Schottky Junction Nanozyme Based on Mn-Bridged Co-Phthalocyanines and Ti3C2Tx Nanosheets Boosts Integrative Type I and II Photosensitization for Multimodal Cancer Therapy.

Cancer phototheranostics have the potential for significantly improving the therapeutic effectiveness, as it can accurately diagnose and treat cancer. However, the current phototheranostic platforms leave much to be desired and are often limited by tumor hypoxia. Herein, a Schottky junction nanozyme has been established between a manganese-bridged cobalt-phthalocyanines complex and Ti3C2Tx MXene nanosheets (CoPc-Mn/Ti3C2Tx), which can serve as an integrative type I and II photosensitizer for enhancing cancer therapeutic efficacy via a photoacoustic imaging-guided multimodal chemodynamic/photothermal/photodynamic therapy strategy under near-infrared (808 nm) light irradiation. The Schottky junction not only possessed a narrow-bandgap, enhanced electron-hole separation ability and exhibited a potent redox potential but also enabled improved H2O2 and O2 supplying performances in vitro. Accordingly, the AS1411 aptamer-immobilized CoPc-Mn/Ti3C2Tx nanozyme illustrated high accuracy and excellent anticancer efficiency through a multimodal therapy strategy in in vitro and in vivo experiments. This work presents a valuable method for designing and constructing a multifunctional nanocatalytic medicine platform for synergistic cancer therapy of solid tumors.

Curcumin-regulated constructing of defective zinc-based polymer-metal-organic framework as long-acting antibacterial platform for efficient wound healing.

A dual-modal antibacterial platform has been established for highly efficient wound healing infected by bacteria based on a defective zinc-based metal-organic framework composite, which was synthesized using 1,4-phthalic acid-based polyether polymer (L8) as ligand, curcumin as regulator, and Zn2+ as metal coordinated center (Cur@Zn-MOF). In addition to the integration of the features of polymer-MOF synthesized using L8 (such as high water stability and controllable and long-term release of Zn2+) and Zn-bioMOF prepared using curcumin as ligand (such as feasible release of curcumin and Zn2+ and good biocompatibility), the Cur@Zn-MOF bioplatform also possessed plenty of structure defects. Comparing with Zn-bioMOF and polyZn-MOF synthesized using the sole ligand, the smaller released amount of curcumin (6.08 µg mL-1) and higher release level of Zn2+ ions (5.68 µg mL-1) were simultaneously achieved for the defective Cur@Zn-MOF within a long-term duration (48 h). The synergistic effect afforded Cur@Zn-MOF the high sterilization performance toward Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) even at the low usage of 125 µg mL-1. The in vivo wound healing effect further confirmed the superior treatment ability of Cur@Zn-MOF toward the bacterium-infected wound. Also, the negligible cytotoxicity and low hemolysis of Cur@Zn-MOF greatly promoted the viability of human skin fibroblasts. Accordingly, this work can provide a new dual-modal bioplatform based on the functional MOF via the controllable release of antibacterial drug and metal ions for the efficient wound healing.

A new strategy for the development of efficient impedimetric tobramycin aptasensors with metallo-covalent organic frameworks (MCOFs).

Two bimetallic CoNi-based metallo-covalent organic frameworks (MCOFs) were prepared and explored as the sensitive platforms of impedimetric aptasensors for efficient detection of tobramycin (TOB). The two CoNi-MCOFs were constructed using metallophthalocyanine tetra-amine (MPc-TA, M = Co2+ or Ni2+) and 4,4'-(1,10-phen-anthroline-2,9-diyl) dibenzaldehyde (PTD) as building units and further coordinating to the secondary metal ions (Ni2+ or Co2+) by phenanthroline. Interestingly, the immobilization ability of CoPc-TA-PTD(Ni) to TOB-targeted aptamer is higher than that of NiPc-TA-PTD(Co) due to its stronger binding interactions to aptamer. As a result, the CoPc-TA-PTD(Ni)-based aptasensor shows the superior TOB detection ability, giving a low detection limit of 0.07 fg mL-1 and satisfied sensing performances, such as high selectivity, good reproducibility, and excellent stability. Also, the aptasensor shows the acceptable applicability for detecting TOB in milk or chicken egg. This MCOFs-based sensing strategy could be extensively applied to detect other analytes by anchoring the corresponding probes.

Conjugated bimetallic cobalt/iron polyphthalocyanine as an electrochemical aptasensing platform for impedimetric determination of enrofloxacin in diverse environments.

The synthesis of bimetallic cobalt/iron polyphthalocyanine (represented by polyCoFePc) network via a modified solid-phase synthesis method is described. It was exploited as a platform for anchoring enrofloxacin (ENR)-targeted aptamer strands, thus, fabricating a label-free impedimetric aptasensor for determination of ENR. The polyCoFePc exhibited a porous two-dimensional (2D) conjugated nanostructure and rich functional groups, and showed a superior binding interaction toward aptamer strands as compared to monometallic polyFePc and polyCoPc networks. This finding was attributed to structural defects and increased active binding sites, thereby giving a highly sensitive detection ability toward ENR. By using electrochemical impedance spectroscopy (EIS), the polyCoFePc-based electrochemical aptasensor exhibited an extremely low detection limit of 0.06 fg mL-1 within the ENR concentration from 0.1 fg mL-1 to 100 pg mL-1, along with high selectivity, good reproducibility, and remarkable stability. Interestingly, the constructed polyCoFePc-based aptasensor also demonstrated wide practicability in various environments. The recoveries of ENR spiked into river water, milk, and pork samples ranged within 91.2 - 107.2%, 90.5 - 109.6%, and 91.2 - 102.3%, respectively.