Heteropore covalent organic framework-based composite membrane prepared by in situ growth on non-woven fabric for sample pretreatment of food non-targeted analysis.

A heteropore covalent organic framework (COF)-based composite membrane material was prepared and proved to have a satisfactory effect on the pretreatment of vegetable samples. The composite membrane was fabricated by in situ growth of a dual-pore COF on the surface of polydopamine (PDA)-aminated non-woven (NW) fabric. Due to the difference in the strength of the interaction between the phytochromes/COF and the pesticides/COF, the removal of phytochromes and the recovery of pesticides can be achieved by adjusting the composition of the solution. Through a simple immersion or filtration operation, NW@PDA@COF composite membrane can quickly and almost completely remove interfering phytochromes in the samples. The recovery of pesticides was determined by HPLC-MS/MS, and the recovery efficiencies were 72.3~101.7% and 67.3~106.7% for immersion and filtration modes of five different vegetable samples, respectively; the RSD is between 1.1 and 19% (n = 3). The limits of detection and quantification for the 13 pesticides investigated were 0.08 µg·L-1 and 0.23 µg·L-1, respectively. A wide linear range of 1~1000 µg·L-1 was observed with R2 values from 0.9774 to 0.9998. The membrane can be repeatedly used for at least 10 times by using a facile elution treatment. Compared to other commonly used sample pretreatment materials, heteropore COF-based composite membrane is superior in terms of sorbent amount, treatment time, operation simplicity, and material reusability.

Facile Removal of Phytochromes and Efficient Recovery of Pesticides Using Heteropore Covalent Organic Framework-Based Magnetic Nanospheres and Electrospun Films.

Nontargeted analysis of food safety requires selective removal of interference matrices and highly efficient recovery of chemical hazards. Porous materials such as covalent organic frameworks (COFs) show great promise in selective adsorption of matrix molecules via size selectivity. Considering the complexity of interference matrices, we prepared crystalline heteropore COFs whose two kinds of pores have comparable sizes to those of several common phytochromes, main interference matrices in vegetable sample analysis. By controlling the growth of COFs on the surface of Fe3O4 nanoparticles or by utilizing a facile co-electrospinning method, heteropore COF-based magnetic nanospheres or electrospun nanofiber films were prepared, respectively. Both the nanospheres and the films maintain the dual-pore structures of COFs and show good stability and excellent reusability. Via simple magnetic separation or immersion operation, respectively, they were successfully used for the complete removal of phytochromes and highly efficient recovery of 15 pesticides from the extracts of four vegetable samples, and the recoveries are in the range of 83.10-114.00 and 60.52-107.35%, respectively. Film-based immersion operation gives better sample pretreatment performance than the film-based filtration one. This work highlights the great application potentials of heteropore COFs in sample pretreatment for nontargeted analysis, thus opening up a new way to achieve high-performance sample preparation in many fields such as food safety analysis, environment monitoring, and so on.

Green Layer-by-Layer Assembly of Porphyrin/G-Quadruplex-Based Near-Infrared Nanocomposite Photosensitizer with High Biocompatibility and Bioavailability.

A simple and green layer-by-layer assembly strategy is developed for the preparation of a highly bioavailable nanocomposite photosensitizer by assembling near-infrared (NIR) light-sensitive porphyrin/G-quadruplex complexes on the surface of a highly biocompatible nanoparticle that is prepared via Zn2+-assisted coordination self-assembly of an amphiphilic amino acid. After being efficiently delivered to the target site and internalized into tumor cells via enhanced permeability and retention effect and interactions between aptamers and tumor markers, the as-prepared nanoassembly can be directly used as an NIR light-responsive photosensitizer for tumor photodynamic therapy (PDT) since the porphyrin/G-quadruplex complexes are exposed on the nanoassembly surface and kept in an active state. It can also disassemble under the synergistic stimuli of an acidic pH environment and overexpressed glutathione, leasing more efficient porphyrin/G-quadruplex composite photosensitizers while reducing the interference caused by glutathione-dependent 1O2 consumption. Since the nanoassembly can work no matter if it is disassembled or not, the compulsory requirement for in vivo photosensitizer release is eliminated, thus resulting in the great improvement of the bioavailability of the photosensitizer. The PDT applications of the nanoassembly were well demonstrated in both in vitro cell and in vivo animal experiments.