(3) (.) 2 EtOH (H2L is the [1 + 1] macrocycle derived from the condensation of 3,3'-(3-oxapentane-1,5diyldioxy)bis(2-hydroxybenzaldehyde) with 1,5-diamino-3-azamethylpentane), which is highly stable and soluble in the alcoholic solution used. Elemental analysis, IR and mass spectrometry have characterized this complex. The homogeneity of the complex and the correct Gd:CI = 1:3 ratio was established by SEM-EDS measurements. Further characterization of the paramagnetic complex has been achieved by measuring the magnetic field dependence of the H-1 longitudinal nuclear magnetic relaxation time of a 1 mM solution in CH3OD with a field-cycling relaxometer. The Gd-111 ion accommodates up to four methanol molecules in its inner coordination sphere, whose rapid exchange with the bulk provides an efficient relaxation mechanism. The addition of about 37 mg of the complex to a solution of ethanol (3.0 g) and tetramethylurea (TMU) (1.5 g) results in the reduction of the experimental time of more than 50% with a S/N ratio compatible with that required for this application. (C) 2003 Elsevier B.V. All rights reserved.
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