Fluorescent covalent organic framework as an ultrasensitive fluorescent probe for tyrosinase activity monitoring and inhibitor screening.

BACKGROUND: As a significant biomarker of melanocytic lesions, tyrosinase (TYR) plays an essential role in the clinical diagnosis and treatment of melanin-related diseases. Thus, it is important to develop robust methods for assessing TYR activity. Covalent organic frameworks (COFs) have garnered considerable attention owing to their unique properties, including high chemical stability, good biocompatibility, and large surface area compared with organic dyes, noble metal nanoclusters, and semiconductor quantum dots. However, most COFs are insoluble in water and exhibit weak or no fluorescence emission. Therefore, the development of a water-soluble fluorescent COF for detecting TYR activity in biological samples remains highly desired. RESULTS: In this work, a sensitive and facile fluorometric method based on fluorescent COF was constructed for the detection of TYR activity in human serum samples. The water-soluble COF was fabricated through the condensation polymerization of 4',4‴,4''''',4'''''''-(1,2-ethene-diylidene) tetrakis [1,1'-biphenyl]-4-carboxaldehyde and 2,4,6-tris-(4-aminophenyl)-triazine. The resulting COF displayed yellow-green fluorescence with a maximum emission peak at 560 nm. Tyrosine was catalyzed by TYR to produce melanin-like polymers which formed a coating on the surface of COF and effectively quenched its fluorescence due to fluorescence resonance energy transfer. The proposed approach demonstrated a strong linear correlation in the range of 0.5-80 U/L with a low detection limit of 0.09 U/L. Additionally, the limit of detection for kojic acid, serving as a representative TYR inhibitor, was determined to be 0.0004 µg/mL. SIGNIFICANCE: Our proposed fluorometric sensing platform exhibited exceptional selectivity, sensitivity, and satisfactory recoveries in human serum samples, which is of paramount importance for the clinical diagnostics of melanin-related diseases. Furthermore, the proposed approach was further employed for the screening of TYR inhibitors, suggesting the potential applications in clinical treatment and pharmaceutical research.

A chiral fluorescent COF prepared by post-synthesis modification for optosensing of imazamox enantiomers.

We report a post-synthesis modification for the preparation of a novel chiral fluorescent covalent organic framework (COF) for selective recognization of imazamox enantiomers. In this study, chiral COF was firstly synthesized via a Schiff-base reaction between 2,5-dihydroxyterephthalaldehyde (Dha) and 1,3,5-tris(4-aminophenyl)benzene (Tab) followed by a nucleophilic substitution using (1S)-(+)-10-camphorsulfonyl chloride as chiral modifier. The resulting regular spherical chiral COF Dha Tab not only presented the high optical efficiency, strong covalent bond structure, good crystallinity, large specific surface area but also showed the specific enantioselectivity and quick identification for imazamox enantiomers among five pesticide enantiomers (S/R-imazamox, acephate, acetochlor, propisochlor and metalaxyl). The detection limits for S- and R-imazamox were 4.20 µmol/L and 3.03 µmol/L, respectively. Meanwhile, the enantiomeric excess value (5.30 %) manifested that the chiral COF Dha Tab had the strong adsorption ability to imazamox enantiomers and more higher affinity for R-imazamox. This chiral fluorescent COF opened up a new way for the recognition of enantiomers.

Chemiluminescence resonance energy transfer determination of uric acid with fluorescent covalent organic framework as energy acceptor.

A simple and feasible strategy was developed for the preparation of fluorescent covalent organic frameworks (COFs) TpPa-1@FL. The TpPa-1-1@FL was prepared via a self-assembly strategy by soaking non-fluorescent COFs TpPa-1 into strong fluorescent fluorescein (FL) solution. A chemiluminescence resonance energy transfer (CRET) system was constructed by the combination strong fluorescent TpPa-1@FL with TCPO-hydrogen peroxide (H2O2) reaction. The chemiluminescence (CL) signal of the system was further improved by the addition of bovine serum albumin (BSA). The CRET system can determine H2O2 with a linear range response from 5.0 µmol/L to 20.0 mmol/L and a detection limit of 1.1 µmol/L. The CRET system was further exploited for indirect detection of uric acid with coupling of uricase. A good linear relationship was obtained for uric acid in the 10.0-400.0 µmol/L concentration range with a detection limit of 3.8 µmol/L. The practicability of this method was assessed by the determination of uric acid in real samples of human serum and urine.

Highly Crystalline Covalent Organic Frameworks Act as a Dual-Functional Fluorescent-Sensing Platform for Myricetin and Water, and Adsorbents for Myricetin.

Selective detection of active ingredients in complex samples has always been a crucial challenge because there are many disturbing compounds, especially structural analogues that interfere with the detection. In this work, a fluorescent covalent organic framework (named COF-TD), which can be used for the selective fluorescence detection and enrichment of myricetin from complex samples, was reported for the first time. The highly crystalline COF-TD with bright blue fluorescence was formed through a solution polymerization method by the condensation reaction between 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde. Due to spatial size selectivity, multisites hydrogen bonding, and π-π interaction, myricetin can quench the fluorescence of COF-TD with an inner filter effect (IFE) and static quenching mechanisms as well as can be enriched on COF-TD. Myricetin can observably eliminate the interference of other compounds and selectively quench the fluorescence of COF-TD with a limit of detection (LOD) of 0.30 µg·mL-1. The high adsorption ability of COF-TD (Q = 124.6 mg·g-1) to myricetin was also obtained. Finally, a sensing platform based on COF-TD for myricetin was successfully developed and applied for the detection of myricetin from vine teas. In addition, COF-TD also showed good water sensing ability and could be used effectively to detect water content in organic solvent (1-18% water in acetone, 0.5-5% water in acetonitrile, 1-4.5% water in ethyl acetate, v/v). To the best of our knowledge, this is the first report where COF-TD was used to detect water in a relatively wide concentration range. In all, this work provided dual-functional fluorescent COFs with the properties of an adsorbent, opening up new methodologies for the simple, selective, and enrichment detection method for myricetin.