To improve the bioavailability of ketoprofen and reduce its clinical risks, this study combined density functional theory (DFT) calculations with experiments and investigated the structure-activity relationship of ketoprofen-based ionic liquids (ILs). Using ketoprofen as the anion and choline, 1-butyl-3-methylimidazole, and benzalkonium as the cations, ketoprofen-based ILs were prepared through a two-step method. Their structures, solubilities, critical micelle concentrations (CMC), cytotoxicity, etc., were determined. The results show that the physical and chemical properties of the ketoprofen-based ILs have changed significantly. For example, their critical micelle concentrations in ethanol and water are 10-6 and 10-5 mol·L-1, respectively, and their solubility (converted to ketoprofen) is more than 103 times that of ketoprofen in water. The IC50 values exhibited the low cytotoxicity of the ketoprofen-based ILs, which was better than 100 μM. The DFT calculation results show that the difference in dipole moments between ketoprofen-based ILs is not significant, but the dipole moment of ketoprofen-based ILs is much larger than that of ketoprofen, which may lead to an increase in the solubility of ketoprofen-based ILs. Both DFT calculations and experimental results indicate that the stronger the ion-pair interaction energy of ILs, the higher their melting points and decomposition temperatures. These preliminary research results can lay a foundation for the application research of ketoprofen ILs (including ketoprofen choline gel and the pharmacokinetics of ketoprofen choline).
Doxycycline (DOX), a highly potent and versatile tetracycline antibiotic extensively utilized as a feed additive in food-producing animals, has posed increasingly severe residue toxicity and potential risks to human health owing to its bioaccumulation through the food chain. Thus, the development of rapid and accurate detection methodologies for DOX residues is imperative. Herein, molecularly imprinted composites anchored on magnetic covalent organic frameworks substrates (MCOFs@MIPs) were elaborately tailored and fabricated to serve as highselectivity sorbents aiming at effective preconcentration and quantification of DOX within pork tissue matrices. This strategy integrated the high surface area, porous structure of MCOFs and specific recognition ability of molecular imprinting technology, overcoming the limitations of traditional adsorbents. Isothermal and kinetic adsorption studies revealed that MCOFs@MIPs achieved a saturated adsorption value of 20.0 mg g-1 after 210 min, with adsorption process conforming to the Langmuir adsorption model and pseudo-first-order kinetic equations. Notably, this adsorbent exhibited excellent selectivity toward DOX, as evidenced by a high imprinting factor (IF) of 4.35 and a distribution coefficient (Kd) of 0.50. Furthermore, MCOFs@MIPs demonstrated good reproducibility, and their coupling with HPLC enabled efficient enrichment of DOX in pork samples with an enrichment factor of 30. The resultant DOX recoveries obtained from pork samples fell between 77.02% and 91.52%. Compared with existing adsorbents, the as-fabricated MCOFs@MIPs exhibited high adsorption capacity, enhanced selectivity and superior enrichment efficiency, demonstrating a novel and reliable analytical approach for antibiotic residue monitoring in complex matrices.
The limited electrocatalytic activity of graphitic carbon nitride (C3N4) constrains its application in electrochemical sensing. Herein, Fe-doped C3N4 (Fe-C3N4) featuring atomically dispersed Fe-N5 sites was synthesized via a one-step solid-state thermal polycondensation approach. Comprehensive structural characterization, including transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and aberration-corrected electron microscopy, confirms both the structural integrity of C3N4 and the atomic dispersion of Fe species. Additionally, synchrotron radiation-based X-ray absorption spectroscopy verifies the Fe-N5 coordination environment. Density functional theory calculations demonstrate that the Fe-N5 sites modulate the local electronic structure, enhance sulfide adsorption, and decrease the limiting free-energy step for hydrogen sulfide (H2S) oxidation. As a result, the Fe-C3N4 electrode exhibits a significantly enhanced anodic response toward H2S, along with excellent selectivity against common biological interferents. Furthermore, reliable electrochemical signals are obtained in bone metastasis tissue homogenates, enabling effective discrimination between tumor and normal tissues. This work presents a scalable strategy for the design of Fe-N5 single-atom catalysts for electrochemical sensing in complex biological environments.
A rapid, selective, and sensitive paper-based fluorescence sensing method was developed for cysteine (Cys) detection. The nitrogen-doped carbon quantum dots (CNQDs) and aspartic acid (Asp) reacted with gold nanoparticles (AuNPs) to synthesize the probe AuNPs@CNQDs@Asp, resulting in an efficient quenching of CNQDs fluorescence. Owing to the strong interaction between Cys and AuNPs, as well as the specific interaction between Cys and Asp, triggering the detachment of CNQDs and the recovery of fluorescence. The images of fluorescence signal were collected within 6 min using a portable fluorescence detector and analyzed via a smartphone-based application. The RGB value increased linearly in the 180 to 260 μM Cys concentration range (R = 0.9990), with a low limit of detection (LOD) of 4 μM. Interference deviations of 12 substances to Cys were in the range of -3.1% to +1.0%. The method was applied to determine Cys in human plasma, showing a recovery between 98.2% and 102.3% and demonstrating its superior reliability. The work highlights the potential of the method to detect Cys in real samples with low cost and high efficiency, providing an effective tool for diseases surveillance and control in resource-limited regions.
In this work, the poly (glycidyl methacrylate)-b-poly (phenylboronic acid) block polymer-coated capillary column was developed for the selective enrichment of glycoproteins in capillary electrophoresis. The polymer coating was fabricated through a two-step consecutive surface-initiated atom transfer radical polymerization (SI-ATRP) using glycidyl methacrylate (GMA) and 3-acrylamidophenylboronic acid (AAPBA) as monomers. The coating was characterized by techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), inverted fluorescence microscopy, scanning electron microscopy (SEM), and electroosmotic flow (EOF) analysis. Evaluations of the column demonstrated that the coating exhibits both anti-nonspecific absorption property and high enrichment towards glycoproteins. The sensitivity enhancement factor (SEF) for immunoglobulin G (IgG) reached 351.89, representing a 173.3-fold improvement over the bare fused silica capillary. The coated column could be used repeatedly for approximately 60 consecutive runs. The relative standard deviations (RSD) of peak area for intra-day (n = 5), inter-day (n = 5), and batch-to-batch (n = 3) were 3.5%, 3.6% and 4.6%, respectively. The method was successfully applied to the online enrichment of glycoproteins in a 1×106-fold diluted egg white sample, thereby confirming its practical applicability.
Pesticide residues in cultivated herbal medicines pose significant health risks, with phorate (PHO) and dichlorodiphenyltrichloroethane (DDT) being of particular concern due to their high toxicity and persistence. Current detection methods, such as gas chromatography and mass spectrometry (GC-MS) and liquid chromatography and mass spectrometry (LC-MS), are often limited by their complexity, time consumption, and the need for specialized equipment, hindering rapid and on-site analysis. In this study, integrated the high sensitity of time-resolved fluorescent microspheres (TRFM) and the simplicity and cost-effectiveness of lateral flow immunoassay (LFIA), we creates a time-resolved immunochromatographic test strip (TRFIS) for simultaneously detection of PHO and DTT residues in herbal medicines. After systematically optimizing the TRFIS preparation and detection parameters and extraction solvents, this TRFIS enables for simultaneously quantitative detection of PHO and DDT within 12 min with limit of detections (LODs) of 0.0975 ng/g for PHO and 0.116 ng/g for DDT. Besides, the detection performance of the TRFIS is highly reproducible, with the intra-batch and inter-batch coefficients of variation (CV)% below 8 %. Additionally, the results of the TRFIS for detecting PHO/DDT residues are credible, with a significantly high correlation to the gold standard methods GC-MS and LC-MS (R2 = 0.9891). Collectively, our developed TRFIS offers a promising platform for simultaneous detection of PHO and DDT residues in herbal medicines, with the advantages of simple operation, high sensitivity, rapid determination, cost-effectiveness, and on-site detection.
Controllable liquid manipulation is of paramount scientific and technological importance in various fields, such as the chemical industry, biomedicine, and agricultural production. Magnetic actuation, characterized by rapid, contactless, and environmentally benign operation, has emerged as a promising approach for precise liquid control. However, conventional magnetic strategies typically govern droplet movement on open surfaces, facing limitations such as restricted liquid volumes, uncertain flow paths, and inevitable evaporation, thereby constraining their broader practical applications. Recently, a variety of magnetic-driven strategies have been developed to dynamically regulate liquids within enclosed spaces, especially through physicochemical mechanisms. These approaches provide efficient control over liquid behavior by leveraging magnetically induced chemical changes, structural deformations, and dragging motions, opening new opportunities for flexible and versatile fluid management. This review explores the design and mechanisms of magneto-responsive confined interfaces for the manipulation of nonmagnetic liquids, highlighting key advancements and potential applications including liquid valves, liquid mixing, liquid flow regulation, and liquid pumping. Finally, the existing challenges and future prospects in this field are presented.
Orientationally immobilized enzyme microreactors (OIMERs), embedded in microfluidic paper-based analytical devices (mu PADs) were developed for improved detection of pesticide residues in food. Acetylcholinesterase (AChE) was orientationally immobilized on the reusable Part I of the mu PADs, using the specific affinity binding of concanavalin A (Con A) to a glycosyl group on AChE. Using the disposable Part II, facile colorimetric quantification was performed with a smartphone and software, or qualitative detection by a naked-eye visual test. The AChE immobilized in OIMERs not only had improved activity and stability, but also high sensitivity, with a limit of detection as low as (0.007 +/- 0.003) mu g/mL. The method was used to detect pesticides residues in real vegetable samples; the recovery (88.6-102.7%) showed high reliability for pesticide residues detection in foods. A molecular docking study and an enzyme kinetic analysis were conducted to characterize the mechanism of action of the OIMERs.
We report the screening of angiotensin converting enzyme (ACE) inhibitors on an origami microfluidic paper-based analytical device (mu PAD) using colorimetric detection. The hydrolysis product reacts with ninhydrin, resulting in a purple color at the detection zones. Images of the mu PADs are captured using a common cell phone and analyzed with Photoshop software. This platform allows six independent colorimetric reactions to take place simultaneously, and the IC(50 )values can be obtained in a single run within 22 min. The relative standard deviations of inhibition efficiencies are generally lower than 4.0 % (n = 5). The IC50 values of captopril and five products from natural plants were obtained and corresponded well with UV methods. The relative deviations between the two methods are within the range of -5 % to +5 %. This work is a proof-of-concept successfully demonstrating the use of mu PADs technology to screen enzyme inhibitors from natural products.
A metal-free, visible-light-catalyzed oxidative cleavage of the CC bond of an alkene by thiobenzoic acid in water under an O 2 atmosphere has been developed.
A capillary column coated with 3-aminophenylboronic acid (APBA)-functionalized gold nanoparticles (AuNPs@APBA) was prepared via electrostatic self-assembly. The coated column exhibited anti-nonspecific adsorption of glycoproteins, enabling selective online enrichment during capillary electrophoresis (CE). First, gold nanoparticles (AuNPs) were synthesized using the sodium citrate reduction method. Then, APBA was self-assembled electrostatically on the surface of the AuNPs to obtain AuNPs@APBA. This nanomaterial was bonded to the inner wall of a capillary through ion adsorption to produce a AuNPs@APBA-coated capillary column. Glycoproteins were adsorbed via bond formation with boric acid groups under alkaline conditions (pH 8) to generate borate esters. Under acidic conditions (pH 3), the borate esters dissociated to release the glycoproteins, thereby achieving the selective online enrichment and separation of glycoproteins. The AuNPs and AuNPs@APBA were characterized using Fourier transform infrared spectroscopy, and their sizes and Zeta potentials were determined. In addition, the electroosmotic flow (EOF) of the AuNPs@APBA-coated capillary column was measured. The results showed that the surface of the AuNPs was successfully modified with APBA and that AuNPs@APBA was adsorbed on the inner wall of the capillary. The peak area of ovalbumin (OVA) on the AuNPs@APBA-coated column was 26.46 times higher than that on a bare column via conventional electrophoresis. In contrast, the peak area of bovine serum albumin (BSA) only increased by 8.47 times, indicating that the AuNPs@APBA coated column selectively enriched glycoproteins. Evaluation of the reproducibility and stability of this method revealed that the AuNPs@APBA coated capillary column could be used continually for 33-67 h. The relative standard deviations (RSDs) of the peak areas for intra-day (n=5) and inter-day (n=6) analyses were 2.2% and 3.0%, respectively. The developed method was successfully applied to enrich glycoproteins in a 1×106-fold diluted egg white sample. Glycoproteins were not detected using conventional electrophoresis on the bare column, whereas the AuNPs@APBA-coated capillary column effectively enriched and separated glycoproteins, resulting in a peak area of 10469 mAU·ms. Furthermore, the entire enrichment and separation process was completed within 3 min. This new online enrichment and separation method for glycoproteins has the advantages of low sample consumption, simple operation, and high separation efficiency.
To improve the binding strength and adsorption capacity, a boronate affinity adsorbent was prepared by atom transfer radical polymerization using acrylamide as monomer, and then decorated with a bidentate boronate ligand (DBA) by post -modification. The materials were characterized by infrared spectrum and X-ray photoelectron spectroscopy, and the adsorption properties of the materials were studied. The results showed that the adsorbent had higher selectivity for cis-diols compounds. Meanwhile, the adsorbent modified with DBA had higher affinity adsorption capacity than that modified by single boric acid ligand adsorbent, indicating that the DBA could promote the affinity strength and adsorption capacity of the material. Static isothermal adsorption and dynamic adsorption showed that the adsorption of nucleosides was in accordance with Freundlich fitting and quasi -secondorder kinetic equation, so it belonged to multilayer adsorption, and the chemical adsorption played a leading role. Under neutral to weakly acidic conditions, the material still had good adsorption capacity for cis-diols molecules, which was conducive to the direct separation and enrichment of biological samples. When the buffer pH=6.5, the optimal adsorbent mass was 30.0 mg for 1.0 mu g/mL mixed solution of four nucleosides. The optimal elution was 0.1 mol/L formic acid -methanol (1: 1, V/V). The elution volume was 0.5 mL for twice, and 5 min each time. The material was applied to the separation and enrichment of nucleosides in human urine. The concentration of adenosine, guanosine, cytidine and uridine in urine was detected to be 8.0, 50.4, 29.3 and 35.2 ng/mL, respectively. The recoveries were 87.6%-107.3% and the relative standard deviations were 2.8%-9.2%, indicating that the method was accurate and reliable.
We introduce a facile method for glycoprotein enrichment, separation, and detection using microfluidic paperbased analytical devices (mu PADs). The mu PADs comprise two distinct components: the enrichment region (Chip I) and the detection section (Chip II). The reusable Chip I is fabricated by immobilizing 3-aminophenylboronic acid (APBA) onto a circular paper substrate, demonstrating exceptional glycoprotein affinity. In disposable Chip II, glycoproteins react with periodic acid, generating carbonyl compounds that produce a purple-colored product upon reacting with the Schiff reagent. Alterations in color intensity are captured using an ordinary cell phone and are subsequently analyzed using Photoshop software. Observations note a linear increase in average color intensities from 1.0 x 10- 3 to 5.0 x 10- 3 mol/L, with an R2 value of 0.9927. The relative standard deviations (RSDs) of inter-day (n = 5) and intra-day (n = 5) assessments stand at 1.5 % and 1.4 %, respectively. Our proposed approach can effectively enrich an ovalbumin (OVA) solution with concentrations as low as 1.0 x 10-11 mol/L, resulting in enrichment rates of 107 to 108 times. The interference deviations of five substances relative to OVA lie within the range of - 2.0 % to + 2.0 %. The methodology successfully enriches glycoproteins from egg white samples diluted by a factor of 1 x 106, demonstrating that the proposed method is remarkably suitable for enriching glycoproteins from authentic samples.
Flemingia philippinensis Merr.et Rolfe (F. philippinensis) is an important food ingredient as well as a traditional Chinese medicine with numerous pharmacological actions. Unfortunately, there was no defined method for monitoring the quality of F. philippinensis in the Chinese Pharmacopoeia. In this study, a magnetic covalent organic framework molecularly imprinted polymers (MCOFs-MIPs) was prepared using MCOFs as a support material, genistein (Gen), which was abundant in F. philippinensis, as a template molecule, and acrylamide as a functional monomer. The preparation process of MCOFs-MIPs was optimized and their structures and adsorption characteristics were characterized. In the selectivity test, the imprinting factor of Gen was 1.93, demonstrating that the imprinting effect of MCOFs-MIPs could selectively enrich Gen in complex samples. Following that, a new and effective quality control method (Gen-MCOFs-MIPs-HPLC) was established to determine Gen content in F. philippinensis roots. The method showed good linearity (R2 = 0.9936) in the range of 0.12-80 mu g mL-1. The recoveries of Gen in F. philippinensis high, medium and low samples were 90.5-91.0 %, 92.1-100.1 and 92.8-100.8, respectively. Stability and reproducibility tests revealed that this method was stable (RSD of 1.20 %) and reproducible (RSD of 0.70 %). Moreover, the calculation showed that the amount of Gen in the F. philippinensis powder was 0.4489 mg g-1. As a result, the approach was shown to be simple, repeatable, and stable, and it provided a sensitive and reliable method for the extraction and detection of Gen in natural products.
A facial and rapid method for glycoproteins enrichment by capillary electrophoresis was developed. The 3-aminophenylboronic acid-functionalized poly(glycidyl methacrylate) microparticles (PGMA@APBA) were attached to the capillary inlet (length of similar to 1.5 cm) by electrostatic self-assemble action to prepare a partially coated capillary column. The process is simple and reversible, allowing for easy renewal of the PGMA@APBA coating when its enrichment efficiency decreases. By utilizing the coated column, glycoproteins can be enriched within 2 min. The column exhibits a specific enrichment for glycoproteins and can be consecutively used for approximately 60 runs. The relative standard deviations (RSDs) of peak area of run-to-run (n = 5) and batch-to-batch (n = 3) were 1.5 % and 1.0%, respectively. The method was successfully applied to enrich glycoproteins from 1 x 10(12)-fold diluted real egg white sample, indicating its practical applicability.
This paper presents a 28nm 1.04pJ/SOP sub-mm 2 spiking and back-propagation hybrid neural network asynchronous olfactory processor enabling few-shot class-incremental on-chip learning for the first time, showing <33.27μW training power budget at 0.55V with gas recognition, concentration estimation, and gas incremental learning tasks. This processor achieves 110.62× and 4.09× energy saving respectively over the state-of-the-art gas recognition and SNN chips.
Chemistry is an experimental science. Practical teaching is a significant link in the cultivation of students majoring in chemistry to foster students' practical, professional application, and innovation abilities. Based on the investigation and analysis of the problems existing in the cultivation of the practical ability of applied chemistry major, take specific measures, such as constructing the practical teaching system of applied chemistry major, explored a better practical teaching system for students of applied chemistry major; applied to the reform and innovation of training mode of students majoring in applied chemistry and achieved good results.
A facial and efficient method for the screening of acetylcholinesterase (AChE) inhibitors by capillary electrophoresis was developed. Based on the specific affinity of concanavalin A (Con A) for binding to the glycosyl group of AChE, enzyme molecules were oriented-immobilized on the surface of gold nanoparticles (AuNPs@Con A@AChE). Then, these modified nanoparticles were bounded to the capillary inlet (about 1.0 cm) by electrostatic self-assembly to obtain the oriented-immobilized enzyme microreactor (OIMER). Compared to an IMER with a free enzyme, the peak area of the product obtained by the OIMER increased by 52.6%. The Michaelis–Menten constant (Km) was as low as (0.061 ± 0.003) mmol/L. The method exhibits good repeatability with a relative standard deviation (RSD) of 1.3% for 100 consecutive runs. The system was successfully applied to detect the IC50 values of donepezil and four components from Chinese medicinal plants. This work demonstrates the potential of this method as a low cost, simple, and accurate screening method for other enzyme inhibitors.
A hydroxypropyl-beta-cyclodextrin (HP-beta-CD) imprinted coating based on polyhedral oligomeric silsesquioxane (POSS) for open tubular electrochromatography was prepared. The mixture of methacryl-POSS (MA0735), HP-beta-CD (template), methacrylic acid (MAA, monomer), N,N '-methylenebisacrylamide (MBA, crosslinker) and toluene-dimethyl sulfoxide (porogen) was used to synthesize the chiral selective coating. The influence of synthesis parameters on the imprinting effect and separation performance, including the amount of HP-beta-CD, POSS, and MAA, was investigated systemically. The optimum polymerization was prepared by mixing HP-beta-CD, MA0735, MAA, and MBA with the molar ratio of 1 : 1.87 : 1.60 : 1.60. Five racemates were separated by the modified capillary columns using aqueous buffer. Column efficiency on the POSS-based MIPs coating column was greater than 22 000 plates/m. MIPs-POSS hybrid coating capillaries had improved resolution (3.36 times) and the greatest resolution was up to 6.15 within 10 min.