Surface-anchored poly(acryloyl-L(D)-valine) with enhanced chirality-selective effect on cellular uptake of gold nanoparticles

Abstract

Chirality is one of the ubiquitous phenomena in biological systems. The left handed (L-) amino acids and right handed (D-) sugars are normally found in proteins, and in RNAs and DNAs, respectively. The effect of chiral surfaces at the nanoscale on cellular uptake has, however, not been explored. This study reveals for the first time the molecular chirality on gold nanoparticles (AuNPs) functions as a direct regulator for cellular uptake. Monolayers of 2-mercaptoacetyl-L(D)-valine (L(D)-MAV) and poly(acryloyl-L(D)-valine (L(D)-PAV) chiral molecules were formed on AuNPs surface, respectively. The internalized amount of PAV-AuNPs was several times larger than that of MAV-AuNPs by A549 and HepG2 cells, regardless of the chirality difference. However, the D-PAV-AuNPs were internalized with significantly larger amount than the L-PAV-AuNPs. This chirality-dependent uptake effect is likely attributed to the preferable interaction between the L-phospholipid-based cell membrane and the D-enantiomers.

Chiral polymer modified nanoparticles selectively induce autophagy of cancer cells for tumor ablation

“…For instance, almost all of amino acids (except glycine) in proteins are “left-handed” ( l -), while all sugars in DNA and RNA are “right-handed” ( d -) [ 16 ]. Our and other previous studies have demonstrated chirality-dependent nature of cellular uptake [ 17 ], cell adhesion [ 18 ], cell differentiation [ 19 , 20 ], protein adsorption [ 21 , 22 ] (i.e., amount and affinity) and cytotoxicity [ 23 ] on flat substrates or nanoparticles coated with chiral molecules. More recently, two studies observed that NPs with surface-anchored chiral molecules could modulate the autophagy [ 24 , 25 ].…”

“…Gold(III) chloride hydrate (HAuCl 4 ) and sodium citrate (C 6 H 5 Na 3 O 7 ·2H 2 O) were purchased from Sinopharm group Co. Ld. Poly(acryloyl- l -valine) ( l -PAV) ( M w 4926 Da, polydispersity 1.24), poly(acryloyl- d -valine) ( d -PAV) ( M w 4997 Da, polydispersity 1.15) were synthesized and were characterized according our previous works [ 17 , 23 ]. High glucose dulbecco’s modified eagle medium (DMEM) and fetal bovine serum (FBS) were obtained from HyClone (USA).…”

Chirality-mediated enhancement of nitric oxide release and regulation of endothelial cells behaviors by cystine immobilization on Ti–O films

“…Chiral discrimination in response to homochiral biological systems has been frequently reported in the literature. 23,24 Herein, NO release catalyzed by samples with different surface chiralities was evaluated using a Sievers 280i chemiluminescence analyzer. A steady and continuous NO release was observed when the samples were pushed into endogenous NO donor solution (Fig.…”

Enantiopure polythiophene nanoparticles. Chirality dependence of cellular uptake, intracellular distribution and antimicrobial activity

“…12 Selective behaviour is also displayed by chiral gold nanoparticles coated with poly(acryloyl-L-valine)-b-poly(2-hydroxyethyl methylacrylate) (L)-PAV-b-PHEMA or its D counterpart in A549 and HepG2 cancer cells. 13 It has been found that magnetic nanoparticles decorated with L-phosphotyrosine (L-pY) are innocuous to cells while D-pY-decorated ones selectively inhibit cancer cells. 14 Recently, graphene quantum dots functionalized with chiral biomolecules have been reported as new efficient selective antimicrobial nanoagents.…”