RESUMEN
Chiral stirred optical and magnetic properties, through the doping of assembled ultrasmall metal clusters (AMCs), are promising discernment to rivet the molecule-like quantum devices. Here, the single manganese (Mn) atom doping and assembly of the gold cluster (Au8), leading to the chirality driven magnetism, has been achieved through a ligand-mediated growth. The X-ray absorption near edge structure and electron paramagnetic resonance studies corroborate the tetrahedral coordinated local structure of Mn dopant in the Au host. The optical and vibrational circular dichroic analysis affirms the modulation of chirality (negative to positive) in the presence of the Mn. A distinct ferromagnetic hysteresis loop at 300 K shows Mn ridden chiral sensitive ferromagnetism in contrary to the ligand influenced superparamagnetic undoped AMCs. The spin-polarized density functional theory level of calculations reveal the partial overlapping of spin-up and -down density of states in the doped AMCs, attributing to the ferromagnetic nature as like a molecular magnet suitable for the opto-spintronics application.
RESUMEN
Protein splicing is a self-catalyzed event where the intervening sequence intein cleaves off, joining the flanking exteins together to generate a functional protein. Attempts have been made to regulate the splicing rate through variations in temperature, pH, and metals. Although metal-regulated protein splicing has been more captivating to researchers, metals were shown to only inhibit splicing reactions that confine their application. This is the first study to show the effect of nanoparticles (NPs) on protein splicing. We found that gold nanoparticles (AuNPs) of various sizes can increase the splicing efficiency by more than 50% and the N-terminal cleavage efficiency by more than 45% in Mycobacterium tuberculosis SufB precursor protein. This study provides an effective strategy for engineering splicing-enhanced intein platforms. UV-vis absorption spectroscopy, isothermal titration calorimetry (ITC), and transmission electron microscopy (TEM) confirmed AuNP interaction with the native protein. Quantum mechanics/molecular mechanics (QM/MM) analysis suggested a significant reduction in the energy barrier at the N-terminal cleavage site in the presence of gold atom, strengthening our experimental evidence on heightened the N-terminal cleavage reaction. The encouraging observation of enhanced N-terminal cleavage and splicing reaction can have potential implementations from developing a rapid drug delivery system to designing a contemporary protein purification system.
