Synthesis and NMR characterization of (<sup>15</sup>N)taurine [2‐(<sup>15</sup>N)aminoethanesulfonic acid]

Philippossian, G.; Welti, Dieter H.; Fumeaux, René; Richli, Urs; Anantharaman, K.

doi:10.1002/jlcr.2580271105

Cited by 8 publications

(4 citation statements)

References 15 publications

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“…The final specific activity of [adenine-8- 14 C]adenosylcobalamin was 1.2 × 10 6 dpm μmol −1 . 2-Bromo[1,1,2,2- 2 H 4 ]ethylamine HBr, 2-bromo[1,2- 13 C 2 ]ethylamine-HBr, 2-bromo[ 15 N]ethylamine-HBr, and unlabeled 2-bromoethylamine-HBr were prepared from the corresponding potassium phthalimide and 1,2-dibromoethane as described (21). Isotopically labeled 4-thia- d - and l -lysine, and unlabeled 4-thia- d -lysine were prepared from the corresponding isotopically labeled or unlabeled d - or l -cysteine and 2-bromoethylamine-HBr as described (22).…”

Section: Methodsmentioning

confidence: 99%

“…The results support catalysis of amino group migration by way of the radical mechanism in Scheme 1. 2-bromoethylamine-HBr were prepared from the corresponding potassium phthalimide and 1,2-dibromoethane as described (21). Isotopically labeled 4-thia-D-and L-lysine and unlabeled 4-thia-D-lysine were prepared from the corresponding isotopically labeled or unlabeled D-or L-cysteine and 2bromoethylamine-HBr as described (22).…”

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confidence: 99%

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Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

et al. 2009

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Lysine 5,6-aminomutase (5,6-LAM) catalyzes the interconversions of D-or L-lysine and the corresponding enantiomers of 2,5-diaminohexanoate, as well as the interconversion of L-β-lysine and L-3,5-diaminohexanoate. The reactions of 5,6-LAM are 5′-deoxyadenosylcobalamin-and pyridoxal-5′-phosphate (PLP)-dependent. Like other 5′-deoxyadenosylcobalamin-dependent enzymes, 5,6-LAM is thought to function by a radical mechanism. No free radicals can be detected by electron paramagnetic resonance (EPR) spectroscopy in reactions of 5,6-LAM with D-or L-lysine or with L-β-lysine. However, the substrate analogs 4-thia-L-lysine and 4-thia-D-lysine undergo early steps in the mechanism to form two radical species that are readily detected by EPR spectroscopy. Cob(II)alamin and 5′-deoxyadenosine derived from 5′-deoxyadenosylcobalamin are also detected. The radicals are proximal to and spin-coupled with low-spin Co 2+ in cob(II)alamin and appear as radical triplets. The radicals are reversibly formed but do not proceed to stable products, so that 4-thia-D-and L-lysine are suicide inhibitors. Inhibition attains equilibrium between the active Michaelis complex and the inhibited radical triplets. The structure of the transient 4-thia-L-lysine-radical is analogous to that of the first substrate-related radical in the putative isomerization mechanism. The second, persistent radical is more stable than the transient species and is assigned as a tautomer, in which a C6(H) of the transient radical is transferred to the carboxaldehyde carbon (C4′) of PLP. The persistent radical blocks the active site and inhibits the enzyme, but it decomposes very slowly at ≤ 1% of the rate of formation to regenerate the active enzyme. Fundamental differences between reversible suicide inactivation by 4-thia-D-or L-4-lysine and irreversible suicide inactivation by D- NIH Public Access Author ManuscriptBiochemistry. Author manuscript; available in PMC 2010 September 1. Figure 1 begins with conversion to D-2,5-DAH by 5,6-LAM and proceeds to the formation of acetate and butyrate (1).5,6-LAM is an adenosylcobalamin-and PLP-dependent enzyme that catalyzes the interconversion of D-or L-lysine with D-or L-2,5-DAH or of L-β-lysine with L-3,5-DAH (1-8).The mechanism of action of 2,3-LAM is well worked out, and the structure of the enzyme is fully compatible with the spectroscopic and chemical evidence supporting the mechanism (9, 10). The 2,3-LAM mechanism inspires the hypothetical chemical mechanism for 5,6-LAM shown in Scheme 1 (2,4,9), wherein the 5′-deoxyadenosyl radical from adenosylcobalamin initiates the chemistry by abstracting a C5(H) from lysine to generate the substrate-related radical 2, which is bound as the N ε -aldimine to PLP. Radical isomerization analogous to that in 2,3-LAM leads through the aziridincarbinyl intermediate 3 to the product-related radical 4, which is quenched by hydrogen transfer from 5′-deoxyadenosine. In contrast to 2,3-LAM, little experimental evidence bearing on the mechanism of action of 5,6-LAM is available, apart fr...

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

et al. 2009

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“…Calibration curves were established using five standard solutions prepared in Millipore water at the following concentrations: [ 14 …”

Section: Calibration Curvesmentioning

confidence: 99%

“…[1,2-13 C 2 ]Taurine was chosen because it has already been used as a suitable tracer to study taurine metabolism in human (12 (14). Standard working solutions were prepared in deionized water and stored at 4°C.…”

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Evaluation of Taurine Metabolism in Cats by Dual Stable Isotope Analysis

Fay

Métairon

Montigon

et al. 1998

Analytical Biochemistry

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Determination of ¹⁵N enrichment of taurine in cat urine by high resolution fast‐atom bombardment mass spectrometry

Stämpfli

Ballèvre

Fay

1992

Rapid Comm Mass Spectrometry

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A method is described for measuring the stable isotopic enrichment of taurine in cat urine samples by high resolution fast-atom bombardment mass spectrometry, after 15N labelled taurine was given to cats for the purpose of investigating taurine metabolism. The 15N enrichment of taurine was measured after hydrolysis and purification of taurine by anion/cation exchange chromatography. The isotopic ratio of taurine was determined by measuring the [M+H]+ ion peaks in the spectra of the unlabelled and labelled compounds under multiple ion scan conditions. The overall standard deviation of the measurement is better than 4%. This method requires no derivation and uses only 500 microL of urine samples.

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Synthesis and NMR characterization of (¹⁵N)taurine [2‐(¹⁵N)aminoethanesulfonic acid]

Cited by 8 publications

References 15 publications

Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

Evaluation of Taurine Metabolism in Cats by Dual Stable Isotope Analysis

Determination of ¹⁵N enrichment of taurine in cat urine by high resolution fast‐atom bombardment mass spectrometry

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Synthesis and NMR characterization of (15N)taurine [2‐(15N)aminoethanesulfonic acid]

Cited by 8 publications

References 15 publications

Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

Radical Triplets and Suicide Inhibition in Reactions of 4-Thia-d- and 4-Thia-l-lysine with Lysine 5,6-Aminomutase

Evaluation of Taurine Metabolism in Cats by Dual Stable Isotope Analysis

Determination of 15N enrichment of taurine in cat urine by high resolution fast‐atom bombardment mass spectrometry

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Synthesis and NMR characterization of (¹⁵N)taurine [2‐(¹⁵N)aminoethanesulfonic acid]

Determination of ¹⁵N enrichment of taurine in cat urine by high resolution fast‐atom bombardment mass spectrometry