Porous organic frameworks (POFs), a general term for covalent-organic frameworks (COFs), covalent triazine frameworks (CTFs), porous aromatic frameworks (PAFs), etc., are constructed from organic building monomers with strong covalent bonds and have generated great interest among researchers. The remarkable features, such as large surface areas, permanent porosity, high thermal and chemical stability, and convenient functionalization, promote the great potential of POFs in diverse applications. A critical overview of the important development in the design and synthesis of COFs, CTFs, and PAFs is provided and their state-of-the-art applications in analytical chemistry are discussed. POFs and their functional composites have been explored as advanced materials in "turn-off" or "turn-on" fluorescence detection and novel stationary phases for chromatographic separation, as well as a promising adsorbent for sample preparation methods. In addition, the prospects for the synthesis and utilization of POFs in analytical chemistry are also presented. These prospects can offer an outlook and reference for further study of the applications of POFs.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201801116

Porous Organic Frameworks: Advanced Materials in Analytical Chemistry

Sensitive and selective detection of chemical and biological analytes is critical in various scientific and technological fields. As an emerging class of multifunctional materials, covalent organic frameworks (COFs) with their unique properties of chemical modularity, large surface area, high stability, low density, and tunable pore sizes and functionalities, which together define their programmable properties, show promise in advancing chemical detection. This review demonstrates the recent progress in chemical detection where COFs constitute an integral component of the achieved function. This review highlights how the unique properties of COFs can be harnessed to develop different types of chemical detection systems based on the principles of chromism, luminescence, electrical transduction, chromatography, spectrometry, and others to achieve highly sensitive and selective detection of various analytes, ranging from gases, volatiles, ions, to biomolecules. The key parameters of detection performance for target analytes are summarized, compared, and analyzed from the perspective of the detection mechanism and structure–property–performance correlations of COFs. Conclusions summarize the current accomplishments and analyze the challenges and limitations that exist for chemical detection under different mechanisms. Perspectives on how future directions of research can advance the COF-based chemical detection through innovation in novel COF design and synthesis, progress in device fabrication, and exploration of novel modes of detection are also discussed.

Covalent organic frameworks as multifunctional materials for chemical detection.

Recent advances in the construction of functionalized covalent organic frameworks and their applications to sensing.

Magnetic solid-phase extraction (MSPE) is considered to be an advancing sample preparation technique for the separation and preconcentration of environmental pollutants at trace-levels. Magnetic composites, as MSPE adsorbents, incorporate the distinct advantages of versatile nanomaterials and magnetic nanoparticles, compared to traditional solid-phase extraction packing materials. The former can afford fast dispersion and efficient recycling when applied in complex sample matrices. In this review, we elaborate the applications of magnetic composites as MSPE adsorbents for the enrichment of environmental pollutants, reported in the last five years.

Recent applications of magnetic composites as extraction adsorbents for determination of environmental pollutants

Adsorption of pharmaceuticals and personal care products by deep eutectic solvents-regulated magnetic metal-organic framework adsorbents: Performance and mechanism

A solid-phase extraction adsorbent based on an aptamer-functionalized magnetic conjugated organic framework (COF) was developed for selective extraction of traces of hydroxylated polychlorinated biphenyls. This material has advantages such as superparamagnetism of the magnetic core, high surface area and porous structure of the COF, and high specific affinity of the aptamer. In combination with HPLC-MS, the aptamer-functionalized magnetic COF was used for the capture of hydroxy-2',3',4',5,5'-pentachlorobiphenyl in human serum. The method provided a linear range of 0.01-40 ng mL-1 with a good correlation coefficient (R2 =0.9973). The limit of detection was as low as 2.1 pg mL-1 . Furthermore, the material showed good reusability and could be applied in at least ten extraction cycles with recoveries greater than 90 %.

Aptamer-Functionalized Magnetic Conjugated Organic Framework for Selective Extraction of Traces of Hydroxylated Polychlorinated Biphenyls in Human Serum.

Immobilized metal affinity chromatography has drawn great attention as a widespread separation and purification approach. In this work, ruthenium was firstly introduced into the preparation of immobilized metal affinity chromatography considering its affinity to N,O-donor ligands. A β-cyclodextrin-functionalized poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was designed and employed as the supporting material in immobilized metal affinity chromatography. Thiosemicarbazide was introduced into the synthesis process, which not only acted as a bridge between β-cyclodextrin and glycidyl methacrylate, but also chelated with ruthenium because of its mixed hard-soft donor characteristics. The developed monolithic ruthenium(III)-immobilized metal affinity chromatography column was utilized for the adsorption and separation of hippuric acid, a biological indicator of toluene exposure. To achieve high extraction capacity, the parameters affecting the extraction efficiency were investigated with an orthogonal experiment design, L9 (34 ). Under the optimized conditions, the enrichment factor of hippuric acid was 16.7-fold. The method reproducibility was investigated in terms of intra- and interday precisions with relative standard deviations lower than 8.7 and 9.5%, respectively. In addition, ruthenium(III)-immobilized metal affinity chromatography material could be used for up to 80 extractions without an apparent change in extraction recovery.

Design of a ruthenium(III) immobilized affinity material based on a β-cyclodextrin-functionalized poly(glycidyl methacrylate-ethylene dimethacrylate) monolith for the enrichment of hippuric acid.

The short lifetime of perovskite solar cell devices limits the application of the technique, which is yet to be resolved, despite many attempts. An important step is made here by the numerical modelling method, which reveals the decomposition kinetics under the protection of halogen bonds from excess PbI2. Irregular diffusion behaviour of water molecules is observed when excessive PbI2 is introduced, possibly due to the passivation and hindrance from the halogen bond, resulting in a lifetime enhancement of at least five times. The detailed kinetics are also obtained by analyzing the decomposition rate curve, offering a possible path towards high-stability PCE perovskite solar devices, by increasing the PbI2 concentration to above the threshold, which opens an unprecedented route in perovskite solar cell research, and is, hopefully, of intrinsic interest to the broad materials research community as well.

/pdf/improved-perovskite-structural-stability-by-halogen-bond-2npllsm6.pdf

Improved Perovskite Structural Stability by Halogen Bond from Excessive Lead Iodide via Numerical Simulation

Amantadine plasma concentrations correlate well with desired therapeutic effects and adverse outcomes; information on amantadine exposure could be useful when multiple amantadine clearance pathways are impaired or non-compliance is suspected. Micro-sampling strategies, like dried plasma spot, would be particularly useful because ambulatory patients that do not attend a clinic can easily sample a few drops of blood by themselves at the required time of the dosing interval. We developed and validated a dried-plasma-spot-based high performance liquid chromatography-tandem mass spectrometry assay to quantify amantadine. This assay met relevant validation requirements within a hematocrit range of 20-50% and was linear from 100 to 2000 ng/mL. Amantadine was stable in dried plasma spots for up to 21 days at room temperature, regardless of whether the dried plasma spot was protected from light or not. The correlation between paired dried and wet plasma concentrations was assessed in 52 patients. Deming regression coefficients between wet plasma and simultaneously pipetted dried plasma spots were used to predict plasma concentrations. Bland-Altman plots revealed a strong agreement between dried and wet plasma concentrations, supporting the clinical usefulness of dried plasma spots for amantadine monitoring with a self-sampling strategy at a convenient time and place for the patient.

Amantadine hydrochloride monitoring by dried plasma spot technique: High-performance liquid chromatography-tandem mass spectrometry based clinical assay.

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Aptamer-Functionalized Magnetic Conjugated Organic Framework for Selective Extraction of Traces of Hydroxylated Polychlorinated Biphenyls in Human Serum.

Design of a ruthenium(III) immobilized affinity material based on a β-cyclodextrin-functionalized poly(glycidyl methacrylate-ethylene dimethacrylate) monolith for the enrichment of hippuric acid.

Improved Perovskite Structural Stability by Halogen Bond from Excessive Lead Iodide via Numerical Simulation

Amantadine hydrochloride monitoring by dried plasma spot technique: High-performance liquid chromatography-tandem mass spectrometry based clinical assay.