MOF@COF Heterostructure Hybrid for Dual-Mode Photoelectrochemical–Electrochemical HIV-1 DNA Sensing

Abstract

We developed a novel metal–organic framework (MOF)@covalent–organic framework (COF) hybrid with a hierarchical nanostructure and excellent photoactivity, which further acted as the bifunctional platform of a dual-mode photoelectrochemical (PEC) and electrochemical (EC) biosensor for detecting HIV-1 DNA via immobilizing the HIV-1 DNA probe. First, the presynthesized Cu-MOF nanoellipsoids were used as the template for the in situ growth of the COF network, which was synthesized using copper-phthalocyanine tetra-amine (CoPc-TA) and 2,9-bis­[p-(formyl)­phenyl]-1,10-phenanthroline as building blocks through the Schiff base condensation. In view of the large specific surface area, abundant reserved amino group, excellent electrochemical activity, and high photoactivity, the obtained Cu-MOF@CuPc-TA-COF heterostructure not only can serve as the sensitive platform for anchoring the HIV-1 DNA probe strands but also can be utilized as the signal transducers for PEC and EC biosensors. Thereby, the constructed biosensor shows the sensitive and selective analysis ability toward the HIV-1 target DNA via the complementary hybridization between probe and target DNA strands. The dual-mode PEC and EC measurements revealed that the Cu-MOF@CuPc-TA-COF-based biosensor displayed a wide linear detection range from 1 fM to 1 nM and an extremely low limit of detection (LOD) of 0.07 and 0.18 fM, respectively. In addition, the dual-mode PEC–EC biosensor also demonstrated remarkable selectivity, high stability, good reproducibility, and preferable regeneration ability, as well as acceptable applicability, for which the detected HIV-1 DNA in human serum showed good consistency with real concentrations. Thereby, the present work can open a new dual-mode PEC–EC platform for detecting HIV-1 DNA based on the porous–organic framework heterostructure.

Electrochemical (Bio)Sensors Based on Covalent Organic Frameworks (COFs)

“…COFs can be used as structural materials to adsorb oligonucleotides and their further use as DNA probes for the development of genosensors. A hybrid MOF/COF nanocomposite material was developed by Miao Du's research group [119] (Figure 7). The developed nanocomposite material has been used on a label free genosensor for HIV-1 DNA probe.…”

MOF/COF hybrids as next generation materials for energy and biomedical applications

“…Timeline of the representative studies on MOF/COF composites (bottom). [34][35][36][37][38][39][40][41][42][43] Figures reprinted with permissions from ref. 34, 35, 38, 39, 42 and 43. This journal is © The Royal Society of Chemistry 2022 MOF/COF hybrid structures have been recently synthesized as core-shell structures (MOF@COF or COF@MOF), heterostructures, and composites.…”

Imidazole encapsulated in core–shell MOF@COFs with a high anhydrous proton conductivity

“…Hybrid materials constructed from both MOFs and COFs, known as MOFs@COFs, combine the advantages both materials, meaning that they are widely used in applications including catalysis, gas separation, and sensing. [24][25][26] Fu et al 27 reported the COFs-300@ZIF-8 composite, which showed the highest separation selectivity performance for H 2 /CO 2 gas mixtures. Lan et al 28 provided an integrated porous NH 2 -UiO-66/TpPa-1-COFs hybrid with good photocatalytic H 2 evolution under visible light.…”