Increasing the sensitivity of time-resolved photo-CIDNP experiments by multiple laser flashes and temporary storage in the rotating frame

Goez, Martin; Kuprov, Ilya; Hore, P. J.

doi:10.1016/j.jmr.2005.06.017

Cited by 15 publications

(10 citation statements)

References 20 publications

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“…These include high applied fields, pulsed Fourier-transform techniques, and cryogenic probes. More recent approaches focused on generating hyperpolarization by transiently shifting the Boltzmann distribution of nuclear spin states. − These strategies include dissolution dynamic nuclear polarization (DNP), para-hydrogen-induced polarization (PHIP) coupled with signal amplification by reversible exchange (SABRE), − optical pumping, , methods relying on the Haupt effect, Overhauser dynamic nuclear polarization (DNP) and photochemically induced dynamic nuclear polarization (photo-CIDNP). , Given its short hyperpolarization time (∼10 –6 s) and highly nonperturbative nature, photo-CIDNP has recently received considerable attention as a hyperpolarization tool for aromatic amino acids, polypeptides, and proteins in solution. ,− …”

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confidence: 99%

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Cavagnero

2016

J. Phys. Chem. B

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Photochemically induced dynamic nuclear polarization (photo-CIDNP) is a powerful approach for sensitivity enhancement in NMR spectroscopy. In liquids, inter-molecular photo-CIDNP depends on the transient bimolecular reaction between photoexcited dye and sample of interest. Hence the extent of polarization is sample-concentration dependent. This study introduces fluorescein (FL) as a photo-CIDNP dye whose performance is exquisitely tailored to data collection at extremely low sample concentrations. The photo-CIDNP resonance intensities of tryptophan in the presence of either FL or FMN (i.e., the routinely employed flavin mononucleotide photosensitizer) in the liquid state show that FL yields superior sensitivity and enables rapid data collection down to an unprecedented 1 micromolar concentration. This result was achieved on a conventional spectrometer operating at 14.1 Tesla, and equipped with a room-temperature probe (i.e., non-cryogenic). Kinetic simulations show that the excellent behavior of FL arises from its long excited-state triplet lifetime and superior photostability relative to conventional photo-CIDNP sensitizers.

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mentioning

confidence: 99%

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Cavagnero

2016

J. Phys. Chem. B

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“…Recent developments in NMR spectroscopy have been dedicated to increase the sensitivity by improving the SNR . For example, an SNR increase by a factor of about 7.5 was achieved by chemically induced dynamic nuclear polarization …”

Section: Resultsmentioning

confidence: 99%

“…Recent developments in NMR spectroscopy have been dedicated to increase the sensitivity by improving the SNR. [15,16] For example, an SNR increase by a factor of about 7.5 was achieved by chemically induced dynamic nuclear polarization. [16] In our eightfold suppression experiment, we were able to set the value of receiver gain (RG = 28.5) significantly higher than that applied in the ZGPR experiment (RG = 1).…”

Section: Performance Of Eightfold Suppression Of Water and Ethanol Simentioning

confidence: 99%

Application of automated eightfold suppression of water and ethanol signals in ¹H NMR to provide sensitivity for analyzing alcoholic beverages

Monakhova

Schäfer

Humpfer

et al. 2011

Magnetic Reson in Chemistry

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The 400 MHz (1)H NMR analysis of alcoholic beverages using standard pulse programs lacks the necessary sensitivity to detect minor constituents such as methanol, acetaldehyde or ethyl acetate. This study investigates the application of a shaped pulse sequence during the relaxation delay to suppress the eight (1)H NMR frequencies of water and ethanol (the OH singlet of both water and ethanol, as well as the CH(2) quartet and CH(3) triplet of ethanol). The sequence of reference measurement for frequency determination followed by the suppression experiment is controlled by a macro in the acquisition software so that a measurement under full automation is possible (12 min per sample total time). Additionally, sample preparation was optimized to avoid precipitation, which is facilitated by 1:1 dilution with ethanol and pH 7.4 buffer. Compared with the standard water presaturation pulse program, the eightfold suppression allowed a significantly higher setting of receiver gain without receiver overflow, which significantly increased the signal-to-noise ratio by an average factor of 10. The signal intensities increased by a factor of 20. The resulting limits of detection (below 1 g/hl of pure alcohol) now allow the control of legal requirements for minor compounds in alcoholic beverages.

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“…One can also run two‐dimensional experiments using coherence transfer, e. g., in the manner of SCOTCH (spin coherence transfer in chemical reactions) experiments, in which cross‐peaks connect the chemical shifts of nuclei in the starting compounds and reaction products. Last but not least, one can exploit sequences of multiple laser flashes, which accumulate polarization generated by laser pulses . To this end, CIDNP is stored in the transverse plane, then put back along the

B_{0}

‐field direction and added to the polarization generated by the subsequent laser flash.…”

Section: Experimental Aspects Of Cidnpmentioning

confidence: 99%

Time‐Resolved Chemically Induced Dynamic Nuclear Polarization of Biologically Important Molecules

Morozova

Ivanov

2018

ChemPhysChem

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In this work, we review the hyperpolarization technique named chemically induced dynamic nuclear polarization (CIDNP), focusing on the time‐resolved variant of this method and its biological applications. We introduce the main principles of polarization formation in liquids at high magnetic fields, provided by the so‐called spin sorting mechanism. Applications of CIDNP to studying fast reactions of short‐lived free radicals of biologically important molecules are discussed, as well as the potential of the method to probe the structure and magnetic parameters of such radicals. We also explain the principles of protein CIDNP and discuss applications of time‐resolved CIDNP to studies of protein structure and dynamics.

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Increasing the sensitivity of time-resolved photo-CIDNP experiments by multiple laser flashes and temporary storage in the rotating frame

Cited by 15 publications

References 20 publications

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Application of automated eightfold suppression of water and ethanol signals in ¹H NMR to provide sensitivity for analyzing alcoholic beverages

Time‐Resolved Chemically Induced Dynamic Nuclear Polarization of Biologically Important Molecules

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Increasing the sensitivity of time-resolved photo-CIDNP experiments by multiple laser flashes and temporary storage in the rotating frame

Cited by 15 publications

References 20 publications

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Fluorescein: A Photo-CIDNP Sensitizer Enabling Hypersensitive NMR Data Collection in Liquids at Low Micromolar Concentration

Application of automated eightfold suppression of water and ethanol signals in 1H NMR to provide sensitivity for analyzing alcoholic beverages

Time‐Resolved Chemically Induced Dynamic Nuclear Polarization of Biologically Important Molecules

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Application of automated eightfold suppression of water and ethanol signals in ¹H NMR to provide sensitivity for analyzing alcoholic beverages