Thiocarbamide conversion-based nitrogen-rich covalent organic framework coatings for electro-enhanced solid-phase microextraction of bisphenols.

Design and preparation of fiber coatings with excellent electrochemical performance and high polarity is significant for efficient extraction of polar targets in electro-enhanced solid-phase microextraction (EE-SPME). In this work, a combination strategy for structure regulation of covalent organic framework (COF) was proposed to fabricate a nitrogen-rich thiocarbamide linked COF coating (Thiocarbamide-TZ-DHTP) via molecular design and post-synthetic thiocarbamide conversion. The prepared COF coating possesses a large number of O, N, and S functional groups, which not only endow the coating with higher polarity but also significantly enhance its electrochemical performance. The COF coating was used for EE-SPME of polar bisphenols (BPs), demonstrating excellent enrichment efficiency and durability. Subsequently, coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS), a sensitive method was developed for determination of trace BPs. The established method possess wide linear ranges (2.0-800.0 ng L-1), good correlation coefficients (0.9985-0.9994) and low detection limits (0.1-2.0 ng L-1). Moreover, the established method had been successfully applied to detection of trace BPs in tea beverage with satisfactory recoveries (81.6 % to 118.6 %). This research provides a feasible pathway for preparing COF coating with excellent electrochemical performance and high polarity for EE-SPME.

Flexible filament winding strategy to prepare COF@polyionic liquid-coated fibers for non-selective exclusion of macromolecules in electro-enhanced solid-phase microextraction.

BACKGROUND: Accurate quantitative analysis of small molecule metabolites in biological samples is of great significance. Hydroxypolycyclic aromatic hydrocarbons (OH-PAHs) are metabolic derivatives of emerging pollutants, reflecting exposure to polycyclic aromatic hydrocarbons (PAHs). Macromolecules such as proteins and enzymes in biological samples will interfere with the accurate quantification of OH-PAHs, making direct analysis impossible, requiring a series of complex treatments such as enzymatic hydrolysis. Therefore, the development of matrix-compatible fiber coatings that can exclude macromolecules is of great significance to improve the ability of solid-phase microextraction (SPME) technology to selectively quantify small molecules in complex matrices and achieve rapid and direct analysis. RESULTS: We have developed an innovative coating with a stable macromolecular barrier using electrospinning and flexible filament winding (FW) technologies. This coating, referred to as the hollow fibrous covalent organic framework@polyionic liquid (F-COF@polyILs), demonstrates outstanding conductivity and stability. It accelerates the adsorption equilibrium time (25 min) for polar OH-PAHs through electrically enhanced solid-phase microextraction (EE-SPME) technology. Compared to the powder form, F-COF@polyILs coating displays effective non-selective large-size molecular sieving. Combining gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS/MS), we have established a simple, efficient quantitative analysis method for OH-PAHs with a low detection limit (0.008-0.05 ng L-1), wide linear range (0.02-1000 ng L-1), and good repeatability (1.0%-7.3 %). Experimental results show that the coated fiber exhibits good resistance to matrix interference (2.5%-16.7 %) in complex biological matrices, and has been successfully used for OH-PAHs analysis in human urine and plasma. SIGNIFICANCE: FW technology realizes the transformation of the traditional powder form of COF in SPME coating to a uniform non-powder coating, giving its ability to exclude large molecules in complex biological matrices. A method for quantitatively detecting OH-PAHs in real biological samples was also developed. Therefore, the filament winding preparation method for F-COF@polyILs coated fibers, along with fibrous COFs' morphology control, has substantial implications for efficiently extracting target compounds from complex matrices.

Mechanochemical synthesis ionic covalent organic frameworks/cotton composites for pipette tip solid-phase extraction of domoic acid in seafood.

Pipette tip solid-phase extraction (PT-SPE) as a miniaturized solid-phase extraction technique have a wide range of applications in the field of sample pretreatment. In this study, ionic covalent organic frameworks@cotton (iCOF@cotton) were facilely synthesized by mechanochemical grinding method only in half an hour, and used as the adsorbents of PT-SPE. The synthesized iCOF@cotton not only had high specific surface area, suitable pore structure and cationic charge groups of iCOF that can extract polar targets quickly, but also reduced the problem of high back pressure of PT-SPE by the addition of cotton, thus accelerating extraction time. Combined with high performance liquid chromatographic tandem mass spectrometry (HPLC-MS/MS), an efficient and sensitive method was established for detection of domoic acid (DA, a toxin produced by algae). Under the optimal conditions, the proposed analysis method displayed excellent analytical performance, including broad range of linearity (10-1000 pg mL-1), low limit of detection (LOD, 5 pg mL-1), high correlation coefficient (0.9993), satisfactory precision (RSDs ≤6.4 %). In addition, the developed method was applied to the detection of DA in marine samples, and detected trace DA (18.6 pg mL-1) with satisfactory recovery (85.7%-107.2 %). The above results indicated that the prepared iCOF@cotton have great potential as the adsorbents for PT-SPE.

Synthesis of stable and efficient amide-based covalent organic frameworks fiber coatings for the improved solid-phase microextraction of polar aromatic amines.

BACKGROUND: Developing facile and general functionalization strategies to improve the durability of covalent organic framework (COF) coatings and their affinity for polar targets is of great significance for solid-phase microextraction (SPME) technology. RESULTS: In this work, a facile and general amidation strategy was developed for conversion from reversible (imine) to irreversible (amide) linkages in COF coatings. After the amidation, the durability of the obtained amide-linked covalent organic framework (Am-P-COF) coating was greatly improved, and the adsorption efficiency for polar aromatic amines (AAs) was also significantly increased. Moreover, this strategy is also applicable to the amidation of other two COF coatings, showing good general applicability. The obtained Am-P-COF coated fiber was used for SPME, and then coupled with gas chromatography tandem mass spectrometry (GC-MS/MS) to detect AAs. Under the optimal SPME conditions (extraction temperature: 50 °C, extraction time: 30 min, stirring rate: 600 rpm, pH: 8, NaCl concentration: 5.0 mg mL-1, desorption temperature: 290 °C and desorption time: 10 min), a detection method for trace AAs was established. The established method possess wide linear ranges (0.5-500.0 ng L-1), good correlation coefficients (0.9986-0.9993) and low detection limits (0.1-0.5 ng L-1). Moreover, the established method had also been successfully applied to detection of trace AAs in bottled tea beverage and plastic bags packed tea with satisfactory recoveries (83.5 %-116.8 %). SIGNIFICANCE AND NOVELTY: This research provides a facile and general pathway for increasing the durability of COF coatings and affinity to the polar AAs. The detection method based on the obtained fibers possesses high sensitivity, satisfactory reproducibility and good precision.

Multimode optical switch based on cascaded Mach-Zehnder interferometer waveguides.

We present a 1 × 1 multimode optical switch for E11, E21, E12, and E22 modes based on cascaded Mach-Zehnder interferometer (MZI) waveguides, where the primary MZI is used to split E11, E21, E12, and E22 modes into E11 or E12 mode and then couple back to the original mode at the output, and the secondary MZIs are the modulation arms of the primary MZI. In addition, the secondary MZIs are designed to be mode-insensitive for switching E11 and E12 modes simultaneously. As a proof of concept, we fabricate the device with polymer material to achieve thermo-optic switching for the four modes. Our experimental device exhibits the extinction ratios of larger than 10.2 dB with a power consumption of 5.5 mW and response times of less than 1.28 ms for each mode. The presented device can be widely applied in mode-division multiplexing (MDM) systems where multimode switching is needed.

Mode-independent thermo-optic switch based on the total-internal-reflection effect.

A broadband mode-independent thermo-optic (TO) switch using the total-internal-reflection (TIR) effect is proposed and experimentally demonstrated on a polymer waveguide platform. By optimizing geometric parameters of the TIR switch, a mode-independent TO switching function with a large bandwidth and extinction ratio can be realized for E11, E12, and E21 modes. The measurement results show an extinction ratio larger than 18.1 dB with a driving power of 160 mW for each mode over the wavelength range of 1500-1620 nm. The designed structure can also be cascaded to form a 1 × N switch network for mode-division multiplexing (MDM) systems, which greatly improves the network flexibility.

1 × 2 mode-independent polymeric thermo-optic switch based on a Mach-Zehnder interferometer with a multimode interferometer.

We present the design and performances of a broadband 1 × 2 mode-independent thermo-optic (TO) switch based on Mach-Zehnder interferometer (MZI) with multimode interferometer (MMI). The MZI adopts a Y-branch structure as the 3-dB power splitter and a MMI as the coupler, which are designed to be insensitive to the guided modes. By optimizing the structural parameters of the waveguides, mode-independent transmission and switching functions for E11 and E12 modes can be implemented in the C + L band, and the mode content of the outputs is the same as the mode content of the inputs. We proved the working principle of our design based on polymer platform, which was fabricated by using ultraviolet lithography and wet-etching methods. The transmission characteristics for E11 and E12 modes were also analyzed. With the driving power of 5.9 mW, the measured extinction ratios of the switch for E11 and E12 modes are larger than 13.3 dB and 13.1 dB, respectively, over a wavelength range of 1530 nm to 1610 nm. The insertion losses of the device are 11.7 dB and 14.2 dB for E11 and E12 modes, respectively, at 1550 nm wavelength. The switching times of the device are less than 840 µs. The presented mode-independent switch can be applied in reconfigurable mode-division multiplexing systems.

Carboxylated mesoporous carbon hollow spheres for the efficient solid-phase microextraction of aromatic amines.

An efficient and stable fiber coating is of great importance for solid-phase microextraction (SPME). In this study, carboxylated mesoporous carbon hollow spheres (MCHS-COOH) were developed as an efficient SPME coating of polar aromatic amines (AAs) for the first time. The MCHS-COOH coating material with high specific surface area (1182.32 m2 g-1), large pore size (10.14 nm), and rich oxygen-containing groups was fabricated via a facile H2O2 post-treatment. The as-prepared MCHS-COOH-coated fiber exhibited fast adsorption rate and excellent extraction properties, mainly due to its π-π interactions, hollow structure, and abundant affinity sites (carboxyl groups). Subsequently, coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS), a sensitive method with low limits of detection (0.08-2.0 ng L-1), a wide linear range (0.3-500.0 ng L-1), and good repeatability (2.0-8.8%, n = 6) was developed for the analysis of AAs. The developed method was validated against three river water samples, with satisfactory relative recoveries being obtained. The above results demonstrated that the prepared MCHS-COOH-coated fiber exhibited good adsorption capacity, suggesting a promising application to monitor trace polar compounds in real environment.

Room temperature synthesis of flower-like hollow covalent organic framework for efficient enrichment of microcystins.

The morphology of nanomaterials is one of essential factors for their unique properties. Herein, a hollow covalent organic framework with a flower-like structure (HFH-COF) was synthesized at room temperature. The synthesized HFH-COF has a very large specific surface area, mesoporous structure, excellent chemical stability, and good crystallinity. The special morphology endowed HFH-COF with high specific surface area utilization and rapid mass transfer rate, resulting in faster equilibration time and better extraction performance than spherical COF (S-COF). Subsequently, combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), an efficient and sensitive method was established for microcystins (MCs) detection. The developed method has low detection limits (0.6-0.8 pg mL-1), wide linear ranges (1.5-1000.0 pg mL-1, R ≥ 0.9993), and acceptable reproducibility (RSD ≤ 7.6%, n = 6). Real biological samples were analyzed by the developed method, and trace levels of MC-YR, MC-RR and MC-LR were detected. The results indicate that the synthesized HFH-COF is an ideal sorbent for efficient extraction of MCs from complex biological samples.

Piperazine-linked metal covalent organic framework-coated fibers for efficient electro-enhanced solid-phase microextraction of chlorophenols.

Conductive covalent organic frameworks (COFs) have received considerable attention and are critical in various applications such as electro-enhanced solid-phase microextraction (EE-SPME). In this work, a novel piperazine-linked copper-doped phthalocyanine metal covalent organic framework (CuPc-MCOF) was synthesized with good stability and high electrical conductivity. The synthesized CuPc-MCOF was then used as an EE-SPME coating material for extraction of five trace chlorophenols (CPs), including 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,4,5-trichlorophenol (2,4,5-TCP) and 2,4,5,6-tetrachlorophenol (2,4,5,6-TCP), exhibiting excellent extraction performance because of various synergistic forces between CuPc-MCOF fibers and CPs. By combining EE-SPME with gas chromatography-tandem mass spectrometry (GC-MS/MS), a sensitive method for CPs detection was established with a low limit of detection (0.8-5 ng L-1) and good reproducibility (RSD≤8.4%, n = 3). This method was then successfully applied to the analysis of trace CPs in real samples of seawater and seafood. Results showed that the developed CuPc-MCOF coating material possessed superior extraction performance and potential application in extraction of trace polar pollutants from complex samples.

Rapidly covalent immobilization of ß-ketoenamine-linked covalent organic framework on fibers for efficient solid-phase microextraction of phthalic acid esters.

Rapid and convenient preparation of covalent organic framework (COF) coated fibers is of great significance to solid-phase microextraction (SPME) technology. In this work, a novel chemical preparation strategy was established for rapid fabrication of ß-ketoenamine-linked COF coatings, in which clay-like starting materials of COFs were first wrapped on the fiber surface through self-viscosity and further fixed on the fiber in an oven via chemical bonding. Based on this strategy, four different COF (TpTph, TpPa-1, TpBD and TpTpb) coated fibers was fabricated within 1 h, which is very rapid compared to the recently reported research. Moreover, the strategy also demonstrates the good general applicability for COF fiber preparation. Subsequently, the TpTph coated fiber was used to develop a new SPME method for gas chromatography-tandem mass spectrometry (GC-MS/MS) of trace phthalic acid esters (PAEs) in environmental water. The developed analytical method compared to the previous SPME methods for PAEs based on other sorbents possesses low limits of detection (LODs, 0.02-0.08 ng L-1), and better or comparable precision (RSD ≤9.4%, n = 6), and relatively short extraction time. Furthermore, the trace PAEs (0.27-11.62 ng L-1) in the real water samples were successfully detected with recoveries of 82.2-117.5%. The above results indicates that the proposed fiber preparation strategy is reliable and opens a potential avenue for rapid and facile fabrication of COF coated fibers.

Experimental Investigation of Bubble Migration near Anisotropic Beams.

In order to resist bubble loading, anisotropic composite materials are the development direction of the future. The objective of this paper was to experimentally investigate the hydrodynamic performance of anisotropic laminate composite plates, with a focus on the effect of its anisotropic characteristics on single bubble migration. In these experiments, the bubble was generated in a transparent water tank filled with sufficiently degassed water by Joule heating at the connecting point of the electrodes through the discharge of a 6600 µF charge to 800 V, and a high-speed camera system with a recording speed of 40,000 frames per second was used to record the temporal evolution of bubble patterns and the dynamic responses of the laminated composite plates. The results are presented for two anisotropic cantilever composite beams with different ply angles, namely, 0° and 30°. Several variables, such as the shapes of the bubble, the curved trail of motion of the bubble center, bubble collapse time, and bubble initial standoff distances were extracted from the photographic images. The results showed that bubble migration near the 30° plate presents a curved bubble trail with an evident tilted angle during the collapse and rebound stages, which is very different from bubbles that all move vertically above the 0° plate. Furthermore, a characterization method for bubble migration was proposed to quantitatively describe the curved bubble trails and the deformation of the composite beams in temporal and spatial scales. This method shows that the curved bubble trails near the 30° plate are closely related to the dynamic response of composite beams, with a focus on the bending-twisting coupling effect.

Polymer/silica hybrid 3D waveguide thermo-optic mode switch based on cascaded asymmetric directional couplers.

A polymer/silica hybrid 3D waveguide thermo-optic (TO) mode switch based on cascaded asymmetric directional couplers (ADCs) is theoretically designed and simulated, where the spatial modes of a few-mode silica waveguide can be switched to various single-mode polymer waveguides placed above the few-mode silica waveguide. A beam propagation method is employed to optimize the dimensional parameters of the mode switch to convert the LP11a and LP11b modes of the few-mode silica waveguide to the LP01 mode of two single-mode polymer waveguides using the cascaded ADC 1 and ADC 2. The coupling ratios are higher than 96.4% (93.4%) and 95.1% (92.8%) for the ADC 1 and ADC 2, respectively, under the TE (TM) polarization within the wavelength range from 1530 to 1570 nm, which shows good wavelength independence. Furthermore, the monolayer graphene is introduced as the heating electrode and buried on the surface of the polymer core to increase the heating efficiency and reduce the power consumption. The power consumption for ADC 1 and ADC 2 is 16.69 mW and 17.35 mW, respectively. Compared to the traditional TO switch with an aluminum (Al) heating electrode, the heating efficiency of the presented device can be improved by ∼30%. Moreover, the response speed of the TO mode switch with a 3D waveguide structure was also significantly improved. Compared to the device with Al electrodes, the introduced graphene electrodes can improve the switching speed of the device by ∼60%. The presented TO mode switch with its small size and easy integration should find applications in reconfigurable mode division multiplexing systems.

In situ room-temperature rapidly fabricated imine-linked covalent organic framework coated fibers for efficient solid-phase microextraction of pyrethroids.

A facile and rapid strategy for preparation of covalent organic framework (COF) coated fibers at ambient temperature is urgently needed for solid-phase microextraction (SPME) technology. In this work, an in situ room-temperature rapid growth strategy was developed to high-efficiently fabricate imine-linked COF (TPB-DVA) coated fibers in as little as 30 min at room temperature, and the thickness of the coating reached 9 µm. The prepared TPB-DVA coated fiber offer high thermal and chemical stability, and outstanding service lifetime. Moreover, we generalize this strategy to other two imine-linked COF (TPB-DMTP and TFPB-TAPB) coated fibers and the fibers were fabricated at room temperature for 3 h and 12 h, respectively, which demonstrate the applicability of this strategy. Subsequently, a SPME-GC-MS/MS analytical method was developed for trace pyrethroids (PYs) detection, which exhibited high enhancement factors (EFs, 2700-13195), wide linear range (0.08-800 ng L-1), low limits of detection (LODs, 0.02-0.20 ng L-1), and good repeatability (RSD ≤ 8.5%, n = 6). Furthermore, the developed analytical method was applied to tea samples and trace PYs (1.31-4.32 ng L-1) were found with satisfactory recovery (80.2-119.8%). The above results demonstrated that the feasibility of the developed strategy for the facile and rapid fabrication of imine-linked COF coated fibers.

[Preparation of covalent organic framework based on room temperature solution-suspension approach and its application to solid-phase microextraction of pyrethroids in tea].

Pyrethroids (PYs) have been widely used to control pests and prevent diseases in tea gardens. However, with the increasingly stringent pesticide testing standards in the import and export trade of tea, there is an urgent need for methods to detect trace amounts of PYs in tea. In this study, a covalent organic framework (COF) material TpBD with excellent thermal/chemical stability, high porosity, and a large specific surface area was prepared by a room-temperature solution-suspension approach (SSA). TpBD-coated solid phase microextraction (SPME) fibers were fabricated by coating the material on etched stainless-steel fibers by a simple physical coating method. The fibers were used in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS) to establish a highly sensitive method for the detection of PYs. The enrichment factors of this method for cyfluthrin, cypermethrin, flucythrinate, fenvalerate, and deltamethrin were 702-2687. The method showed low LODs (0.1-0.5 ng/L), wide linear ranges (0.2-800 ng/L), good linearities (correlation coefficients (R)≥0.9991) and acceptable repeatabilities (RSD≤11.0%, n=3). Green tea and oolong tea samples were analyzed using the developed method, and trace levels of the five PYs were successfully detected. The recoveries of the spiked PYs in the real green tea and oolong tea samples were in the range of 80.2%-109.5%. Experimental results showed that the established analytical method is suitable for the determination of PY pesticides in tea. Furthermore, the TpBD material was successfully prepared by the SSA method, demonstrating that the method has good universality and excellent potential for the simple synthesis of other COF materials.

Thermodynamic effect of single bubble near a rigid wall.

The objective of this paper is to numerically investigate the thermodynamic effect during bubble collapse near a rigid boundary. A compressible fluid model is introduced to accurately capture the transient process of bubble shapes and temperature, as well as corresponding pressure, and velocity. The accuracy of the numerical model is verified by the experimental data of bubble shapes, and Keller-Kolodner equation as well as its thermodynamic equation. The results show that a bubble near the rigid boundary presents high-speed jet in collapse stage and counter jet in rebound stage, respectively. In the collapse stage, the bubble margin will shrink rapidly and do the positive work on the compressible vapor inside the bubble, then a significant amount of heat will be generated, and finally the generation of high-speed jet drives the low-temperature liquid outside the bubble to occupy the position of high-temperature vapor inside the bubble. In the rebound stage, the counter jet moving away from the rigid boundary takes part of heat away from the sub-bubble, which avoids the external work of the expansion of the sub-bubble and the temperature reduction caused by the dissipation effect of the vortex structure. In addition, the initial standoff has a significant effect on the thermodynamics of bubble oscillation. The temperature keeps increasing with the increase of the initial standoff in the collapse stage, while it shows a downward trend with the increase of the initial standoff in the rebound stage. That's because the high-speed jet and counter jet of bubble gradually disappear when the initial standoff increases, which is the important reason for the opposite evolution trend of temperature in collapse and rebound stage.

PIV-Based Acoustic Pressure Measurements of a Single Bubble near the Elastic Boundary.

The objective of this paper was to investigate acoustic pressure waves and the transient flow structure emitted from the single bubble near an elastic boundary based on the particle image velocimetry (PIV). A combination of an electric-spark bubble generator and PIV were used to measure the temporal bubble shapes, transient flow structure, as well as the mid-span deflection of an elastic boundary. Results are presented for three different initial positions near an elastic boundary, which were compared with results obtained using a rigid boundary. A formula relating velocity and pressure was proposed to calculate the acoustic pressure contours surrounding a bubble based on the velocity field of the transient flow structure obtained using PIV. The results show the bubbles near the elastic boundary presented a "mushroom" bubble and an inverted cone bubble. Based on the PIV-measured acoustic pressure contours, a significant pressure difference is found between the elastic boundary and the underside of the bubble, which contributed to the formation of the "mushroom" bubble and inverted cone bubble. Furthermore, the bubbles had opposite migration direction near rigid and elastic boundaries, respectively. In detail, the bubble was repelled away from the elastic boundary and the bubble was attracted by the rigid boundary. The resultant force made up of a Bjerknes force and buoyancy force dominated the migration direction of the bubble.

Comparison of electron capture-atmospheric pressure chemical ionization and electrospray ionization for the analysis of gambogic acid and its main circulating metabolite in dog plasma.

Gambogic acid (GA), a promising anticancer candidate, is a polyprenylated xanthone abundant in the resin of Garcinia morella and Garcinia hanburyi. Electron capture-atmospheric pressure chemical ionization (EC- APCI) and electrospray ionization (ESI) techniques, both in the negative ion mode, were evaluated regarding ionization, fragmentation patterns and sensitivity for simultaneous liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of GA and its main circulating metabolite, 10-hydroxygambogic acid (10-OHGA) in dog plasma. Both analytes underwent extensive in-source fragmentation in EC-APCI, which was not desirable for reliable quantification of these analytes, whereas the substitution of ESI for EC-APCI almost eliminated the source instability of both analytes. Negative ion ESI was, therefore, chosen for the development of an LC-MS/MS method for simultaneous determination of these analytes. After protein precipitation by acetonitrile, all analytes were separated on a Luna C18 HST column (50 x 2.0 mm i.d., 2.5 microm) with a mobile phase of 20 mmol L(-1) ammonium acetate water solution containing 0.2% acetic acid:acetonitrile (18:82, v/v). The detection was performed on a tandem mass spectrometer using selective reaction monitoring mode. Calibration curves were linear over the range of 10-6000 ng mL(-1) for GA and 3-2000 ng mL(-1) for 10-OHGA. The method was successfully applied to the pharmacokinetics study of GA injection in six beagle dogs.