Soft Matter Materials Branch, Materials and Manufacturing Directorate, Air Force Research Lab, Wright Patterson Air Force Base, Ohio 45433-7750, United States.
Department of Physics and Astronomy, Ohio University, Athens, Ohio 45701, United States.
ACS Biomater Sci Eng. 2020 May 11;6(5):2612-2620. doi: 10.1021/acsbiomaterials.9b00933. Epub 2019 Nov 13.
The use of biomolecules has been invaluable at generating and controlling optical chirality in nanomaterials; however, the structure and properties of the chiral biotemplate are not well understood due to the complexity of peptide-nanoparticle interactions. In this study, we show that the complex interactions between d-peptides and gold nanomaterials led to a chiral restructuring of peptides as demonstrated by circular dichroism and proteolytic cleavage of d-peptides via gold-mediated inversion of peptide chirality. The gold nanoparticles synthesized using d-peptide produce a highly ordered atomic surface and restructured peptide bonds for enzyme cleavage. Differences in gold nanoparticle catalyzed reduction of 4-nitrophenol were observed on the basis of the chiral peptide used in nanoparticle synthesis. Notably, the proteolytic cleavage of d-peptides on gold provides an opportunity for designing nanoparticle based therapeutics to treat peptide venoms, access new chemistries, or modulate the catalytic activity of nanomaterials.
生物分子在纳米材料中产生和控制光学手性方面发挥了巨大的作用；然而，由于肽-纳米颗粒相互作用的复杂性，手性生物模板的结构和性质还没有得到很好的理解。在这项研究中，我们表明，d-肽与金纳米材料之间的复杂相互作用导致了肽的手性重排，这一点通过圆二色性和肽的蛋白水解切割得到证明，肽的蛋白水解切割是通过金介导的肽手性反转实现的。使用 d-肽合成的金纳米粒子产生了高度有序的原子表面，并重构了用于酶切割的肽键。基于用于纳米粒子合成的手性肽，观察到了金纳米粒子催化 4-硝基苯酚还原的差异。值得注意的是，金上 d-肽的蛋白水解切割为设计基于纳米颗粒的治疗肽毒液、获得新化学物质或调节纳米材料的催化活性提供了机会。
