Engineering Multifunctional DNA Hybrid Nanospheres through Coordination‐Driven Self‐Assembly

Abstract

Developing simple and general approaches for the synthesis of nanometer-sized DNAm aterials with specific morphologies and functionalities is important for various applications.H erein, an ovel approachf or the synthesis of anew set of DNA-based nanoarchitectures through coordination-driven self-assembly of Fe II ions and DNAm olecules is reported. By fine-tuning the assembly,F e-DNAn anospheres of precise sizes and controlled compositions can be produced. The hybrid nanoparticles can be tailored for delivery of functional DNAt oc ells in vitro and in vivo with enhanced biological function. This highlights the potential of metal ion coordination as at ool for directing the assembly of DNA architectures,w hichc onceptualizes an ew pathway to expand the repertoire of DNA-based nanomaterials.This methodology will advance both the fields of DNAn anobiotechnology and metal-ligand coordination chemistry.The past decade has witnessed worldwide interest in the construction of DNA-based nanomaterials due to their numerous applications ranging from biomedicine to biotechnology. [1][2][3][4][5] Because DNAi su nable to penetrate cell membranes,integration of DNAwith functional nanocarriers (e.g. cationic polymeric and liposomal systems) to promote the delivery is of interest. [2] Recently,D NA-nanotechnologyenabled nanomaterials (e.g., DNAo rigami and spherical nucleic acids), which enable delicate structure tailoring and good biocompatibility, [3][4][5] have shown great potential to transport therapeutic nucleic acids or molecular cargos into cells for various applications. [1] However,t he current approaches are often limited by sophisticated materials synthesis and formulation processes.S trategies aiming at reducing complexity in the synthesis process and increasing scalability and functionality remain ac entral theme in the field of DNA-based nanomaterials.Coordination-driven self-assembly has proven to be one of the most attractive strategies in supramolecular chemistry for the bottom-up construction of functional molecular architectures and materials. [6] Examples of such ensembles range from coordination polymers (CPs), [7] metal-organic frameworks (MOFs), [8] to supramolecular polymer gels. [9] The integration of organic and inorganic components into these materials at the molecular level could increase their structural complexity and endow them with advanced functionalities and broader applications. [6][7][8][9] In particular, nanoscale CPs are rapidly emerging as one of the most active research fields among the chemistry and materials communities,a sd emonstrated by versatile applications for catalysis,o ptical and magnetic materials,a nd nanomedicine. [7] To date,m ost of such systems are built from small organic molecules and metal ions. [7a-f] Most recently,s mall biomolecules (e.g,t annic acid and dipeptides) have been explored for the assembly of functional CP nanoparticles (NPs) for potential bioimaging and drug delivery applications. [7g-i] Despite successful attempts,t oo ur knowledge,c ontrolled syn...

Metal–DNA Coordination‐Driven Self‐Assembly: A Conceptual Methodology to Expand the Repertoire of DNA Nanobiotechnology

“…TEM images of the Fe-DNA NPs synthesized with a) A20, b) C20, and c) G20. Adapted with permission from reference [14].Copyright 2019 Wiley-VCH Verlag GmbH &C o. KGaA, Weinheim. proach ultimately facilitates the design of multifunctional biomaterials.…”

“…Inspired by metal-ligand coordinationc hemistry,o ur group has synthesizedanew type of DNA nanomaterial by the use of ac oordination-drivens elf-assembly technique ( Figure 4a). [14] Such an approachi sv ery simple and direct, allowing for largescale production of Fe-DNA nanospherest hrough ao ne-pot reaction of DNA moleculesa nd Fe II ions in water at ap roper temperature. Spherical Fe-DNA NPs with adiametero fapproximately (191 AE 30) nm were clearly observed by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) (Figures 4b and c).…”

“…b) SEM image,c)TEM image, and d) HRTEMi mage of the Fe-DNA NPs.T he inset in d) shows the SAED patternoft he Fe-DNA NPs. e) HAADF-STEMimage of the Fe-DNA NPs, along with the corresponding EDS element maps for f) Fe, g) P, h) N, and i) superimposed Fe, P, and N. Adapted with permission from reference[14].Copyright 2019 Wiley-VCH Verlag GmbH &C o. KGaA, Weinheim.…”

A Biomimetic Coordination Nanoplatform for Controlled Encapsulation and Delivery of Drug–Gene Combinations

“…These approaches are often limited by the restriction of the pore size and possible degradation of cargos by exterior surroundings. Recently, encapsulation of biomacromolecules in MOF NPs with small pore size was achieved via a mild de novo approach, such as biomimetic mineralization . Despite the progress made, these delivery systems suffer from low drug loading efficiency (DLE) and low drug‐loading content (DLC, usually less than 10 %) in MOF NPs.…”

Design of Targeted Nanostructured Coordination Polymers (NCPs) for Cancer Therapy

“…These special features make AuNC@CPs interesting materials for near-infrared (NIR)-driven photothermal therapy (PTT) guided by photoacoustic (PA) and magnetic resonance (MR) imaging in vivo [96]. Other interesting examples include DNA-Iron based NCPs tailored for the delivery of functional DNA to cells in vitro and in vivo and used for diagnostic and therapeutic applications [97].…”