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Efficient NAD+ regeneration facilitated by synergistically intensified charge generation and transfer in fullerene/porphyrin assemblies

富勒烯/卟啉组装体内协同增强的电荷生成与转移实现NAD+高效再生

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Abstract

Enzymatic catalysis exhibits the merits of high catalytic rates and specificity, whereas a major obstacle that hampers commercialization is the need for expensive nicotinamide adenine dinucleotide (NAD+) cofactor; thus the regeneration of NAD+ is necessary. Here, we report a fullerene-based photocatalyst (C60-ZnTPP) capable of regenerating NAD+ through oxidation of NADH by photogenerated holes, accompanied by simultaneous hydrogen formation. Zinc meso-tetraphenylporphine (ZnTPP) and C60 are combined as a donor–acceptor (D–A) structure with a robust internal electric field (IEF, 5.67 times greater than that of ZnTPP), ensuring ultrafast (∼1 ps) and long-lived charge separation (>3 ns) and transfer, which is conducive to improving the performance of photocatalytic regeneration of NAD+. NADH is used as the sole hole sacrificial agent in the system, achieving up to 98.6% NAD+ regeneration within 5 h under visible light (≥420 nm) illumination. Equivalent oxidation of ethanol is catalyzed by alcohol dehydrogenase, a key enzyme in human alcohol metabolism, to verify the enzymatic activity of photocatalyzed NAD+. This work provides an extended choice of materials available for photocatalytic NAD+ regeneration, offering valuable insights into optimizing efficient cofactor regeneration pathways.

摘要

昂贵的辅因子烟酰胺腺嘌呤二核苷酸(NAD+)是限制酶催化商业化应用的主要障碍, 因此高效再生NAD+具有重要意义. 本文利用液液界面沉积法制备了一种富勒烯-锌卟啉光催化剂(C60-ZnTPP), 通过光生空穴氧化NADH再生NAD+. C60-ZnTPP给受体结构具有强大的内建电场(是ZnTPP的5.67倍), 最大限度地减少了电荷复合, 保证了超快(~1 ps)电荷分离与长寿命的电荷传输(>3 ns), 有利于提高光催化NAD+再生性能. 本体系以NADH作为唯一的空穴牺牲剂, 在可见光照射5小时内达到98.6%的转化率, 随后利用在人体解酒中起重要作用的乙醇脱氢酶催化乙醇氧化验证NAD+的酶活性, 获得了化学当量的醛.本工作扩展了光催化再生NAD+材料的选择, 为完善辅因子的高效再生途径提供了重要指导.

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Acknowledgements

This work is dedicated to Prof. Chunli Bai on the occasion of his 70th birthday. This work was supported by the National Natural Science Foundation of China (52072374, 52322204 and 51832008), the Ministry of Science and Technology of China (2022YFA1205900). Wu B thanks the Youth Innovation Promotion Association of Chinese Academy of Sciences (CAS, Y2022015). We thank Dr. Jing Li, Dr. Heng Lu, Dr. Qian Wan and Dr. Meng Di Liu at the Technical Institute of Physics and Chemistry, CAS for the help of transient absorption measurements.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Ying Jiang  (蒋颖), Chong Wang  (王冲), Zihui Hua  (华紫辉), Bo Wu  (吴波) & Chunru Wang  (王春儒)

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Ying Jiang  (蒋颖), Chong Wang  (王冲), Zihui Hua  (华紫辉), Yupeng Song  (宋玉朋), Bo Wu  (吴波) & Chunru Wang  (王春儒)

  3. Key Laboratory of Photochemical Conversion and Optoelectronic Materials and CityU-CAS Joint Laboratory of Functional Materials and Devices, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Yupeng Song  (宋玉朋)

  4. College of Chemistry and Life Sciences, Chifeng University, Chifeng, 024000, China

    Qiqige Wulan  (乌兰其其格) & Chunru Wang  (王春儒)

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  1. Ying Jiang  (蒋颖)
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Contributions

Author contributions Jiang Y, Wu B and Wang C designed and engineered the experiments; Wu B and Wang C supervised the research; Jiang Y synthesized and characterized the samples; Jiang Y, Wang C, Hua Z, Song Y and Wulan Q participated in the data analysis; Jiang Y wrote the paper with support from Wu B and Wang C. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Bo Wu  (吴波) or Chunru Wang  (王春儒).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Ying Jiang is currently a PhD candidate at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS). She received her Bachelor’s degree from Xiangtan University in 2017. Her PhD research focuses on the synthesis and design of fullerene-relevant nanomaterials and their applications in photocatalysis.

Bo Wu received her PhD degree from ICCAS in 2016. She is now an associate professor at ICCAS. Her research focuses on the photoelectric properties of fullerene-based nanocomposites.

Chunru Wang received his PhD degree in physical chemistry in 1992 from CAS. Currently, he is a professor at ICCAS. His research interests include the synthesis, isolation, and characterization of endohedral fullerenes and the industrial applications of fullerenes and metallofullerenes.

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40843_2023_2671_MOESM1_ESM.pdf

Supporting Information: Efficient NAD+ regeneration facilitated by synergistically intensified charge generation and transfer in fullerene/porphyrin assemblies

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Jiang, Y., Wang, C., Hua, Z. et al. Efficient NAD+ regeneration facilitated by synergistically intensified charge generation and transfer in fullerene/porphyrin assemblies. Sci. China Mater. 67, 188–196 (2024). https://doi.org/10.1007/s40843-023-2671-5

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