SABRE is a nuclear spin hyperpolarization technique based on the reversible association of a substrate molecule and para-hydrogen (p-H2) to a metal complex. During the lifetime of such a complex, generally fractions of a second, the spin order of p-H2 is transferred to the nuclear spins of the substrate molecule via a transient scalar coupling network, resulting in strongly enhanced NMR signals. This technique is generally applied at relatively high concentrations (mM), in large excess of substrate with respect to metal complex. Dilution of substrate ligands below stoichiometry results in progressive decrease of signal enhancement, which precludes the direct application of SABRE to the NMR analysis of low concentration (μM) solutions. Here, we show that the efficiency of SABRE at low substrate concentrations can be restored by addition of a suitable coordinating ligand to the solution. The proposed method allowed NMR detection below 1 μM in a single scan.
Nuclear magnetic resonance is often the technique of choice in chemical analysis because of its sensitivity to molecular structure, quantitative character, and straightforward sample preparation. However, determination of trace analytes in complex mixtures is generally limited by low sensitivity and extensive signal overlap. Here, we present an approach for continuous hyperpolarization at high magnetic field that is based on signal amplification by reversible exchange (SABRE) and can be straightforwardly incorporated in multidimensional NMR experiments. This method was implemented in a 2D correlation experiment that allows detection and quantification of analytes at nanomolar concentration in complex solutions.
SABRE hyperpolarizes substrates by polarization transfer from para-hydrogen in a metal complex. We have measured the signal enhancement of pyridine and its exchange rate in various [Ir(NHC)(Py)3(H)2](+) complexes to gain insight into their dependence on the N-Heterocyclic Carbene (NHC) ligand's steric and electronic properties.
Signal amplification by reversible exchange (SABRE) is an emerging nuclear spin hyperpolarization technique that strongly enhances NMR signals of small molecules in solution. However, such signal enhancements have never been exploited for concentration determination, as the efficiency of SABRE can strongly vary between different substrates or even between nuclear spins in the same molecule. The first application of SABRE for the quantitative analysis of a complex mixture is now reported. Despite the inherent complexity of the system under investigation, which involves thousands of competing binding equilibria, analytes at concentrations in the low micromolar range could be quantified from single-scan SABRE spectra using a standard-addition approach.
When dealing with trace analysis of complex mixtures, NMR suffers from both low sensitivity and signal overlap. NMR chemosensing, in which the association between an analyte and a receptor is "signaled" by an NMR response, has been proposed as a valuable analytical tool for biofluids and natural extracts. Such chemosensors offer the possibility to simultaneously detect and distinguish different analytes in solution, which makes them particularly suitable for analytical applications on complex mixtures. In this study, we have combined NMR chemosensing with nuclear spin hyperpolarization. This was realized using an iridium complex as a receptor in the presence of parahydrogen: association of the target analytes to the metal center results in approximately 1000-fold enhancement of the NMR response. This amplification allows the detection, identification, and quantification of analytes at low-micromolar concentrations, provided they can weakly associate to the iridium chemosensor. Here, our NMR chemosensing approach was applied to the quantitative determination of several flavor components in methanol extracts of ground coffee.
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