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was then electrochemically oxidized at À0.2 V for 5 min. By ToF- Conflicts of interest
SIMS analysis, we found that the ion peak at 125.07 sharply
decreased and the ion peak at 123.05 reappeared (Fig. 3C),
There are no conflicts to declare.
which demonstrated that the generated NADH was reoxidized to
NAD+ on the surface of the electrode. In addition, a controlled
experiment was performed using the NAD+ dimer. As shown in
Fig. S6 (ESI†), the ToF-SIMS spectrum of the NAD+ dimer was
recorded, and a significant special peak of the NAD+ dimer was
observed at 269.04. The characteristic peak at 269.04 could be
attributed to the reduced nicotinamide dimer part from the
NAD+ dimer, which demonstrated that the generation of a NAD+
dimer was successfully blocked in this system. Thus, an electro-
chemically reversible redox of NAD+/NADH derivatives was
realized on the electrode surface.
Notes and references
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For the generated NADH on the surface of the electrode, we
also investigated its coenzyme activity for ADH. Generally, ADH
could catalyze the reduction of acetaldehyde to ethanol in the
presence of NADH, which is oxidized to NAD+.15 Here, we
performed an enzymatic experiment of the electrochemically
generated NADH by immersing the reduced NAD+ derivative
modified electrodes in a mixture of acetaldehyde and ADH.
Thus the enzymatic triggered changes of NADH/NAD+ could be
monitored by ToF-SIMS. As described above, a typical fragment
ion peak was detected at 125.07 for the reduced NAD+ derivative
modified electrodes (Fig. 3B). However, after incubating the
reduced NAD+ modified electrodes in the mixture solution of
acetaldehyde and ADH at 37 1C for 30 min, the fragment ion
peak of NADH significantly degraded and another typical
fragment ion peak of NAD+ emerged at 123.05 (Fig. S7, ESI†),
demonstrating that the generated NADH maintained favorable
coenzyme activity.16
In conclusion, we have synthesized a special benzyl sulfide-
modified NAD+ derivative, PhSNAD, and realized the electro-
chemically reversible inter-conversion between NADH and
NAD+ using NAD+ derivative modified electrodes. The CVs of the
NAD+ modified gold electrode shows a couple of quasi-reversible
redox peaks, demonstrating the reversible inter-conversion of the
NAD+/NADH derivatives. In addition, we monitored the corres-
ponding electrochemical redox products of the NAD+ molecules
modified on the surface of the electrode and researched the
enzymatic activity of the regenerated NADH on the surface of the
electrode using ToF-SIMS. Therefore, this work provides a different
method to monitor the electrochemically reversible redox of NAD+/
NADH derivatives simultaneously on an electrode surface, showing
great potential for the further investigation of NAD+/NADH-evolved
biopathways.
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This research was supported by the National Natural Science
Foundation of China (21421004, 21327807, 21605048), the
Program of Introducing Talents of Discipline to Universities
(B16017), the Innovation Program of Shanghai Municipal Education
Commission (2017-01-07-00-02-E00023), the Fundamental Research
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525–526, 69–71.
Funds for the Central Universities (222201718001, 222201717003), 15 (a) W. Gao, Y. Chen, J. Xi, S. Lin, Y. Chen, Y. Lin and Z. Chen,
Biosens. Bioelectron., 2013, 41, 776–782; (b) X. Wang, L. Li, Y. Wang,
C. Xu, B. Zhao and X. Yang, Food Chem., 2013, 138, 2195–2200.
16 (a) S. Hayward and A. Kitao, Biophys. J., 2006, 91, 1823–1831; (b) V. Flexer,
the Chenguang Program (16CG35), and the Shanghai Education
Development Foundation and the Shanghai Municipal Education
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13948 | Chem. Commun., 2018, 54, 13945--13948
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