A novel online two-dimensional supercritical fluid chromatography/reversed phase liquid chromatography-mass spectrometry method for lipid profiling.

A novel online two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography-triple-quadrupole mass spectrometry (2D SFC/RPLC-QQQ MS) method based on a vacuum solvent evaporation interface was developed for lipid profiling in human plasma, in which lipid classes were separated by the first-dimension SFC and different lipid molecular species were further separated by the second-dimension RPLC. All separation condition parameters were carefully optimized, and their influence on the chromatographic behavior of lipids is discussed. Finally, the recoveries of 11 lipid standards were all more than 88% for the interface. Besides, the limit of detection for these lipid standards was on the order of nanograms per milliliter, and the relative standard deviations of the peak area and retention time ranged from 1.54% to 19.85% and from 0.00% to 0.10%, respectively. The final 2D SFC/RPLC-QQQ MS method allowed the identification of 370 endogenous lipid species from ten lipid classes, including diacylglycerol, triacylglycerol, ceramide, glucosylceramide, galactosylceramide, lactosylceramide, sphingomyelin, acylcarnitine, phosphatidylcholine, and lysophosphatidylethanolamine, in human plasma within 38 min, which was used for screening potential lipid biomarkers in breast cancer. The 2D SFC/RPLC-QQQ MS method is a potentially useful tool for in-depth studies focused on complex lipid metabolism and biomarker discovery. Graphical Abstract.

TiO2 nanoparticles functionalized monolithic capillary microextraction online coupled with inductively coupled plasma mass spectrometry for the analysis of Gd ion and Gd-based contrast agents in human urine.

In this work, a novel method of TiO2 nanoparticles (NPs) functionalized monolithic capillary microextraction (CME) online coupling with inductively coupled plasma mass spectrometry (ICPMS) was developed for the sequential determination of Gd(3+) and Gd-based contrast agents in human urine samples. The monolithic capillary was prepared by embedding anatase TiO2 NPS in the poly(methacrylic acid-ethylene glycol dimethacrylate) (MAA-EDMA) framework. The Gd(3+) and Gd-based contrast agents (such as gadolinium-diethylene triamine pentaacetic acid (Gd-DTPA) and Gd-DTPA-bismethylamide (Gd-DTPA-BMA)) display different adsorption behaviors on the prepared monolithic capillary which possesses the adsorption properties of both anatase TiO2 NPS and poly(MAA-EDMA) monolith. Under the optimized conditions, the limits of detection (LODs) were found to be 3.6, 3.2, and 4.5 ng L(-1) for Gd(3+), Gd-DTPA, and Gd-DTPA-BMA, respectively, which are the lowest up to date. The enrichment factor was 25-fold with the sample throughput of 5 h(-1). The proposed method was validated by the analysis of Gd(3+) and Gd-DTPA in the healthy human urine samples as well as Gd(3+) and Gd-DTPA-BMA in patient urine samples. It was found that only a small amount of the free Gd(3+) was released from Gd-DTPA-BMA, and accurate results could be obtained since no oxidation/reduction or subtraction is involved in this method. This method is simple, sensitive, and rapid and provides a very attractive nonchromatography strategy for the speciation of Gd(3+) and Gd-based contrast agents in urine samples.

Robust model-based sensor fault monitoring system for nonlinear systems in sensor networks.

A new model-based sensor fault diagnosis (FD) scheme, using an equivalent model, is developed for a kind of Multiple Inputs Multiple Outputs (MIMO) nonlinear system which fulfills the Lipschitz condition. The equivalent model, which is a bank of one-dimensional linear state equations with the bounded model uncertainty, can take the place of a plant's exact nonlinear model in the case of sensor FD. This scheme shows a new perspective whereby, by using the equivalent model, it doesn't have to study the nonlinear internal structure character or get the exact model. The influence of the model uncertainty on the residuals is explained in this paper. A method, called pretreatment, is utilized to minimize the model uncertainty. The eigenstructure assignment method with assistant state is employed to solve the problem of perfect decoupling against the model uncertainty, disturbance, system faults, the relevant actuator faults, or even the case of no input from the relevant actuator. The realization of the proposed scheme is given by an algorithm according to a single sensor FD, and verified by a simulation example. Depending on the above, a sensor fault monitoring system is established by the sensor network and diagnosis logic, then the effectiveness is testified by a simulation.

[Advances in the development of the sample preparation techniques in lipidomics].

Lipids play an important physiological role in living system. They are the major components of cellular membranes, in addition to participating in energy storage as well as signal recognition and transmission. In recent years, an increasing number of studies have shown that disturbances in lipid metabolism are closely related to the development of some diseases. Lipid analysis is of great significance for understanding the mechanism and the process of diseases. Because of the matrix interference and low concentration of analytes, existing techniques require sample preparation steps to ensure good analytical performance. In the present study, sample preparation methods in lipidomics used in various fields are reviewed, including lipid extraction methods, such as liquid-liquid extraction and solid phase extraction, as well as the chemical derivatization techniques for different lipid categories. In addition, the development of the sample preparation in lipidomics is also prospected.

A Versatile Integrated Ambient Ionization Source Platform.

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.