A ratiomectic aptasensor with enhanced signals based on peroxidase-like enzymes and NH2-MIL-101@MoS2 for trace detection of deoxynivalenol in traditional Chinese herbs.

The accumulation of the deoxynivalenol (DON) in the human body poses a significant health risk that is often overlooked, and we urgently need an ultra-sensitive rapid detection platform. Due to the porosity of NH2-MIL-101@MoS2, an increased loading of toluidine blue (TB) serves to create a signal reference. Cobalt@carbon (CoC) derived from metal organic frameworks was combined with NH2-MIL-101(NH2-MIL-101@CoC) to form an enzyme-free Nanoprobe (Apt-pro) with significant catalytic properties. The ratio (IBQ /ITB) was changed by varying the electrochemical signal of benzoquinone (BQ) (IBQ) and the amount of TB deposition (ITB). This aptasensor was successfully applied to detect DON in malt and peach seed, which exhibited a great linear range from 1 fg/mL to 10 ng/mL and low detection limit of 0.31 fg/mL for DON.

Synthesis of composite materials combining magnetic metal-organic frameworks and conjugated organic frameworks for selective extraction of carbendazim and thiabendazole residues from Chinese herbal medicine samples.

A magnetic metal-organic framework MIL-68(Al) and a covalent organic framework were used as magnetic solid-phase extraction (MSPE) adsorbents in combination with high-performance liquid chromatography ultraviolet detection (HPLC-UV) to detect carbendazim (CBZ) and thiabendazole (TBZ). The main parameters affecting the extraction in the MSPE process were studied and optimized. Fe3O4@MIL-68(Al) coated with 1,3,5-tris(4-aminophenyl)benzene and terephthaldehyde (Fe3O4@MIL-68(Al)@TAPB-PDA-COF) was analyzed and verified. The material was proven to be suitable for adsorbing CBZ and TBZ. Various adsorption models were used to study its adsorption mechanism. The adsorption results were in good agreement with the pseudo-second-order kinetic model and Langmuir isotherm model. The maximum adsorption capacities of Fe3O4@MIL-68(Al)@TAPB-PDA-COF over CBZ and TBZ were 54.24 and 67.87 mg g-1, respectively, and the equilibrium adsorption time was 200 min. Fe3O4@MIL-68(Al)@TAPB-PDA-COF with excellent recyclability showed higher adsorption capacity and selectivity. A method based on Fe3O4@MIL-68(Al)@TAPB-PDA-COF combined with HPLC-UV was established under the optimal extraction conditions and used to separate and detect trace imidazole drugs in Chinese herbal samples, achieving a low limit of detection (0.65-1.30 µg L-1) with excellent linear correlation (r > 0.999). The recovery rate and relative standard deviation were 86.05-99.78 % and 0.15-4.90 %, respectively. Therefore, the Fe3O4@MIL-68@TAPB-PDA-COF can be regarded as an effective adsorbent for the pretreatment of CBZ and TBZ drugs in Chinese herbal samples.

An Electrochemical Sensor Based on Cu-MOF-199@MWCNTs Laden with CuNPs for the Sensitive Detection of Creatinine.

In this study, the synthesis of Cu-MOF-199@multiwalled carbon nanotubes (Cu-MOF-199@MWCNTs) composites was achieved and utilized to create an advanced electrochemical sensor for creatinine (Cre) detection. The composites were modified on a glassy carbon electrode surface through direct drip coating, followed by the deposition of copper nanoparticles (CuNPs) via constant potential deposition. Characterized by various techniques and electrochemical analyses, the Cu-MOF-199@MWCNTs composite increased the CuNPs load, improving the detection sensitivity for Cre. Under optimal conditions, the modified electrode exhibited good linearity across a broad range of Cre concentrations (0.05-40.0 µM) with a low detection limit of 11.3 nM. The developed sensor demonstrated remarkable stability, reproducibility, and selectivity, showing promise in sensitive and accurate Cre detection in serum samples.

MWCNTs and ZnO-based Ce-MOF nanocomposites as enhanced sensing platform for electrochemical detection of carbendazim in Chinese traditional herbs samples.

A facile and novel Ce-MOF@MWCNTs@ZnO-modified glassy carbon electrode was prepared through drop coating and used for accurate and sensitive electrochemical detection of carbendazim. The modification of ZnO nanospheres and Ce-based metal-organic frameworks (Ce-MOFs), which possess vast surface/bulk ratio, large surface area, and excellent catalytic ability, provided more active sites for reaction. The combination of multi-walled carbon nanotubes endowed the modified electrode with excellent conductivity and greatly accelerated the electron transfer. The promotion of electrochemical response and the significant improvement of peak current indicated the outstanding electrocatalytic ability of the modified electrode. The oxidation peak current of carbendazim which was measured by DPV in a potential range from 0.5 to 1.0 V produced a good linear relationship in the concentration ranges 0.05-10.0 µM and 10.0-50.0 µM under  optimized experimental conditions. The detection limit was 13.2 nM (S/N = 3). The constructed electrode was successfully applied to the detection of carbendazim in Lithospermum and Glycyrrhiza uralensis real samples and exhibited satisfactory RSD (2.7-3.6% and 1.6-4.8%, respectively) and recovery (102-106% and 97.7-107%, respectively).

An electrochemical aptasensor based on P-Ce-MOF@MWCNTs as signal amplification strategy for highly sensitive detection of zearalenone.

In this research, a signal-off electrochemical aptasensor with high sensitivity was constructed for trace detection of zearalenone (ZEN). Specifically, Ce-based metal-organic framework and multi-walled carbon nanotubes nanocomposite was functionalized with polyethyleneimine (P-Ce-MOF@MWCNTs) and served as sensing platform for its high surface area and excellent electrochemical active. Subsequently, toluidine blue (TB) was electrodeposited as the signal probe, and platinum@gold nanoparticles (Pt@Au) were dropped for the attachment of aptamer (ZEA). In the presence of ZEN, the ZEA would specifically recognize and combine with the target, causing a decrease of electrochemical signal from TB. Under the optimal conditions, the aptasensor exhibited good linear relationship for ZEN in a concentration range from 5.0 × 10-5 to 50.0 ng/mL, while the limit of detection (LOD, S/N = 3) and limit of quantitation (LOQ, S/N = 10) were 1.0 × 10-5 ng/mL and 2.9 × 10-5 ng/mL, respectively. Ultimately, the aptasensor was successfully applied into ZEN detection in semen coicis real samples.

An electrochemical sensor for purine base detection with ZIF-8-derived hollow N-doped carbon dodecahedron and AuNPs as electrocatalysts.

In this paper, a novel electrochemical sensor was constructed for the detection of purine bases. Ultrafine carbide nanocrystals confined within porous nitrogen-doped carbon dodecahedrons (PNCD) were synthesized by adding molybdate to ZIF-8 followed by annealing. With MoC-based PNCDs (MC-PNCDs) as the carrier, gold nanoparticles (AuNPs) were deposited on the electrode surface via potentiostatic deposition as the promoter of electron transfer, forming a AuNPs/MC-PNCDs/activated glassy carbon electrode (AGCE) sensor. MC-PNCDs had a large specific surface area, which combined with the excellent electrocatalytic activity of AuNPs, synergistically improved the electrocatalytic activity. The morphology and structure of the electrode surface modifier were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray photoelectron spectroscopy, infrared spectroscopy, X-ray diffraction, nitrogen adsorption-desorption analysis, and electrochemical characterization. Under the optimal conditions, the linear detection range of guanine (G) and adenine (A) was 0.5-160.0 µM, and the detection limits (S/N=3) were 72.1 and 69.6 nM, respectively. AuNPs/MC-PNCDs/AGCE was successfully constructed, and was used to simultaneously detect G and A with high sensitivity and selectivity. Moreover, the sensor was successfully used to detect G and A in herring sperm DNA samples.

Simultaneous determination of flavonoids and anthraquinones in honey by using SPE-CE-LIF.

Based on advantages of capillary electrophoresis (CE), a new solid-phase extraction (SPE) coupled with CE has been developed for preconcentration, enrichment and determination of anthraquinones and flavonoids (rutin, emodin, quercetin, 1,8-dihydroxyanthraquinone) in honey. The environmental-friendly chitin activated after an easy processing is selected as the adsorbent to enrich analytes. Then, chitin was filled into the filter as the solid phase. To improve the extraction effect, some key parameters of extraction were optimized. Under the optional extraction conditions, the chitin showed excellent adsorption capacity and selectivity over rutin, emodin, quercetin, and 1,8-dihydroxyanthraquinone, with enrichment factors reaching 5 folds. The CE coupled with fluorescence detection was used for the detection. Results prove the method is simple, fast, and highly sensitive, with the limit of detection (LOD) is 3.00-200.0 ng/mL; the recovery is 90.0-107.0%, and relative standard deviation of (RSD) is 1.8-8.3%.

Sensitive analysis of doxorubicin and curcumin by micellar electromagnetic chromatography with a double wavelength excitation source.

Doxorubicin has been extensively used to treat cancers, and there are recent findings that the anticancer activities can be enhanced by curcumin. Although the two compounds have native fluorescence, they can hardly be quantified directly simultaneously using the laser-induced fluorescence (LIF) detection method. To avoid complex fluorescence derivatization and introduction of interfering components, a highly sensitive double wavelength excitation source LIF (D-W-Ex-LIF) detector composed of a 445-nm and 488-nm commercial laser diode was constructed to detect them simultaneously. Rhodamine 6G was selected as an internal standard, because its fluorescence can be excited at 445 nm and 488 nm. The native fluorescence of doxorubicin and curcumin and their resolution were enhanced by introducing mixed micelles. The optimal electrophoretic separation buffer was 10 mM borate buffer containing 20 mM Triton X-100, 5 mM sodium dodecyl sulfate, and 30% (v/v) methanol at pH 9.00. Therefore, the developed method was specific, accurate, and easily operable. Its limits of detection for doxorubicin and curcumin in human urine samples were 4.00 × 10-3 and 1.00 × 10-2 µg/mL, respectively, and the limits of quantification were 1.00 × 10-2 and 3.00 × 10-2 µg/mL, respectively. The recoveries were 94.9-109.1%. Graphical abstract.

A simple and highly sensitive masking fluorescence detection system for capillary array electrophoresis and its application to food and medicine analysis.

A high sampling rate, good stability, high throughput masking fluorescence detection system with easy positioning of each channel for capillary array electrophoresis was prepared and studied. A special mask combined with convex lenses was designed to modulate signals, without using any extra device to position each channel. The signal of each channel was detected by a photomultiplier tube, classified and saved by software. The design was used to evidently reduce the rotational vibration of optical components and to stabilize the system, so a high sampling rate was obtained by increasing the DC motor speed. To improve the optical system, optical fibers instead of conventional bulky optical components were used to transmit optical signal and to collect fluorescences in multiple directions, which greatly raised the sensitivity. Other important parameters including sampling rate, rotating speed and driven voltage laser diode (LDs) have also been investigated. Under optimal conditions, the performance of the detection system was evaluated. This novel system had a well-designed structure, and allowed independent multiple capillary operations and easy microanalysis. Its limit of detection for rhodamine 6G was 2.0 × 10-2 µg/mL.

A nanocomposite consisting of ionic liquid-functionalized layered Mg(II)/Al(III) double hydroxides for simultaneous electrochemical determination of cadmium(II), copper(II), mercury(II) and lead(II).

An electrochemical sensor is described for the simultaneous determination of Cd2+, Cu2+, Hg2+ and Pb2+ using square wave anodic stripping voltammetry. A glassy carbon electrode (GCE) was modified with N,N-dimethyl-N-2-propenyl-2-propen-1-aminium chloride homopolymer ionic liquid doped into magnesium(II)-aluminium(III) layered double hydroxides. The morphology investigations suggest that the material possesses typical interconnected laminated micropores and a mesoporous architecture dispersed on the surface of the GCE. This accelerates mass diffusion and facilitates the deposition-stripping process of metal ions. Key operational parameters including pH, deposition potential, deposition time and the quantity of nanomaterial on the GCE were optimized. The following figures of merit for the ions Cd2+, Cu2+, Hg2+ and Pb2+ are obtained under optimum conditions: (a) detection limits of 250, 25, 250 and 16 ng L-1; (b) linear ranges from 0.5 to 20, 0.05 to 20, 0.5 to 20 and 0.05 to 20 µg L-1, and (c) peak potentials of -768, +42, +302 and - 541 mV (vs. Ag/AgCl). The modified GCE was successfully applied to the determination of these ions in spiked black tea extract and in dried tangerine peel. Graphical abstractSchematic representation of novel electrochemical sensor based on a glassy carbon electrode modified with IL-Mg/Al-LDHs composites for the simultaneous detection of Pb2+, Cd2+, Cu2+ and Hg2+.

Novel coordination imprinted polymer monolithic column applied to the solid-phase extraction of flumequine from fish samples.

In this study, a coordination imprinted polymer (CIP) solid-phase extraction (SPE) method was developed to determine the residues of flumequine (FLU) in fish samples. Silanized graphene oxide-doped CIP (SGO-CIP) monolithic column was prepared using FLU-Zn2+ as template in the presence of SGO. The synthesis conditions of SGO-CIP column were optimized by the response surface methodology. Under the optimum conditions, this column showed high specificity to FLU, and the adsorption capacity reached 61.74 ng mg-1. The enrichment factor of the monolithic column was over 40-fold. Various factors affecting the extraction efficiency of SGO-CIP column during SPE were tested to achieve optimal enrichment and to reduce non-specific adsorption. FLU in fish was detected by using a high-performance liquid chromatography-fluorescence detection system. The detection limit was as low as 0.32 ng g-1 and the recovery was as high as 95.2%, with relative standard deviations of below 5.9%. This simple and sensitive method may be applicable to the determination of FLU residues in foods.

Synthesis of carbon quantum dots-doped dummy molecularly imprinted polymer monolithic column for selective enrichment and analysis of aflatoxin B1 in peanut.

In this study, a novel method was proposed to sensitively determine aflatoxin B1 (AFB1) in peanut sample by using a carbon quantum dots-coated dummy molecularly imprinted polymer (CDs-DMIP) monolithic column for pretreatment coupled with high performance liquid chromatography-fluorescence detection (HPLC-FLD). The CDs-DMIP monolithic column was prepared by in-situ polymerization in a water bath using 5,7-dimethoxycoumarin as dummy template molecule. The CDs-DMIP monolithic column was applied to determine AFB1 by HPLC-FLD. Satisfactory linearity was obtained over 0.5-2000ngmL-1, with a high correlation coefficient of 0.9999. The recoveries of AFB1 in peanut sample ranged from 79.5% to 91.2%, and the intraday and interday relative standard deviation ranged from 1.2% to 4.9%. Limit of detection (S/N=3) and limit of quantitation (S/N=10) were 0.118ngmL-1 and 0.393ngmL-1, respectively. Under the optimized conditions, the enrichment factor was over 71-fold. AFB1 in peanut sample and even some other samples could be sensitively determined by CDs-DMIP-HPLC-FLD method.

Chip-based molecularly imprinted monolithic capillary array columns coated GO/SiO2 for selective extraction and sensitive determination of rhodamine B in chili powder.

A novel solid-phase extraction chip embedded with array columns of molecularly imprinted polymer-coated silanized graphene oxide (GO/SiO2-MISPE) was established to detect trace rhodamine B (RB) in chili powder. GO/SiO2-MISPE monolithic columns for RB detection were prepared by optimizing the supporting substrate, template, and polymerizing monomer under mild water bath conditions. Adsorption capacity and specificity, which are critical properties for the application of the GO/SiO2-MISPE monolithic column, were investigated. GO/SiO2-MIP was examined by scanning electron microscopy (SEM) and Fourier transform-infrared spectroscopy. The recovery and the intraday and interday relative standard deviations for RB ranged from 83.7% to 88.4% and 2.5% to 4.0% and the enrichment factors were higher than 110-fold. The chip-based array columns effectively eliminated impurities in chili powder, indicating that the chip-based GO/SiO2-MISPE method was reliable for RB detection in food samples using high-performance liquid chromatography. Accordingly, this method has direct applications for monitoring potentially harmful dyes in processed food.

Chip-based dual-molecularly imprinted monolithic capillary array columns coated Ag/GO for selective extraction and simultaneous determination of bisphenol A and nonyl phenol in fish samples.

An analytical technique for selective, simultaneous determination of bisphenol A (BPA) and nonyl phenol (NP) in fish samples was established by a solid-phase extraction chip integrated with array columns of dual-molecularly imprinted polymer-coated silver-modified graphene oxide (Ag/GO-dual-MISPE-chip). Ag/GO dual-molecularly imprinted polymers (Ag/GO-dual-MIPs) were synthesized by in situ polymerization using Ag/GO as the supporting matrix which extracted templates easily. The affinity and specificity on the Ag/GO-dual-MISPE monolithic column were also investigated. The array extraction chip showed high binding capacity and selectivity to BPA and NP, with the imprinting factors of BPA and NP reaching 2.6 and 2.9, respectively. Ag/GO-dual-MIPs were characterized by scanning electron microscopy and Fourier transform-infrared (FT-IR) spectroscopy. As Low as 2.4ngL-1 BPA and 4.7ngL-1 NP were detected by high performance liquid chromatography coupled with fluorescence detection. The enrichment factor was 113-fold for BPA and 92-fold for NP. Therefore, the chip-based array columns are feasibly applicable to facile extraction of BPA and NP and effective clean-up of impurities in fish samples.

A simple and compact fluorescence detection system for capillary electrophoresis and its application to food analysis.

A novel fluorescence detection system for CE was described and evaluated. Two miniature laser pointers were used as the excitation source. A Y-style optical fiber was used to transmit the excitation light and a four-branch optical fiber was used to collect the fluorescence. The optical fiber and optical filter were imported into a photomultiplier tube without any extra fixing device. A simplified PDMS detection cell was designed with guide channels through which the optical fibers were easily aligned to the detection window of separation capillary. According to different requirements, laser pointers and different filters were selected by simple switching and replacement. The fluorescence from four different directions was collected at the same detecting point. Thus, the sensitivity was enhanced without peak broadening. The fluorescence detection system was simple, compact, low-cost, and highly sensitive, with its functionality demonstrated by the separation and determination of red dyes and fluorescent whitening agents. The detection limit of rhodamine 6G was 7.7 nM (S/N = 3). The system was further applied to determine illegal food dyes. The CE system is potentially eligible for food safety analysis.

Molecularly imprinted coated graphene oxide solid-phase extraction monolithic capillary column for selective extraction and sensitive determination of phloxine B in coffee bean.

A method was developed to sensitively determine phloxine B in coffee bean by molecularly imprinted polymers (MIPs) coated graphene oxide (GO) solid-phase extraction (GO-MISPE) coupled with high-performance liquid chromatography and laser-induced fluorescence detection (HPLC-LIF). The GO-MISPE capillary monolithic column was prepared by water-bath in situ polymerization, using GO as supporting material, phloxine B, methacrylic acid (MAA), and ethylene dimethacrylate (EDMA) as template, functional monomer, and cross-linker, respectively. The properties of the homemade GO-MISPE capillary monolithic column, including capacity and specificity, were investigated under optimized conditions. The GO-MIPs were characterized by scanning electron microscopy (SEM) and Fourier transform-infrared spectroscopy (FT-IR). The mean recoveries of phloxine B in coffee bean ranged from 89.5% to 91.4% and the intra-day and inter-day relative standard deviation (RSD) values all ranged from 3.6% to 4.7%. Good linearity was obtained over 0.001-2.0 µg mL(-1) (r=0.9995) with the detection limit (S/N=3) of 0.075 ng mL(-1). Under the selected conditions, enrichment factors of over 90-fold were obtained and extraction on the monolithic column effectively cleaned up the coffee bean matrix. The results demonstrated that the proposed GO-MISPE HPLC-LIF method can be applied to sensitively determine phloxine B in coffee bean.

Molecularly imprinted solid-phase extraction monolithic capillary column for selective extraction and sensitive determination of safranine T in wolfberry.

A method was developed to sensitively determine safranine T in wolfberry by molecularly imprinted solid-phase extraction (MISPE) coupled with high-performance liquid chromatography and laser-induced fluorescence detection (HPLC-LIF). The MISPE capillary monolithic column was prepared by water-bath in situ polymerization, using safranine T, methacrylic acid (MAA), and ethylene dimethacrylate (EDMA) as template, functional monomer, and cross-linker, respectively. The properties of the homemade MISPE capillary monolithic column, including capacity and specificity, were investigated under optimized conditions and the morphologies of inner polymers were characterized by scanning electron microscopy (SEM). The mean recoveries of safranine T in wolfberry ranged from 91.2 % to 92.9 % and the intraday and interday relative standard deviation (RSD) values all ranged from 3.4 % to 4.2 %. Good linearity was obtained over 0.001-1.0 µg mL(-1) (r = 0.9999) with a detection limit (S/N = 3) of 0.4 ng g(-1). Under the selected conditions, enrichment factors of over 90-fold were obtained and the extraction on the monolithic column effectively cleaned up the wolfberry matrix. The results demonstrated that the proposed MISPE-HPLC-LIF method could be applied to sensitively determine safranine T in wolfberry.

Preparation and evaluation of a novel molecularly imprinted SPE monolithic capillary column for the determination of auramine O in shrimp.

A novel method combining molecular imprinting and SPE was developed in a capillary column for the determination of auramine O in shrimp. The capillary monolithic column was prepared by UV-initiated in situ polymerization, using auramine O as template and methacrylic acid and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The properties of the prepared capillary monolithic column were investigated under the optimized conditions coupled with HPLC, and then the morphologies of the inner polymers were characterized by SEM. The calibration curve was expressed as A = 103C + 19.8 (r = 0.9992) with a linear range of 0.25-25.0 µg/mL, and the recoveries of auramine O at different concentrations in shrimp ranged from 90.5 to 92.4% with RSDs ranging from 2.1 to 4.4%. The capacities of the molecularly imprinted polymer and nonimprinted polymer columns were 0.722 and 0.147 µg/mg, respectively, and the LOD (S/N = 3) of auramine O in shrimp was 17.85 µg/kg. Under the selected conditions, the enrichment factors obtained were higher than 70-fold. The results indicate that the prepared molecularly imprinted capillary monolithic column was reliable and applicable to the analysis of auramine O in shrimp.