Bioinspired Polydopamine Sheathed Nanofibers for High-Efficient in Vivo Solid-Phase Microextraction of Pharmaceuticals in Fish Muscle

In this study, electrospun nanofibers were used as solid-phase microextraction (SPME) fiber coatings after substituting the water-soluble sheath of the emulsion electrospun polystyrene (PS)@Plurinic F-127 core–sheath nanofibers with biocompatible and water-stable polydopamine (PDA) and subsequently being appropriately cross-linked with glutaraldehyde (GA) to enhance the strength of the electrospun architecture. The novel custom-made PS@PDA-GA coating was wettable in aqueous solutions and thus exhibited much higher extraction efficiency than the nonsheathed PS nanofiber coating and the thicker polydimethylsiloxane (PDMS) coating. The novel coating also possessed excellent stability (relative standard deviations (RSDs) less than 7.3% for six sampling-desorption cycles), interfiber reproducibility (RSDs less than 14.3%), and antibiofouling ability, which were beneficial for in vivo sampling. The PS@PDA-GA fiber was used to monitor pharmaceuticals in dorsal-epaxial muscle of living fish, and satisfactory sensitivities with the limits of detection in the range of 1.1 (mefenamic acid) to 8.9 (fluoxetine) ng·g^–1 and comparable accuracies to liquid extraction were achieved. In general, this study explored a convenient and effective method to sheath nanofibers for high-efficient in vivo SPME of analytes of interest in semisolid tissues

Novel Magnetic Microprobe with Benzoboroxole-Modified Flexible Multisite Arm for High-Efficiency <i>cis</i>-Diol Biomolecule Detection

With regard to regulating a variety of biological events, including molecular recognition, signal transduction, cell adhesion, and immune response, <i>cis</i>-diol biomolecules, such as saccharides and glycoproteins, play vital roles. However, saccharides and glycoproteins in living systems usually exist in very low abundance, along with abundant interfering components. High-efficiency detection of saccharides and glycoproteins is a challenging yet highly impactful area of research. Herein, we reported a novel magnetic microprobe with a benzoboroxole-modified flexible multisite arm (PEG 2000-grafted PAMAM dendrimers; the microprobe was denoted as BFMA-MNP) for high-efficiency saccharides detection. The extraction capacity was significantly improved by ∼2 orders of magnitude, because of the integration of the enhanced hydrophilicity and multivalency effects in benzoboroxoles and the enhanced accessibility of the binding sites within the PEG 2000-grafted PAMAM dendrimers. As a result, the proposed approach possessed several advantages, compared with previous boronic acid-based methods, including ultrahigh sensitivity (limit of detection was <1 ng/mL), wide linear range (ranged from 0.5 μM to 2000 μM), and applicable in physiological pH condition. Furthermore, we established a general BFMA-MNP/glycoproteins/AuNPs sandwich assay to realize the visual glycoprotein qualitative screening for the first time. The unique sandwich assay possessed the dual nature of the magnetic separation by BFMA-MNPs and specific coloration by citrate-coated AuNPs. This visual sandwich assay enabled fast differentiation of the existence of glycoproteins in complicated samples without any advanced instruments. We believe the proposed BFMA-MNP microprobe herein will advance the ideas to detect and identify trace saccharides and glycoproteins in important fields such as glycomics and glycoproteomics

Novel Electrosorption-Enhanced Solid-Phase Microextraction Device for Ultrafast In Vivo Sampling of Ionized Pharmaceuticals in Fish

Decreasing the tedious sample preparation duration is one of the most important concerns for the environmental analytical chemistry especially for in vivo experiments. However, due to the slow mass diffusion paths for most of the conventional methods, ultrafast in vivo sampling remains challenging. Herein, for the first time, we report an ultrafast in vivo solid-phase microextraction (SPME) device based on electrosorption enhancement and a novel custom-made CNT@PPY@pNE fiber for in vivo sampling of ionized acidic pharmaceuticals in fish. This sampling device exhibited an excellent robustness, reproducibility, matrix effect-resistant capacity, and quantitative ability. Importantly, the extraction kinetics of the targeted ionized pharmaceuticals were significantly accelerated using the device, which significantly improved the sensitivity of the SPME in vivo sampling method (limits of detection ranged from 0.12 ng·g^–1 to 0.25 ng·g^–1) and shorten the sampling time (only 1 min). The proposed approach was successfully applied to monitor the concentrations of ionized pharmaceuticals in living fish, which demonstrated that the device and fiber were suitable for ultrafast in vivo sampling and continuous monitoring. In addition, the bioconcentration factor (BCF) values of the pharmaceuticals were derived in tilapia (<i>Oreochromis mossambicus</i>) for the first time, based on the data of ultrafast in vivo sampling. Therefore, we developed and validated an effective and ultrafast SPME sampling device for in vivo sampling of ionized analytes in living organisms and this state-of-the-art method provides an alternative technique for future in vivo studies

Novel Electrosorption-Enhanced Solid-Phase Microextraction Device for Ultrafast In Vivo Sampling of Ionized Pharmaceuticals in Fish

Decreasing the tedious sample preparation duration is one of the most important concerns for the environmental analytical chemistry especially for in vivo experiments. However, due to the slow mass diffusion paths for most of the conventional methods, ultrafast in vivo sampling remains challenging. Herein, for the first time, we report an ultrafast in vivo solid-phase microextraction (SPME) device based on electrosorption enhancement and a novel custom-made CNT@PPY@pNE fiber for in vivo sampling of ionized acidic pharmaceuticals in fish. This sampling device exhibited an excellent robustness, reproducibility, matrix effect-resistant capacity, and quantitative ability. Importantly, the extraction kinetics of the targeted ionized pharmaceuticals were significantly accelerated using the device, which significantly improved the sensitivity of the SPME in vivo sampling method (limits of detection ranged from 0.12 ng·g^–1 to 0.25 ng·g^–1) and shorten the sampling time (only 1 min). The proposed approach was successfully applied to monitor the concentrations of ionized pharmaceuticals in living fish, which demonstrated that the device and fiber were suitable for ultrafast in vivo sampling and continuous monitoring. In addition, the bioconcentration factor (BCF) values of the pharmaceuticals were derived in tilapia (<i>Oreochromis mossambicus</i>) for the first time, based on the data of ultrafast in vivo sampling. Therefore, we developed and validated an effective and ultrafast SPME sampling device for in vivo sampling of ionized analytes in living organisms and this state-of-the-art method provides an alternative technique for future in vivo studies

In Situ Hydrothermally Grown TiO₂@C Core–Shell Nanowire Coating for Highly Sensitive Solid Phase Microextraction of Polycyclic Aromatic Hydrocarbons

Nanostructured materials have great potential for solid phase microextraction (SPME) on account of their tiny size, distinct architectures and superior physical and chemical properties. Herein, a core–shell TiO₂@C fiber for SPME was successfully fabricated by the simple hydrothermal reaction of a titanium wire and subsequent amorphous carbon coating. The readily hydrothermal procedure afforded in situ synthesis of TiO₂ nanowires on a titanium wire and provided a desirable substrate for further coating of amorphous carbon. Benefiting from the much larger surface area of subsequent TiO₂ and good adsorption property of the amorphous carbon coating, the core–shell TiO₂@C fiber was utilized for the SPME device for the first time and proved to have better performance in extraction of polycyclic aromatic hydrocarbons. In comparison to the polydimethylsiloxane (PDMS) and PDMS/divinylbenzene (DVB) fiber for commercial use, the TiO₂@C fiber obtained gas chromatography responses 3–8 times higher than those obtained by the commercial 100 μm PDMS and 1–9 times higher than those obtained by the 65 μm PDMS/DVB fiber. Under the optimized extraction conditions, the low detection limits were obtained in the range of 0.4–7.1 ng L^–1 with wider linearity in the range of 10–2000 ng L^–1. Moreover, the fiber was successfully used for the determination of polycyclic aromatic hydrocarbons in Pearl River water, which demonstrated the applicability of the core–shell TiO₂@C fiber

Study on the Diffusion-Dominated Solid-Phase Microextraction Kinetics in Semisolid Sample Matrix

Solid-phase microextraction (SPME) kinetics in semisolid samples should be different from that in aqueous and gaseous samples, as convection is negligible in semisolid samples but dominates mass transfer in bulk phases of aqueous and gaseous samples. This study developed a mathematical model for describing SPME kinetics in semisolid samples by considering the diffusion of analytes in two compartments, i.e., the fiber coating and the ever-increasing diffusion domain in the sample matrix. The mathematical model predicted that SPME and the desorption of preloaded analytes from the fiber would be isotropic in semisolid samples, while SPME in semisolid samples would not follow the first order kinetics as in aqueous and gaseous samples. The predictions were proven true in the experiment of four pharmaceuticals in agarose gel. In return, it was observed in the experiment that SPME kinetics would deviate more significantly from the first order kinetics for the analytes with higher partition coefficients between the fiber and the sample matrix, which was well explained by the mathematical model developed in this study. In addition, SPME kinetics predicted by the model coincided well with the experimental results when the diffusion coefficients were at reasonable levels, which demonstrated that the model could be satisfactory for describing SPME kinetics in semisolid samples. The illustration of the nonfirst order SPME kinetics in semisolid samples can be valuable for evaluating the applicability of the existing pre-equilibrium calibration methods in semisolid samples

<i>In Vivo</i> Tracing Uptake and Elimination of Organic Pesticides in Fish Muscle

Bioconcentration factors (BCFs) measured in the laboratory are important for characterizing the bioaccumulative properties of chemicals entering the environment, especially the potential persistent organic pollutants (POPs), which can pose serious adverse effects on ecosystem and human health. Traditional lethal analysis methods are time-consuming and sacrifice too many experimental animals. In the present study, <i>in vivo</i> solid-phase microextraction (SPME) was introduced to trace the uptake and elimination processes of pesticides in living fish. BCFs and elimination kinetic coefficients of the pesticides were recorded therein. Moreover, the metabolism of fenthion was also traced with <i>in vivo</i> SPME. The method was time-efficient and laborsaving. Much fewer experimental animals were sacrificed during the tracing. In general, this study opened up an opportunity to measure BCFs cheaply in laboratories for the registering of emerging POPs and inspecting of suspected POPs, as well as demonstrated the potential application of <i>in vivo</i> SPME in the study of toxicokinetics of pollutants

Observing Discrete Blocking Events at a Polarized Micro- or Submicro-Liquid/Liquid Interface

Single-entity collisional electrochemistry (SECE), a subfield of single-entity electrochemistry, enables directly characterizing entities and particles in the electrolyte solution at the single-entity resolution. Blockade SECE at the traditional solid ultramicroelectrode (UME)/electrolyte interface suffers from a limitation: only redox-inactive particles can be studied. The wide application of the classical Coulter counter is restricted by the rapid translocation of entities through the orifice, which results in a remarkable proportion of undetected signals. In response, the blocking effect of single charged conductive or insulating nanoparticles (NPs) at low concentrations for ion transfer (IT) at a miniaturized polarized liquid/liquid interface was successfully observed. Since the particles are adsorbed at the liquid/liquid interface, our method also solves the problem of the Coulter counter having a too-fast orifice translocation rate. The decreasing quantal staircase/step current transients are from landings (controlled by electromigration) of either conductive or insulating NPs onto the interface. This interfacial NP assembly shields the IT flux. The size of each NP can be calculated by the step height. The particle size measured by dynamic light scattering (DLS) is used for comparison with that calculated from electrochemical blocking events, which is in fairly good agreement. In short, the blocking effect of IT by single entities at micro- or submicro-liquid/liquid interface has been proven experimentally and is of great reference in single-entity detection

Polyelectrolyte Microcapsules Dispersed in Silicone Rubber for in Vivo Sampling in Fish Brains

Direct detection of fluoxetine and its metabolite norfluoxetine in living fish brains was realized for the first time by using a novel solid-phase microextraction fiber, which was prepared by mixing the polyelectrolyte in the oligomer of silicone rubber and followed by in-mold heat-curing. The polyelectrolyte was finally encased in microcapsules dispersed in the cured silicone rubber. The fiber exhibited excellent interfiber reproducibility (5.4–7.1%, <i>n</i> = 6), intrafiber reproducibility (3.7–4.6%, <i>n</i> = 6), and matrix effect-resistant capacity. Due to the capacity of simultaneously extracting the neutral and the protonated species of the analytes at physiological pH, the fiber exhibited high extraction efficiencies to fluoxetine and norfluoxetine. Besides, the effect of the salinity on the extraction performance and the competitive sorption between the analytes were also evaluated. Based on the small-sized custom-made fiber, the concentrations of fluoxetine and norfluoxetine in the brains of living fish, which were exposed to waterborne fluoxetine at an environmentally relevant concentration, were determined and found 4.4 to 9.2 and 5.0 to 9.2 times those in the dorsal-epaxial muscle. The fiber can be used to detect various protonated bioactive compounds in living animal tissues

Enhanced Photocatalytic Degradation of Environmental Pollutants under Visible Irradiation by a Composite Coating

Although nanotechnology has offered effective and efficient solutions for environmental remediation, the full utilization of sustainable energy and the avoidance of secondary pollution are still challenges. Herein, we report a two-step modification strategy for TiO₂ nanoparticles by first forming a thin, surface-adherent polydopamine (PDA) shell onto the nanoparticles and then assembling core–shell nanoparticles as a photodegradation coating. The composite coating modified from TiO₂ could not only realize the highly efficient utilization of photons from the visible region but also avoid the secondary pollution of nanoparticles during application. Additionally, improvements in the adsorption ability after modification greatly facilitated the photocatalytic process of the modified materials. A preliminary in vivo study on <i>Daphnia magna</i> and a wastewater treatment experiment suggest that treatment with the composite coating can effectively eliminate fluorene and significantly reduce its lethality. We believe the two-step modification scheme can open new avenues for the facile modification of nanomaterials for designed purposes, especially in the field of environmental remediation