Size-Dependent Deformation and Competition H-Bond Site-Induced Individual Fluorescence Response of a Single-Crystal Three-Dimensional Covalent Organic Framework.

Understanding the individual fluorescence response mechanism of covalent organic frameworks (COFs) at a single-crystal level is of great significance for the rational design of COF-based microsensors but unreachable because all previous COF-based sensors are performed with average fluorescence response behavior of various sized polycrystalline COFs. Herein, we design to explore the fluorescence response of a monodisperse single-crystal COF and further reveal the individual heterogeneity of the response mechanism. Three-dimensional single-crystal COF-301 (SCOF-301) with an intramolecular H-bond-induced excited-state intramolecular proton-transfer effect is selected as a proof-of-concept SCOF. With ethanol, benzene, and ammonia as model analytes, three different deformation and competition H-bond site-induced fluorescence response mechanisms related to crystal size are revealed. Small single particles of SCOF-301 (SSCOF-301) exhibit a more flexible structure, leading to the dominant role of deformation in the fluorescence response of small-sized SSCOF-301. The decreasing flexibility of SSCOF-301 with the increase of crystal size results in involvement of competition of the H-bond site to the fluorescence response besides deformation. Further increase of the crystal size makes the large-sized SSCOF-301 difficult to deform; thus, the competition of the H-bond site dominates the fluorescence response. This work provides a deep understanding of the individual fluorescence response mechanism of COFs to guide the design of a functional COF sensor with suitable size and mechanism for different structural analytes.

Integrating Ordered Two-Dimensional Covalent Organic Frameworks to Solid-State Nanofluidic Channels for Ultrafast and Sensitive Detection of Mercury.

Grafting specific recognition moieties onto solid-state nanofluidic channels is a promising way for selective and sensitive sensing of analytes. However, the time-consuming interaction between recognition moieties and analytes is the main hindrance to the application of nanofluidic channel-based sensors in rapid detection. Here, we show the integration of ordered two-dimensional covalent organic frameworks (2D COFs) to solid-state nanofluidic channels to achieve rapid, selective, and sensitive detection of contaminants. As a proof of concept, a thiourea-linked 2D COF (JNU-3) as the recognition unit is covalently bonded on the stable artificial anodic aluminum oxide nanochannels (AAO) to fabricate a JNU-3@AAO-based nanofluidic sensor. The rapid and selective interaction of Hg(II) with the highly ordered channels of JNU-3 allows the JNU-3@AAO-based nanofluidic sensor to realize ultrafast and precise determination of Hg(II) (90 s) with a low limit of detection (3.28 fg mL-1), wide linear range (0.01-100 pg mL-1), and good precision (relative standard deviation of 3.8% for 11 replicate determination of 10 pg mL-1). The developed method was successfully applied to the determination of mercury in a certified reference material A072301c (rice powder), real water, and rice samples with recoveries of 90.4-99.8%. This work reveals the great potential of 2D COFs-modified solid-state nanofluidic channels as a sensor for the rapid and precise detection of contaminants in complicated samples.

Aptamer Self-Assembly-Functionalized Nanochannels for Sensitive and Precise Detection of Chloramphenicol.

Sensitive and precise determination of chloramphenicol (CAP) is of great significance for human health due to its high risk in trace amounts. Solid-state artificial nanochannels are expected to be highly promising sensing devices owing to single-molecule sensitivity, target-specific selectivity, and portability. Herein, we report an aptamer self-assembly-functionalized artificial nanochannel-based sensor for highly sensitive and precise determination of CAP. Aptamer self-assembly (AAs) served as the specific recognition component and were in situ grown on the surface of stable anodic aluminum oxide (AAO) nanochannels to develop an AAs@AAO nanochannel-based sensor. Selective interaction with CAP led to the disassembly of AAs and sensitive current change of AAs@AAO nanochannels, allowing sensitive and precise sensing of CAP in complex food samples. The developed AAs@AAO nanochannel-based sensor showed a wide linear range from 0.32 to 1600 pg. mL-1, low limit of detection (LOD) of 0.1 pg. mL-1, high precision with relative standard deviation of 2.9%, and quantitative recoveries of 93.4-102.2% for CAP in milk, milk powder, and honey samples. This work proposes a versatile nanochannel-based platform for facile, sensitive, and precise sensing of hazardous residues in food samples.

Engineering of molecularly imprinted cavity within 3D covalent organic frameworks: An innovation for enhanced extraction and removal of microcystins.

The scarcity of selective adsorbents for efficient extraction and removal of microcystins (MCs) from complex samples greatly limits the precise detection and effective control of MCs. Three-dimensional covalent organic frameworks (3D COFs), characterized by their large specific surface areas and highly ordered rigid structure, are promising candidates, but suffer from lack of specific recognition. Herein, we design to engineer molecularly imprinted cavities within 3D COFs via molecularly imprinted technology, creating a novel adsorbent with exceptional selectivity, kinetics and capacity for the efficient extraction and removal of MCs. As proof-of-concept, a new CC bond-containing 3D COF, designated JNU-7, is designed and prepared for copolymerization with methacrylic acid, the pseudo template L-arginine and ethylene dimethacrylate to yield the JNU-7 based molecularly imprinted polymer (JNU-7-MIP). The JNU-7-MIP exhibits a great adsorption capacity (156 mg g-1) for L-arginine. Subsequently, the JNU-7-MIP based solid-phase extraction coupled with high performance liquid chromatography-mass spectrometry achieves low detection limit of 0.008 ng mL-1, wide linear range of 0.025-100 ng mL-1, high enrichment factor of 186, rapid extraction of 10 min, and good recoveries of 92.4%-106.5% for MC-LR. Moreover, the JNU-7-MIP can rapidly remove the MC-LR from 1 mg L-1 to levels (0.26-0.35 µg L-1) lower than the WHO recommended limit for drinking water (1 µg L-1). This work reveals the considerable potential of 3D COF based MIPs as promising adsorbents for the extraction and removal of contaminants in complex real samples.

Irreversible fluorine covalent organic framework based probe nanoelectrospray ionization mass spectrometry for direct and rapid determination of perfluoroalkyl carboxylic acids.

Probe nanoelectrospray ionization mass spectrometry (PESI-MS) is practically desirable for rapid and ultra-sensitive analysis of trace contaminants in environment, but limited with the stable and selective probe coating. Herein, we show the design and preparation of irreversible fluorine-based covalent organic framework (TFPPA-F4) covalently bonded probe to couple with ESI-MS (TFPPA-F4-PESI-MS) for direct and rapid determination of perfluoroalkyl carboxylic acids (PFCAs) in environmental water. Chemical bonding coating of irreversible crystalline TFPPA-F4 not only improved stability of the probe, but also offered accessible multiple interactions including hydrophobic, hydrogen bonding and F-F interactions to promote the kinetics and selectivity for PFCAs. The proposed TFPPA-F4-PESI-MS realized rapid determination of PFCAs (about 4 min) with low limits of detection of 0.06-0.88 ng L-1 and wide linear range of 1-5000 ng L-1 (R2 of 0.9982-0.9998). Recoveries for the spiked lake and pond water were 85.9-111.1 %. TFPPA-F4 based probe can maintain the extraction performance after 100 times of extraction. This work shows the great potential of the irreversible covalent organic framework based PESI-MS in rapid and ultra-sensitive determination of contaminants in environmental samples.

Pure Covalent-Organic Framework Membrane as a Label-Free Biomimetic Nanochannel for Sensitive and Selective Sensing of Chiral Flavor Substances.

Chiral flavor substances play an important role in the human perception of different tastes. Here, we report a pure covalent-organic framework (COF) membrane nanochannel in combination with a chiral gold nanoparticles (AuNPs) selector for sensing chiral flavor substances. The pure COF membrane with a proper pore size is selected as the nanochannel, while l-cysteine-modified AuNPs (l-Cys-AuNPs) are used as the chiral selector. l-Cys-AuNPs show stronger binding to the S-enantiomer than the R-enantiomer, causing current reduction to different degrees for the R- and S-enantiomer to achieve chiral sensing due to the synergistic effect of the size exclusion of the COF nanochannel and the chiral selectivity of l-Cys-AuNPs. The developed COF membrane nanochannel sensing platform not only allows an easy balance of the permeability and selectivity, which is difficult to achieve in traditional polymer membrane nanochannel sensors, but also exhibits better chiral performance than commercial artificial anodic aluminum oxide (AAO) nanochannel sensors. The developed nanochannel sensor is successfully applied for sensing flavor enantiomers such as limonene, propanediol, methylbutyric acid, and butanol with the enantiomer excess values of 55.2% (propanediol) and 72.4% (limonene) and the low detection limits of 36 (limonene) and 71 (propanediol) ng L-1. This study provides a new idea for the construction of nanochannel platforms based on the COF for sensitive and selective chiral sensing.

Engineering linkage as functional moiety into irreversible thiourea-linked covalent organic framework for ultrafast adsorption of Hg(II).

Development of novel functionalized covalent organic frameworks (COFs) as adsorbent for removal of mercury from environment is of great significance, but the conventional strategies for functionalizing COFs always sacrifice porous properties and suppress the exposure of functional sites, which goes against the rapid adsorption of Hg(II). Here, we show the rational design and preparation of the first thiourea-linked COFs via engineering the COFs linkage as functional moiety for ultrafast and selective adsorption of Hg(II). Two thiourea-linked COFs JNU-3 and JNU-4 were prepared via tautomerism reaction of 1,3,5-triformylphloroglucinol with 1,4-phenylenebis(thiourea) and 1,4-biphenylenebis(thiourea), respectively. The thiourea serves as not only linkage to connect the building block into irreversible crystalline structure, but also functional moiety to give no occupation of the COF pore and full exposure to Hg(II) with strong affinity, offering the JNU-3 and JNU-4 large adsorption capacity (960 and 561 mg g-1, respectively) and ultrafast kinetics (equilibrium time of 10 s) for Hg(II). The proposed strategy for the design of functional COFs with inherent linkage as functional moiety largely promotes the performance of COFs for diverse applications.