AI Article Synopsis
- Photo-CIDNP (photo-chemically induced dynamic nuclear polarization) enhances NMR spectroscopy sensitivity, particularly in biological systems, but traditionally offers lower signal enhancement compared to other hyperpolarization methods like DNP and SABRE.
- A new photo-oxidation product of tryptophan, identified as 3α-hydroxypyrroloindole, shows significant signal enhancements of up to 380-fold for hydrogen at 200 MHz, leading to measurement time reductions of up to 144,400-fold.
- The research reveals that this oxidation product is highly effective under continuous wave light irradiation, providing insights into mechanisms behind its improved signal performance over regular tryptophan.
Article Abstract
Photo-chemically induced dynamic nuclear polarization (photo-CIDNP) is a promising solution to the inherent lack of sensitivity in NMR spectroscopy. It is particularly interesting in biological systems since it operates in water, at room temperature, and it can be repeated if the bleaching of the system can be controlled. However, the photo-CIDNP signal enhancement is well below those of other hyperpolarization techniques. While DNP, PHIP, and SABRE reach polarization enhancements of 10 to 10-fold, photo-CIDNP enhancement is typically only one order of magnitude for H and two orders of magnitude for C in the amino-acids tryptophan and tyrosine. Here we report on a photo-oxidation product of tryptophan that is strongly photo-CIDNP active under continuous wave light irradiation. In conjunction with the dye Atto Thio 12, a H signal enhancement of 120-fold was observed on a 600 MHz spectrometer, while at 200 MHz the enhancement was 380-fold. These enhancements in signal to noise correspond to a reduction in measurement time of 14 400-fold and 144 400-fold, respectively. The enhancement for C is estimated to be over 1200-fold at 600 MHz which corresponds to an impressive measurement time reduction of 1 440 000-fold. This photo-CIDNP active oxidation product of tryptophan has been identified to be 3α-hydroxypyrroloindole. The reasons for its improved signal enhancement compared to tryptophan have been further investigated.
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| http://dx.doi.org/10.1039/d0cp06068b | DOI Listing |
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