Molybdenum disulfide nanosheet induced reactive oxygen species for high-efficiency luminol chemiluminescence.

BACKGROUND: Luminol chemiluminescence (CL) sensing system remains an excellent candidate for application in bioanalysis due to its good water solubility. However, traditional luminol CL system usually requires the addition of oxidizing agents and sensitizers to obtain high efficiency for the improvement of detection sensitivity. Although numerous studies on the nanomaterial-enhanced luminol CL systems have been carried out, there is still great potential to develop inexpensive, readily available and easily handled catalysts to construct simple and effective CL platform for biomolecular sensing. RESULTS: Few-layered MoS2 nanosheets (NS) prepared by sonication-assisted exfoliation of commercially available bulk MoS2 were found to significantly enhance the CL of luminol‒dissolved oxygen in the absence of additional oxidants. The mechanism study demonstrated that exfoliated MoS2 NS could catalyze the decomposition of dissolved oxygen by virtue of its exposed active sites on the surface, generating increased reactive oxygen intermediates, which then oxidize luminol and produce intense CL emission. The proposed high-efficiency luminol CL system was then employed for the extremely sensitive identification of dopamine based on the quenching of CL by dopamine. The limit of detection (LOD) for dopamine can be as low as 2.07 nM. Besides, it also works well in the actual urine sample with good recoveries (99.6-100.6 %), confirming the practicability of the method. SIGNIFICANCE: As a new type of CL catalyst, MoS2 NS developed in this work are easy to obtain, simple to prepare and can be produced in large quantities, which lays a foundation for extending applicability of MoS2 NS in the CL field, and provides a new idea for developing simple and highly sensitive CL sensing system.

Three-dimensional fluorinated covalent organic frameworks coated capillary for the separation of fluoroquinolones by capillary electrochromatography.

In this work, a three-dimensional fluorinated covalent organic frameworks (3D FCOFs) JUC-515 was synthesized from tetra(4-aminophenyl)methane (TAM) and 2,3,5,6-tetrafluoroterephthalol (TFA) by an ionic liquid method. JUC-515 was introduced into the capillary column and bonded to the inner wall of the capillary column by chemical bonding. Through a variety of characterization results, JUC-515 was successfully synthesized and introduced into the capillary column. The effects of buffer solution concentration, organic additive content and pH of the buffer solution on the separation of fluoroquinolones (FQs) were investigated in detail. The JUC-515-coated capillary column showed good resolution (>1.5) and reproducibility. The relative standard deviations (RSDs) of the retention time for intraday, interday, column-to-column and interbatch precision were less than 0.88%, 2.45%, 2.74% and 3.32%, respectively. The RSDs of the peak area for intraday, interday, column-to-column and interbatch precision were less than 3.79%, 4.31%, 3.33% and 5.62%, respectively. The JUC-515-coated capillary column could be used no less than 150 times. The results showed that the JUC-515-coated capillary column had good separation performance. In addition, by separating fluorinated ß-phenylalanine analogs, ß-phenylalanine and trifluoromethyl ß-phenylalanine analogs, the separation mechanism based on fluorine interactions was discussed. In conclusion, JUC-515 had good potential as a stationary phase for capillary electrochromatography.

Recent Advances in Nanomaterial-Based Chemiluminescence Probes for Biosensing and Imaging of Reactive Oxygen Species.

Reactive oxygen species (ROS) play important roles in organisms and are closely related to various physiological and pathological processes. Due to the short lifetime and easy transformation of ROS, the determination of ROS content in biosystem has always been a challenging task. Chemiluminescence (CL) analysis has been widely used in the detection of ROS due to its advantages of high sensitivity, good selectivity and no background signal, among which nanomaterial-related CL probes are rapidly developing. In this review, the roles of nanomaterials in CL systems are summarized, mainly including their roles as catalysts, emitters, and carriers. The nanomaterial-based CL probes for biosensing and bioimaging of ROS developed in the past five years are reviewed. We expect that this review will provide guidance for the design and development of nanomaterial-based CL probes and facilitate the wider application of CL analysis in ROS sensing and imaging in biological systems.

Systematic study of tissue section thickness for MALDI MS profiling and imaging.

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) has become a powerful method for studying the spatial distribution of molecules. Preparation of tissue sections is a critical step for obtaining high-quality imaging data. The thickness of the slice of tissue affects the feature quality of MALDI MSI. However, few studies involved in-depth and systematic examination of slice thickness. Herein, we investigate the effect of tissue slice thickness on MALDI MSI detection. We found that the thicker the slice, the worse the results obtained by MALDI MS, which we attributed to the charging effect. The optimal slice thickness of brain tissue obtained in this work is 2-6 µm. Comparisons of the effects of slice thickness on atmospheric pressure and vacuum MALDI assays indicated that the ion signals and imaging quality of vacuum MALDI were more seriously affected by the thickness, with atmospheric pressure (AP) MALDI having a greater tolerance for slice thickness than vacuum MALDI. The MALDI MSI of peptides after enzymatic digestion of tissue sections of different thicknesses was also studied, revealing that the most suitable tissue thickness for enzyme digestion is about 10 µm. Finally, we optimized the slice thicknesses of six tissues in mice to provide a reference for MALDI MSI studies. It is worth mentioning that in our study the values of slice thickness range from the nanometer level (400 nm) at the minimum to 150 µm at the maximum, values which were unprecedented. Detailed in-depth and systematic studies of slice thickness will promote the development of sample preparation technology of AP and vacuum MALDI MSI, which will provide important references for the selection of tissue section thickness.

Label-free microRNA detection using a locked-to-unlocked transforming system assembled by microfluidics.

MicroRNA (miRNA) is a potential biomarker for the early screening and diagnosis of cancers and is widely present in human blood, urine and saliva. Here, we report a microfluidics-assembled tool for miRNA detection based on the regulation of DNA locked and unlocked states and explore its application in complex samples. Microfluidic techniques are used to continuously assemble the locked-to-unlocked transforming system using a rapid one-step method. It only takes 2 min to produce enough locked-to-unlocked systems for a miRNA detection experiment. DNA molecules with a recognition sequence and a G-rich reporter sequence (G4m) are locked by attaching both ends to the surface of magnetic beads (MBs) in microchannels. The presence of the target miRNA can initiate the specific cleavage of one end of G4m by duplex-specific nuclease, resulting in the transition of G4m from a locked state to an unlocked state. This transition enables G4m to freely fold into a G-quadruplex, which can participate in the catalysis of ABTS oxidation and result in a turquoise color. During the whole process, the target miRNA remains intact and continuously initiate specific cleavage, facilitating signal amplification. Magnetic separation steps are employed to assist in miRNA enrichment and interference reduction. As a proof of concept, we quantified miRNA-21 using the locked-to-unlocked system. The assay allows specific detection of miRNA-21 in the range of 3.2-570 pM with a detection limit of 2.01 pM (S/N = 3). Furthermore, the locked-to-unlocked system is used to analyze miRNA-spiked urine, saliva and serum samples and shows robust performance in different matrices.

Fluorinated covalent organic frameworks as a stationary phase for separation of fluoroquinolones by capillary electrochromatography.

A fluorinated covalent organic framework composed of 2,3,5,6-tetrafluoroterephthaldehyde (TFA) and 1,3,5-tri(4-aminophenyl)benzene (TAPB) is proposed for electrochromatographic separation. TFA-TAPB is for the first time regarded as the stationary phase of capillary electrochromatography. The TFA-TAPB-coated capillary columns exhibited satisfactory separation (resolution values > 1.5) and good reproducibility towards fluoroquinolones. The intraday relative standard deviations (RSDs) of retention time and peak areas were 0.54-0.68% and 1.69-2.82%, respectively. The interday RSDs of retention time and peak areas were less than 1.79% and 2.30%, respectively. The column-to-column RSDs of retention time and peak areas were 0.22-0.73% and 0.74-1.86%, respectively. And, the inter-batch RSDs of retention time and peak areas were less than 0.39% and 1.67%, respectively. Moreover, the possible separation mechanism was discussed, and it was found that the π-π stacking effect, hydrophobic interaction, hydrogen bonding, and fluorous interactions were the main factors. Overall, these results demonstrated that TFA-TAPB has high prospect for CEC separation.

Adsorption behavior and mechanism of sulfonamides on controllably synthesized covalent organic frameworks.

In this work, four kinds of covalent organic framework (COF) materials (TpPa-1, TpBD, TpDT, and TFBBD) with different pore sizes or functional groups were synthesized by an ultrasonic method for the adsorption of five sulfonamides. Optimization experiments regarding the adsorption time, vortex speed, and pH were carried out to improve adsorption efficiency. In addition, kinetic and thermodynamic experiments were conducted to explore the adsorption mechanism of the sulfonamides on the different COFs. The adsorption processes of the five sulfonamides on the four COFs fit the pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Additionally, pore filling, hydrogen bond interactions, and electrostatic attraction were found to be the main adsorption mechanisms.

Capillary coated with three-dimensional covalent organic frameworks for separation of fluoroquinolones by open-tubular capillary electrochromatography.

The Schiff-base reaction of 1,3,5-triformylphloroglucinol (Tp) and tetra(4-aminophenyl)methane (TAM) was performed for the synthesis of a three-dimensional covalent organic framework named 3D TpTAM, which was obtained by an ultrasound-assisted method for the first time. The morphology and structure of the synthesized TpTAM were characterized through various methods. Then, TpTAM-coated capillary columns were subsequently prepared by a covalent bonding method within a short time and applied for the separation of fluoroquinolones by capillary electrochromatography (CEC) with good resolution and reproducibility. The intraday relative standard deviations (RSDs) of the retention time and peak areas were 0.88%-0.95% and 2.27%-3.81%, respectively. The interday RSDs of retention time and peak areas were 0.71%-0.89% and 0.88%-3.60%, respectively. The column-to-column RSDs of retention time and peak areas were less than 1.90% and 13.56%, respectively. The interbatch RSDs of retention time and peak areas were less than 3.48% and 3.89%, respectively. The TpTAM-coated capillary columns could be used for no less than 100 runs with no observable changes in the separation efficiency. The separation mechanism was also studied, which indicated that π-π stacking effects, hydrophobic interactions and hydrogen bonding were the main factors. The results revealed that 3D TpTAM should have superior potential as the stationary phase in CEC for chromatographic separation.

Molybdenum disulfide-graphene oxide composites as dispersive solid-phase extraction adsorbents for the enrichment of four paraben preservatives in cosmetics.

Molybdenum disulfide-graphene oxide composite (MoS2/GO) was synthesized and used as the adsorbent in dispersive solid-phase extraction. Four paraben preservatives, namely, methylparaben, ethylparaben, propylparaben, and butylparaben, were enriched with MoS2/GO and determined by ultra-high-performance liquid chromatography. Molybdenum disulfide was intercalated into graphene oxide layers to reduce self-aggregation by using the solvothermal method. The experimental results indicated that the as-prepared MoS2/GO composite exhibited great enrichment capability toward those four paraben preservatives, and the adsorption time was 10 min and the elution time was as short as 1 min. The mechanism of MoS2/GO composite and parabens is attributed to hydrogen bonding and electrostatic attraction. The relative standard deviation (RSD, n = 9) of this method was below 7.6%. Limits of detection and limits of quantification were in the range 0.4-2.3 ng/mL and 1.4-7.6 ng/mL, respectively. The recoveries obtained from the parabens of cosmetic sample were in the range 91.3-124% with RSDs below 10%. The developed method has great potential for the determination of emerging contaminants with low cost and high sensitivity.

A graphene oxide-molybdenum disulfide composite used as stationary phase for determination of sulfonamides in open-tubular capillary electrochromatography.

A graphene oxide-molybdenum disulfide (GO-MoS2) composite was synthesized and utilized as the highly efficient stationary phase of open-tubular capillary electrochromatography (OT-CEC). The characterization results indicated that GO-MoS2 composite was successfully synthesized. The GO-MoS2-coated capillary column was prepared by covalent immobilization method for the determination of seven sulfonamides. The baseline separation of seven sulfonamides was achieved by GO-MoS2-coated capillary column. The linear range was 0.05-100 µg/mL for sulfisomidine, sulfathiazole, sulfamerazine, phthalylsulfathiazole and sulfacetamide, 0.1-100 µg/mL for sulfamonomethoxine and sulfachloropyridazine with a satisfactory correlation coefficients (R2) > 0.9994. This developed OT-CEC method was successfully applied to determinate of seven sulfonamides in environmental water and milk samples with good recoveries of 85.77% - 109.10% and 80.03% - 109.97%, respectively. These results indicated that GO-MoS2-coated capillary column possessed good stability and repeatability.

Ambient temperature fabrication of a covalent organic framework from 1,3,5-triformylphloroglucinol and 1,4-phenylenediamine as a coating for use in open-tubular capillary electrochromatography of drugs and amino acids.

A covalent organic framework (COF) named TpPa-1 was designed and synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). It was utilized as a stationary phase in open-tubular capillary electrochromatography (OT-CEC). The column was coated with TpPa-1 using a covalent bonding strategy. The coated capillary was characterized by morphology, crystallography, and mesoporous analysis to confirm the successful fabrication. The OT-CEC method was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution (Rs > 1.81) and good precision (RSD < 4.9%). It takes about 12 h from COF preparation to OT-CEC separation. Graphical abstract A covalent organic framework (COF) named TpPa-1 was synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). COF-TpPa-1 modified capillary column was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution and good precision.

Label free aptasensor for ultrasensitive detection of tobramycin residue in pasteurized cow's milk based on resonance scattering spectra and nanogold catalytic amplification.

TOB aptamer can be adsorbed on the AuNPs surface to form AuNPs-aptamer complexation to prevent AuNPs aggregation in high salt solution. When TOB was added to the AuNPs solution, the aptamer would bind with TOB and depart from the AuNPs surface. The amount of the AuNPs-aptamer complexation depends on the TOB concentration. Different concentration of AuNPs-aptamer can catalyze the reduction reaction of CuSO4 to produce different size Cu2O particle. The resonance scattering peak intensities are correlated with the Cu2O size. Large size Cu2O particle as a resonance scattering spectroscopy probe can remarkable improve the TOB detection sensitivity. We have succeeded to detect the trace TOB in aqueous solutions. The linear range and limit of detection were 0.50-17 nM and 0.19 nM, respectively. This simple and inexpensive method exhibited high sensitivity and selectivity, which was successfully used to detect TOB in milk. The results indicated the accuracy and precision were satisfied.

Fast and simple determination of moroxydine residues in pig and chicken samples by ultra-performance liquid chromatography-tandem mass spectrometry.

A general solid-phase extraction (SPE) method using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the determination of moroxydine residues in pig and chicken samples has been developed. After extraction and purification of real samples, moroxydine residues were detected using a hydrophobic interaction liquid chromatography column with an optimised mobile phase composition. The extraction reagents, the kind of SPE columns and the type of eluents were optimised to achieve the maximum extraction efficiency. The matrix effects from the animal tissue influenced the quality of the quantitative data obtained. Under the optimised conditions, the moroxydine residues in pig and chicken samples spiked at three levels (1.0 µg/kg, 5.0 µg/kg and 10.0 µg/kg) were determined with good recoveries (61.5%-105.4%) and adequate relative standard deviations (3.2%-13.0%). In pig and chicken samples, the limit of detection (LOD) was 0.3 µg/kg, and the limit of quantification (LOQ) was 1.0 µg/kg. A sufficiently linear relationship in the range of 1.0 µg/kg-20.0 µg/kg was achieved with a good correlation coefficient (R2 ≥ 0.99).

Covalent bonding of Schiff base network-1 as a stationary phase for capillary electrochromatography.

Covalent organic frameworks (COFs), featuring low densities, high surface areas, and good thermal and chemical stabilities, are gradually attracting interest in the field of analytical chemistry. A type of microporous polymer network material named Schiff base network-1 (SNW-1) was introduced into a capillary column through covalent bonding. The obtained SNW-1-coated capillary column was characterized by thermogravimetric analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. Then, the SNW-1-coated capillary column was successfully utilized for the open-tubular capillary electrochromatography (OT-CEC) separation of sulfonamides, cephalosporins, amino acids and parabens. The fabricated capillary column showed good separation efficiency (Rs > 1.4), stability and reproducibility (relative standard deviation (RSD) < 5.88%). To the best of our knowledge, this is the first report of a covalent bonding strategy to bond an SNW material to a capillary column for OT-CEC.

Determination of sulfonamides in milk by capillary electrophoresis with PEG@MoS2 as a dispersive solid-phase extraction sorbent.

A synthetic polyethylene glycol-molybdenum disulfide (PEG@MoS2) composite was prepared using a simple method, and the application of this material in dispersive solid-phase extraction (DSPE) was investigated for the enrichment of eight sulfonamides (SAs) in milk samples. The composite was characterized by energy dispersive spectroscopy, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller measurements. The results showed that the MoS2 synthesized in the presence of PEG has the advantage of a larger surface area and that the adsorption effect of this MoS2 was enhanced. After extraction, the eight SAs were separated by capillary zone electrophoresis with a good linear relationship (R2 > 0.9902) in the range of 0.3-30 µg ml-1 and good precision (between 0.32% and 9.83%). Additionally, good recoveries (between 60.52% and 110.91%) were obtained for the SAs in the milk samples. The developed PEG@MoS2-based DSPE method could be applied for the enrichment of SAs in real milk samples.

Open-tubular capillary electrochromatographic determination of ten sulfonamides in tap water and milk by a metal-organic framework-coated capillary column.

In this study, a metal-organic framework (MOF), [Mn(cam)(bpy)], was synthesized and characterized by thermogravimetric analysis, scanning electron microscopy, and Fourier transform infrared spectrometry. An open-tubular capillary column was fabricated from [Mn(cam)(bpy)] via the amide coupling method. Ten types of sulfonamides were separated through the fabricated capillary column, which showed a good limits of detection (<0.07 µg/mL) and linear ranges (1-100 or 5-100 µg/mL) with a high correlation coefficients (R2 > 0.9987). The intra-day, inter-day and column-to-column relative standard deviations (RSDs) in the migration times ranged from 0.44 to 4.87%, and the peak area RSDs ranged from 0.80 to 7.28%. The developed capillary electrochromatography method can be successfully utilized for the determination of sulfonamides in tap water and milk samples.

Recent advances in metal-organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis.

In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF- or COF-based solid-phase extraction (SPE), solid-phase microextraction (SPME), gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation.

Covalent bonding of homochiral metal-organic framework in capillaries for stereoisomer separation by capillary electrochromatography.

In this work, a [Cu(mal)(bpy)]⋅H2O (mal, L-(-)-malic acid; bpy, 4,4'-bipyridyl) homochiral metal-organic frameworks (MOFs) was synthesized and used for modifying the inner walls of capillary columns by utilizing amido bonds to form covalent links between the MOFs particles and capillary inner wall. The synthesized [Cu(mal)(bpy)]⋅H2 O and MOFs-modified capillary column were characterized by X-ray diffraction, thermogravimetric analysis, particle size distribution analysis, nitrogen absorption characterization, FTIR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy (EDX). The MOFs-modified capillary column was used for the stereoisomer separation of some drugs. The LODs and LOQs of six analytes were 0.1 and 0.25 µg/mL, respectively. The linear range was 0.25-250 µg/mL for ephedrine, 0.25-250 µg/mL for pseudoephedrine, 0.25-180 µg/mL for D-penicillamine, 0.25-120 µg/mL for L-penicillamine, 0.25-180 µg/mL for D-phenylalanine, and 0.25-160 µg/mL for L-phenylalanine, all with R(2) > 0.999. Finally, the MOFs-modified capillary column was applied for the analysis of active ingredients in a real sample of the traditional Chinese medicine ephedra.

Investigation of the adsorption mechanism and preconcentration of sulfonamides using a porphyrin-functionalized Fe3O4-graphene oxide nanocomposite.

In this work, a novel type of porphyrin-functionalized Fe3O4-graphene oxide (TCPP/Fe3O4-GO) nanocomposite was synthesized. The adsorption mechanism of the prepared TCPP/Fe3O4-GO material was investigated and predicted. The π-π stacking and electrostatic attraction between the positively charged analytes and the negatively charged porphyrin-functionalized Fe3O4-GO accelerated the electron transfer between the materials. In addition, to investigate the preconcentration of the prepared TCPP/Fe3O4-GO, it was used as a magnetic solid-phase extraction adsorbent for the preconcentration of seven sulfonamides (SAs) from environmental water samples. Parameters that significantly affected the extraction of the SAs onto the sorbent, such as the elution solvent, extraction time and elution time, were optimized. Under the optimal conditions, the SAs in the environmental water samples were effectively detected. The linear range for the seven SAs was 0.5-20 µg mL(-1), and the limits of detection for all seven SAs were 0.2 µg mL(-1). Good reproducibility was obtained, along with relative standard deviations that ranged from 0.01 to 8.25%. The present method was applied to the determination of SAs in tap and river water samples, and the recoveries were satisfactory (83.7-116.7%).

Capillary coated with graphene oxide as stationary phase for the separation of brucine and strychnine by capillary electrophoresis.

A new capillary electrophoresis (CE) method was developed by using graphene oxide (GO) as a stationary phase for the separation of brucine and strychnine. The separation performance, reproducibility and stability of GO-coated capillary were investigated for the analysis of brucine and strychnine. After optimization of the separation conditions, a phosphate solution (40 mM, pH 7.0) containing 25% (v/v) acetonitrile was selected as the running buffer. Compared with uncoated capillary, higher separation efficiency was achieved by GO-coated capillary as a result of the increasing interactions between the analytes and the stationary phase of capillary. The linear ranges of these two alkaloids were 4.0-100.0 µg mL(-1) with a satisfied correlation coefficients (R > 0.9994), and this novel method provided an efficient separation of brucine and strychnine as well as a good reproducibility and stability. Finally, the developed method was successfully applied for the determination of these two alkaloids in a pharmaceutical formulation of traditional Chinese medicines.