Using Nucleobase Pairing as Supermolecule Linker to Assemble the Bionic Copolymer Nanoparticles with Small Size

Abstract

The specificity hydrogen bonds of nucleobase pairs are the main linker in DNA and RNA. Compared with conventional covalent‐linking polymer to prepare nanoparticles (NPs), nucleobase pairs as supermolecule linker to assemble the bionic copolymer NPs may be an innovative way. Adenine (A) modified poly(ε‐caprolactone) and thymine (T) modified poly(ethylene glycol) are prepared to assemble multiple hydrogen bonds linked NPs in situ. The introduction of multiple hydrogen bonds into NPs results in a unique method to prepare NPs replacing the conventional assemble method. These NPs exhibit narrow size distribution with the average diameter of 45 nm under pH 7.4. The chemical shift of T NH proton moves from 11.30 to 11.05 ppm with increasing temperature from 25 to 80 °C, and the same phenomenon also appears in A NH2 proton resonance, which demonstrate the existence of hydrogen bonds. The low cytotoxicity of NPs is confirmed by MTT assay using MCF7 tumor cells. Collectively, the novel method opens the possibilities to combine bionics in assembling small size nanoparticles.

X‐ray‐Controlled Bilayer Permeability of Bionic Nanocapsules Stabilized by Nucleobase Pairing Interactions for Pulsatile Drug Delivery

“…The first step in fabricating PETAzo was the synthesis and purification of the carboxyl group‐functionalized nucleobases (3‐(9‐adeninyl)‐propionic acid (A‐COOH) and 1‐(carboxymethy)thymine (T‐COOH)) (Figures S1–S5, Supporting Information), followed by preparation of 4‐methacryloyloxyazobenzene and its characterization using nuclear magnetic resonance (NMR), liquid chromatography‐mass spectrometry, high performance liquid chromatography, and gas chromatography‐mass spectrometry (Figures S6–S11, Supporting Information). Poly(ethylene glycol)‐ b ‐polyhydroxyethyl methacrylate‐ b ‐polyazobenzene was synthesized by reversible addition–fragmentation chain transfer polymerization (RAFT) of poly(ethylene glycol) methyl ether methacrylate, polyhydroxyethyl methacrylate, and 4‐methacryloyloxyazobenzene with cyanomethyl dodecyl trithiocarbonate as the RAFT agent (Figures S12–S14, Supporting Information).…”

Nucleobase-Interaction-Directed Biomimetic Supramolecular Self-Assembly

“…Another novel approach to form supramolecular nanostructures is to impart amphiphilicity in the polymer chains by harnessing the nucleobase interactions. For example, Deng and co-workers 32 synthesized adenine-modified poly(ε-caprolactone) (PCL) and thymine-modified PEG and prepared nanoparticles in situ by comixing the polymers. Moreover, they highlighted the advantage of complementary base pairing to achieve polymer micelles with a very narrow size distribution compared with conventional amphiphilic assembly of diblock polymers.…”

Functional Systems Derived from Nucleobase Self‐assembly

“…Zheng and co‐workers described the preparation of H‐bonded crosslinked nanoparticles from a polymeric precursor by post‐polymerization reactions . Specifically, the T‐decorated poly(ethylene glycol)‐ block ‐poly(allyl glycidylether‐ β ‐mercaptoethanol‐thymine) polymer ( mPEG‐T ) and the A‐decorated benzyl alcohol‐ block ‐(poly( ϵ ‐caprolactone)‐ graft ‐poly(2‐hydroxyethylacrylate‐adenine)) polymer ( PCL‐A ) were mixed in aqueous buffers.…”