Glutathione Nanosphere: Self-Assembly of Conformation-Regulated Trigonal-Glutathiones in Water

Abstract

A novel trigonal conjugate of glutathiones with a 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene core was synthesized and its self-assembling behavior was investigated in water. Three glutathione units were regulated to orient on the same side of the benzene ring, through steric repulsions between ethyl groups attached on the benzene core. Concentration dependence of 1H NMR chemical shifts in D2O revealed formation of molecular assemblies with two affinity constants (Ka = 4.75 × 102 and 6.76 × 104 M−1), which reflect stepwise assembly directed by electrostatic interactions, hydrophobic interactions, and hydrogen bonding. In scanning electron microscopy, hard spherical assemblies with the size of 310 ± 50 nm were observed at high concentration (10 mM), whereas slightly disordered spherical assemblies were obtained at lower concentrations. The spherical assemblies self-assembled from the conformation-regulated trigonal glutathiones showed regular morphology and enhanced rigidity compared to those formed from conformationally non-regulated trigonal glutathiones.

Guest-binding behavior of peptide nanocapsules self-assembled from viral peptide fragments

“…We developed virus-inspired C 3 -and C 5 -symmetric b-sheet-forming peptide conjugates [25][26][27][28] and C 3 -symmetric glutathione conjugates [29][30][31] and reported their characteristic self-assembling behavior in water. 32 Recently, we also synthesized a 24-mer peptide fragment 1 (INHVGGTGGAIMAPVAVTRQLVGS), which participates in the b-annulus motif in the tomato bushy stunt virus (TBSV) and found that 1 self-assembles in water into virus-like nanocapsules with a diameter of 30-50 nm.…”

Peptide Nanomaterials Designed from Natural Supramolecular Systems

“…A simple tripeptide motif glutathione has also been utilized for the construction of nanospheres . Trigonal conjugation of glutathione (Trigonal‐glutathione, TG) formed spherical assemblies with sizes of 100–250 nm in water (Figure c) .…”

Construction of Functional Biomaterials by Biomolecular Self-Assembly

“…52 In order to construct more regular nano-assemblies from glutathione derivatives, 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene was employed as the core of a new TG ( Figure 7B). 53 The glutathione arms on the 1,3,5-positions were assembled on one side of the scaffold due to the alternative conformation of the core. The conformation-regulated trigonal glutathione selfassembled into hard spherical structures with sizes of 310 « 50 nm, which had regular morphologies and enhanced rigidity compared with those formed from conformationally nonregulated trigonal glutathione ( Figure 7B).…”