Yiding Zhang

Online Coupling of In-Tube Solid-Phase Microextraction with Direct Analysis in Real Time Mass Spectrometry for Rapid Determination of Triazine Herbicides in Water Using Carbon-Nanotubes-Incorporated Polymer Monolith

Online coupling of in-tube solid phase microextraction (IT-SPME) with direct analysis in real time mass spectrometry (DART-MS) was realized for the first time and applied in the analysis of triazine herbicides in lake water and orange juice. We incorporated single-wall carbon nanotubes (SWNTs) into a polymer monolith containing methacrylic acid (MAA) and ethylene dimethacrylate (EDMA) to form a novel poly(methacrylic acid-co-ethylene dimethacrylate-co-single wall carbon nanotubes) (poly(MAA-EDMA-SWNT)) monolith, which was then used in IT-SPME for enrichment of six triazine herbicides from water samples. With the online combination of IT-SPME with DART-MS, the analytes desorbed from the monolith were directly ionized by DART and transferred into MS for detection, thus rapid determination was achieved. Compared with regular DART-MS method, this online IT-SPME-DART-MS method was more sensitive and reproducible, because of the IT-SPME procedures and the isotope-labeled internal standard used in the experiment. Six triazine herbicides were determined simultaneously using this method with good linearity (R(2) > 0.998). The limit of quantification (signal-to-noise ratio of S/N = 10) of the six herbicides were only 0.06-0.46 ng/mL. The proposed method has been applied to determine triazine herbicides in lake water and orange juice, showing satisfactory recovery (85%-106%) and reproducibility (relative standard deviation of RSD = 3.1%-10.9%).

Rapid analysis of four Sudan dyes using direct analysis in real time-mass spectrometry

A simple direct analysis in a real time-mass spectrometry (DART-MS) method was developed for the rapid determination of four Sudan dyes (I–IV) in chili powder. Simple liquid extraction by hexane without further clean-up was used for sample preparation. DART parameters were systematically optimized to achieve the best detection performance. A DIP-it sampler was used for automatic sampling. The matrix effect was measured by comparing the limit of detection (LOD) in matrix solution with that in pure organic solution. Eventually, the identification of the Sudan dyes was confirmed by MS/MS results and the LODs for four analytes in matrix solution were ∼0.5 μg mL−1. The method showed good linearity with correlation coefficients (R2) greater than 0.99 for concentrations ranging from 1 to 20 μg mL−1. The whole analytical process could be completed within 15 minutes with good recoveries (88–116%) and satisfactory repeatability (<26%, n = 3).

Interface for Online Coupling of Surface Plasmon Resonance to Direct Analysis in Real Time Mass Spectrometry

The online coupling of surface plasmon resonance (SPR) with mass spectrometry (MS) has been highly desired for the complementary information provided by each of the two techniques. In this work, a novel interface for direct and online coupling of SPR to direct analysis in real time (DART) MS was developed. A spray tip connected with the outlet of the SPR flow solution was conducted as the sampling part of the DART-MS, with which the online coupling interface of SPR-MS was realized. Four model samples, acetaminophen, metronidazole, quinine, and hippuric acid, dissolved in three kinds of common buffers were used in the SPR-DART-MS experiments for performance evaluation of the interface and the optimization of DART conditions. The results showed consistent signal changes and high tolerance of nonvolatile salts of this SPR-MS system, demonstrating the feasibility of the interface for online coupling of SPR with MS and the potential application in the characterization of interaction under physiological conditions.

NiCoMnO4: A Bifunctional Affinity Probe for His-Tagged Protein Purification and Phosphorylation Sites Recognition

A bifunctional affinity probe NiCoMnO4 was designed and prepared with controllable morphology and size using facile methods. It was observed that the probe could be applied in His-tagged proteins purification and phosphopeptides enrichment simply through the buffer modulation. NiCoMnO4 particles showed satisfactory cycling performance for His-tagged proteins purification and broad pH-tolerance of loading buffer for phosphopeptides affinity. Therefore, a high-throughput, cost-effective, and efficient protein/peptide purification method was developed within 10 min based on the novel bifunctional affinity probe.

Study on the interaction of uranyl with sulfated beta-cyclodextrin by affinity capillary electrophoresis and molecular dynamics simulation.

The study on sulfated beta‐cyclodextrin binding to uranyl ion helps to get a better understanding of uranyl compounds’ intermolecular interaction mechanism and facilitates the structure‐based design of uranyl binding molecules. Here we investigated the electromigration of the inclusion complex by using affinity capillary electrophoresis in acidic solution. The binding constant was determined to be logK = 2.96 ± 0.02 (R2 = 0.996) through nonlinear regression approach. The possible configurations and structural features of the inclusion complex were further studied by molecular dynamics simulation. The results suggest the distinctions of coordination environment and hydration compared with bare uranyl ion in aqueous solution. Thus, two water oxygen atoms coordinated with uranyl in the first hydration shell at 2.55 angstrom instead of five in the same distance range. The binding free energy was calculated as –12.10 ± 1.46 kcal/mol by means of thermodynamic perturbation method. The negative value indicates that the process of S‐β‐CD capture uranyl ion in the aqueous media is spontaneous.

An interface for online coupling capillary electrophoresis to dielectric barrier discharge ionization mass spectrometry

The online combination of capillary electrophoresis (CE) with mass spectrometry (MS) has long been desired for the capability of direct and simultaneous separation and detection with high efficiency, accuracy, and throughput. In this work, a novel CE-MS interface was developed, using dielectric barrier discharge ionization (DBDI). The interface employed a spray tip with a coaxial three-layer structure, into which the CE sample solution, the sheath liquid, and the nebulizing gas were introduced. The spray tip was put between the DBDI outlet and the MS inlet, thus the CE sample solution could be blended with the sheath liquid, then nebulized. The nebulized sample could be ionized by DBDI, and finally analyzed by MS. The key parameters of the interface were optimized. Then, proof-of-concept experiments separating and detecting the mixture of metronidazole and acetaminophen solutions were conducted. The results showed high separation efficiency, low time consumption, high reproducibility, and convenience in operation. In addition, the interface exhibited a high tolerance of non-volatile salts and surfactants, which would be widely used in CE analyses. All of these results demonstrated that the newly developed CE-DBDI-MS interface could be successfully used in CE-MS studies, and could be further utilized in multiple areas involving efficient separation and detection.

Online coupling techniques in ambient mass spectrometry.

Since ambient mass spectrometry (AMS) has been proven to have low matrix effects and high salt tolerance, great efforts have been made for online coupling of several analytical techniques with AMS. These analytical techniques include gas chromatography (GC), liquid chromatography (LC), capillary electrophoresis (CE), surface plasmon resonance (SPR), and electrochemistry flow cells. Various ambient ionization sources, represented by desorption electrospray ionization (DESI) and direct analysis in real time (DART), have been utilized as interfaces for the online coupling techniques. Herein, we summarized the advances in these online coupling methods. Close attention has been paid to different interface setups for coupling, as well as limits of detection, tolerance to different matrices, and applications of these new coupling techniques.

Magnetization of 3-dimentional homochiral metal-organic frameworks for efficient and highly selective capture of phosphopeptides

Enrichment of phosphopeptides based on various affinity probes prior to mass spectrometry detection is usually required due to the low abundance and low ionization efficiency of phosphopeptides. In this work, a 3-dimentional homochiral metal-organic frameworks (MOFs) was modified with magnetic nanoparticles using a facile method and then utilized for phosphopeptides capture with high efficiency and specificity. Based on magnetic solid phase extraction, a rapid and efficient method was developed and the whole enrichment procedure could be easily finished within 10min. Efficient and highly selective capture of phosphopeptides from tryptic digests and human serum was achieved. This affinity probe showed satisfactory reproducibility of the particle synthesis and could be recycled for at least seven times. With all the advantages mentioned above, this strategy is of great potential for routine application in phosphoproteomes.

Binding constant determination of uranyl-citrate complex by ACE using a multi-injection method.

The binding constant determination of uranyl with small‐molecule ligands such as citric acid could provide fundamental knowledge for a better understanding of the study of uranyl complexation, which is of considerable importance for multiple purposes. In this work, the binding constant of uranyl–citrate complex was determined by ACE. Besides the common single‐injection method, a multi‐injection method to measure the electrophoretic mobility was also applied. The BGEs used contained HClO4 and NaClO4, with a pH of 1.98 ± 0.02 and ionic strength of 0.050 mol/L, then citric acid was added to reach different concentrations. The electrophoretic mobilities of the uranyl–citrate complex measured by both of the two methods were consistent, and then the binding constant was calculated by nonlinear fitting assuming that the reaction had a 1:1 stoichiometry and the complex was [(UO2)(Cit)]−. The binding constant obtained by the multi‐injection method was log K = 9.68 ± 0.07, and that obtained by the single‐injection method was log K = 9.73 ± 0.02. The results provided additional knowledge of the uranyl–citrate system, and they demonstrated that compared with other methods, ACE using the multi‐injection method could be an efficient, fast, and simple way to determine electrophoretic mobilities and to calculate binding constants.