Banerjee Samya, Chakraborty Supratim, Jacinto Marco Paolo, Paul Michael D, Balster Morgan V, Greenberg Marc M
Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.
Biochemistry. 2017 Jan 10;56(1):14-21. doi: 10.1021/acs.biochem.6b01144. Epub 2016 Dec 22.
DNA is rapidly cleaved under mild alkaline conditions at apyrimidinic/apurinic sites, but the half-life is several weeks in phosphate buffer (pH 7.5). However, abasic sites are ∼100-fold more reactive within nucleosome core particles (NCPs). Histone proteins catalyze the strand scission, and at superhelical location 1.5, the histone H4 tail is largely responsible for the accelerated cleavage. The rate constant for strand scission at an abasic site is enhanced further in a nucleosome core particle when it is part of a bistranded lesion containing a proximal strand break. Cleavage of this form results in a highly deleterious double-strand break. This acceleration is dependent upon the position of the abasic lesion in the NCP and its structure. The enhancement in cleavage rate at an apurinic/apyrimidinic site rapidly drops off as the distance between the strand break and abasic site increases and is negligible once the two forms of damage are separated by 7 bp. However, the enhancement of the rate of double-strand break formation increases when the size of the gap is increased from one to two nucleotides. In contrast, the cleavage rate enhancement at 2-deoxyribonolactone within bistranded lesions is more modest, and it is similar in free DNA and nucleosome core particles. We postulate that the enhanced rate of double-strand break formation at bistranded lesions containing apurinic/apyrimidinic sites within nucleosome core particles is a general phenomenon and is due to increased DNA flexibility.
在温和碱性条件下,DNA在无嘧啶/无嘌呤位点会迅速断裂,但其在磷酸盐缓冲液(pH 7.5)中的半衰期为几周。然而,在核小体核心颗粒(NCP)中,无碱基位点的反应活性要高约100倍。组蛋白催化链断裂,在超螺旋位置1.5处,组蛋白H4尾巴在很大程度上导致了断裂加速。当无碱基位点作为包含近端链断裂的双链损伤的一部分时,其在核小体核心颗粒中的链断裂速率常数会进一步提高。这种形式的断裂会导致极具危害性的双链断裂。这种加速取决于无碱基损伤在NCP中的位置及其结构。随着链断裂与无碱基位点之间的距离增加,无嘧啶/无嘌呤位点的断裂速率增强迅速下降,一旦两种损伤形式相隔7个碱基对,这种增强就可以忽略不计。然而,当缺口大小从一个核苷酸增加到两个核苷酸时,双链断裂形成速率的增强会增加。相比之下,双链损伤中2-脱氧核糖内酯的断裂速率增强较为适度,在游离DNA和核小体核心颗粒中相似。我们推测,在核小体核心颗粒中包含无嘧啶/无嘌呤位点的双链损伤处,双链断裂形成速率的增强是一种普遍现象,并且是由于DNA柔韧性增加所致。