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

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

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(C_(60)-ZnTPP),通过光生空穴氧化NADH再生NAD^(+).C_(60)-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.

Enzymatic catalysis exhibits the merits of high catalytic rates and specificity,whereas a major obstacle that hampers commercialization is the need for expensive nicoti-namide adenine dinucleotide(NAD^(+))cofactor;thus the re-generation of NAD^(+)is necessary.Here,we report a fullerene-based photocatalyst(C_(60)-ZnTPP)capable of regenerating NAD^(+)through oxidation of NADH by photogenerated holes,accompanied by simultaneous hydrogen formation.Zinc meso-tetraphenylporphine(ZnTPP)and C_(60)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 pho-tocatalyzed NAD^(+).This work provides an extended choice of materials available for photocatalytic NAD^(+)regeneration,of-fering valuable insights into optimizing efficient cofactor re-generation pathways.