Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part II

This is the part II of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS–MS) detection in LC (as opposed to the “conventional” detectors). The Part II starts with briefly introducing the main quantitation methods and then addresses the performance related to quantification: linearity of signal, sensitivity, precision, trueness, accuracy, stability and measurement uncertainty. The last section is devoted to practical considerations in validation. With every performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to handle it, specifically in the case of LC–MS methods.     

An overview of analytical methodologies for the determination of antibiotics in environmental waters

The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes.     

Impact of information sharing and lead time on bullwhip effect and on-hand inventory

This work analyzes a two echelon (warehouse–retailer) serial supply chain to study the impact of information sharing (IS) and lead time on bullwhip effect and on-hand inventory. The customer demand at the retailer is assumed to be an autoregressive (AR(1)) process. Both the echelons use a minimum mean squared error (MMSE) model for forecasting lead time demand (LTD), and follow an adaptive base-stock inventory policy to determine their respective order quantities. For the cases of without IS and inter as well as intra echelon IS, expressions for the bullwhip effect and on-hand inventory for the warehouse are obtained, considering deterministic lead-time. The results are compared with the previous research work and an easy analysis of the various bullwhip effect expressions under different scenarios, is done to understand the impact of IS on the bullwhip effect phenomenon. It is shown that some part of bullwhip effect will always remain even after sharing both inter as well as intra echelon information. Further, with the help of a numerical example it is shown that the lead time reduction is more beneficial in comparison to the sharing of information in terms of reduction in the bullwhip effect phenomenon.     

Ultra high performance liquid chromatography-quadrupole-time of flight analysis for the identification and the determination of resveratrol and its metabolites in mouse plasma

Resveratrol is a polyphenol that has numerous interesting biological properties, but, per os, it is quickly metabolized. Some of its metabolites are more concentrated than resveratrol, may have greater biological activities, and may act as a kind of store for resveratrol. Thus, to understand the biological impact of resveratrol on a physiological system, it is crucial to simultaneously analyze resveratrol and its metabolites in plasma. This study presents an analytical method based on UHPLC-Q-TOF mass spectrometry for the quantification of resveratrol and of its most common hydrophilic metabolites. The use of ¹³C- and D-labeled standards specific to each molecule led to a linear calibration curve on a larger concentration range than described previously. The use of high resolution mass spectrometry in the full scan mode enabled simultaneous identification and quantification of some hydrophilic metabolites not previously described in mice. In addition, UHPLC separation, allowing run times lower than 10 min, can be used in studies that requiring analysis of many samples.     

Separation and determination of m-phenoxybenzaldehyde reaction products by capillary gas chromatography

A capillary GC method employing an internal standard has been developed and successfully used for quantitative determination both of the raw materials used for the manufacture of m-phenoxybenzaldehyde and for the components of the reaction mixtures obtained at various stages of the development of the process. A complete analysis can be performed in a single temperature programmed run.     

热化学循环分解水制氢研究进展

热化学循环分解水制氢是利用核能或太阳能进行大规模、无污染制氢的有前景的方法 ,已经提出了多种流程.本文对热化学制氢流程及其评价标准进行了综述,重点介绍了碘硫循环、UT-3循环和Westinghouse循环等先进流程的研究进展.     

Investigation of the electrical properties of a new PPV derivative-based on a sandwich structure for opto-electronic applications

The opto-electronic properties of native poly(p-phenylene vinylene) (PPV) were tuned by the confinement of the π-conjugation and the incorporation of a sulphur group as a spacer in order to obtain a blue-green emitting polymer (PPVS). The energy band gap of the PPVS thin film has been measured by UV-vis absorption spectroscopy and evaluated to 2.87 eV. Current-voltage characteristics and impedance spectroscopy measurements performed on sandwich structures [ITO/PPVS/Al] are used to elucidate the conduction mechanisms. The static electrical characterisations showed a space charge limited conduction (SCLC) and a conductivity with low power frequency behaviour characteristic of a hopping transport in disordered materials. The impedance spectra can be discussed in terms of an equivalent circuit model designed as a parallel resistor R_P and capacitor C_P network in series with a resistor R_S. We extract numerical values of these parameters by fitting experimental data. Their evolution with bias voltages has shown that the SCLC mechanism is characterised by an exponential trap distribution.     

Mathematische und Graphische Methoden zur Bewertung des [15N]Methacetin-Testes für die klinische Praxis

Im Zusammenhang mit der Einführung eines nichtinvasiven ¹⁵N-Leberfunktionstests entstand die Notwendigkeit, durch Interpretation der Meßergebnisse bestimmte Kenngrößen zu ermitteln, die eine spezifische Leberfunktion in einem Wert widerspiegeln.

Es wurden drei Auswertemethoden erprobt, ein graphischer Meßwertausgleich, eine Regressionsrechnung unter alleiniger Verwendung der Eliminationsgleichung sowie die Auswertung auf der Grundlage eines Kompartmentmodells, welches Invasion und Elimination des Diagnostikums berücksichtigt. Zur Realisierung der zuletzt genannten Methode wurde das Computerprogramm PATMETH entwickelt. Vergleichende Betrachtungen, die auf der Grundlage der Ergebnisse von 250 ausgewerteten Tests vorgenommen wurden, zeigen die Überlegenheit der computergestützten Auswertemethode. Sie basiert auf einer einheitlichen theoretischen Grundlage, welche Willkür ausschliet, ermöglicht exakte Fehlerangaben der Testparameter und ist wesentlich zeitsparender.

In connection with the introduction of a non-invasive ¹⁵N liver function test the necessity arose to evaluate certain parameters reflecting a specific liver function by interpretation of the measured values.

There were tested three evaluation methods: a graphic fit of measured values, a linear regression by using only the elimination equation and the evaluation on the basis of a compartment model, which is considering invasion and elimination of the diagnostic agent. For realizing the last method there was developed the computer program PATMETH. Comparative investigations based on the evaluation of 250 tests show the superiority of the computer based calculation method. It is founded on a uniform theoretical basis excluding arbitrariness, it permits exact information about the error values of the test parameters and it is substantial time-sparing.     

Streamlined sample cleanup using combined dispersive solid-phase extraction and in-vial filtration for analysis of pesticides and environmental pollutants in shrimp

A new method of sample preparation was developed and is reported for the first time. The approach combines in-vial filtration with dispersive solid-phase extraction (d-SPE) in a fast and convenient cleanup of QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts. The method was applied to simultaneous analysis of 42 diverse pesticides and 17 environmental contaminants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), and flame retardants, in shrimp as the sample matrix. Final extracts were analyzed by both low-pressure gas chromatography – triple quadrupole tandem mass spectrometry (LPGC-MS/MS), and high-performance liquid chromatography – triple quadrupole tandem mass spectrometry (HPLC-MS/MS) to provide a wide scope of analysis for targeted analytes. During method development, several different commercial sorbents for d-SPE were investigated and compared with respect to analyte recoveries. The method was validated at 10, 50, and 100 ng g⁻¹ spiking levels (10-fold lower for PCBs), and the results for nearly all analytes were between 70 and 115% recoveries with ≤17% relative standard deviations. The method was shown to be simple, fast, and effective for multi-application analysis of chemical residues in the representative food and environmental marker matrix.