qPeaks: A Linear Regression-Based Asymmetric Peak Model for Parameter-Free Automatized Detection and Characterization of Chromatographic Peaks in Non-Target Screening Data.

We present qPeaks (quality peaks), a novel, user-parameter-free algorithm for peak detection and peak characterization applicable to chromatographic data. The algorithm is based on a linearizable regression model that analyzes asymmetric peaks and estimates the specific uncertainties associated with the peak regression parameters. The uncertainties of the parameters are used to derive a data quality score DQSpeak, rendering low reliability results more transparent during processing and allowing for the prioritization of generated features. High DQSpeak chromatographic peaks have a lower chance of being classified as false-positive and show higher repeatability over multiple measurements. The high efficiency of the algorithm makes it particularly useful for application within processing routines of nontarget screening through chromatography coupled with high-resolution mass spectrometry. qPeaks is integrated into the qAlgorithms nontarget screening processing toolbox and appends a parameter-free chromatographic peak detection and characterization step to it. With qAlgorithms, now high-resolution mass spectra are centroided using the qCentroids algorithms, centroids are clustered to form extracted ion chromatograms (EICs) with the qBinning algorithm, and chromatographic peaks are found on the generated EICs with qPeaks. However, all tools from qAlgorithms can also be used independently.

Evaluation of GC-EI&CI-TOFMS for Nontarget Analysis of Industrial Wastewater Using Hydrophilic-Lipophilic-Balanced SPME.

The evaluation of nontarget analysis (NTA) techniques for the monitoring of wastewater is important as wastewater is an anthropogenic pollution source for aquatic ecosystems and a threat to human and environmental health. This study presents the proof-of-concept NTA of industrial wastewater samples. A prototype hydrophilic-lipophilic-balanced (HLB) SPME and gas chromatography interfaced with time-of-flight high-resolution mass spectrometry (GC-TOFMS) with electron ionization (EI) and chemical ionization (CI) in parallel are employed. The HLB-SPME consists of a poly(divinylbenzene-co-N-vinylpyrrolidone) structure, allowing the extraction of hydrophilic as well as lipophilic substances. As the combination of parallel CI and EI data provides a comprehensive data set as a unique feature, this study is strongly focused on the compound identification procedure and confidence reporting of exemplary substances. Furthermore, the use of three different CI reagent ions, including [N2H]+/[N4H]+, [H3O]+, and [NH4]+, enables a broad range of analytes to be ionized in terms of selectivity and softness. The complementary information provided by EI and CI data allows a level 3 identification or higher in 69% of cases. The polarity coverage based on the physicochemical properties of the analytes (such as volatility, water solubility, hydrophilicity, and lipophilicity) was visualized by using Henry's law and octanol-water partitioning constants. In conclusion, the presented approach is shown to be valuable for water analysis and allows enhanced and accelerated compound identification compared to utilizing only one type of ionization.

Impact of Chemical and Physical Properties of Organic Solvents on the Gas and Hydrogen Formation during Laser Synthesis of Gold Nanoparticles.

Laser ablation in liquids has been established as a scalable preparation method of nanoparticles for various applications. Particularly for materials prone to oxidation, it is established to suppress oxidation by using organic solvents as a liquid medium. While this often functionalizes the nanoparticles with a carbon shell, the related chemical processes that result from laser-induced decomposition reactions of the organic solvents remain uncertain. Using a systematic series of C6 solvents complemented by n-pentane and n-heptane during the nanosecond laser ablation of gold, the present study focuses on the solvent-dependent influence on gas formation rates, nanoparticle productivity, and gas composition. Both the permanent gas and hydrogen formation was found to be linearly correlated with ablation rate, ΔHvap , and pyrolysis activation energy. Based on this, a decomposition pathway linked to pyrolysis is proposed allowing the deduction of first selection rules for solvents that influence the formation of carbon or permanent gases.

Isotope-labeling in situ derivatization and HS-SPME arrow GC-MS/MS for simultaneous determination of fatty acids and fatty acid methyl esters in aqueous matrices.

Fatty acids (FAs) and fatty acid methyl esters (FAMEs) co-occur in many samples, and analysis of both substance classes is frequently of high interest. To this end, this study introduces the first method for simultaneous determination of FAs and FAMEs including fully automated solvent-free solid-phase microextraction (SPME) arrow headspace extraction combined with isotope-labeling in situ FA derivatization with deuterated methanol (CD3OD). By using the chromatographic isotope effect (ΔRt = 0.03 min) and the + 3 m/z mass shift, FAs can be selectively differentiated from the FAMEs during gas chromatography tandem-mass spectrometry (GC-MS/MS) operated in the multiple reaction monitoring (MRM) aquisition mode. Additionally, an approach is presented to predict the retention times of deuterated compounds. Optimization of the derivatization conditions was accomplished by design of experiments and found to be 20 min, 50 °C, 4 v/v% CD3OD, and pH 2.1. During method validation, FAs and FAMEs were calibrated in different concentration ranges by standard addition in five real matrices and ultrapure water leading to good linearities and method detection limits for FAs ranging from 1-30 µg L-1 and for FAMEs from 0.003-0.72 µg L-1. FAs and FAMEs were detected in real samples from surface water, wastewater treatment plant effluent, and three different bioreactor samples and could be quantified in concentrations ranging from 2-1056 µg L-1 for FAs and 0.01-14 µg L-1 for FAMEs.

Optimization and automation of rapid and selective analysis of fatty acid methyl esters from aqueous samples by headspace SPME arrow extraction followed by GC-MS/MS analysis.

The analysis of fatty acid methyl esters (FAMEs) is of high relevance for monitoring and control of various industrial processes and biological systems. In this study, a novel, green analytical approach for the determination of 24 FAMEs from aqueous samples is proposed, which is based on a headspace solid-phase microextraction (SPME) arrow followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The method was substantially accelerated to a run time of 44 min per sample by thorough optimization and automation of the relevant parameters. The limiting parameters, mostly based on expediting equilibrium attainment, were found to be parameters of extraction: material, pH, time, and temperature, which were optimized to divinylbenzene polydimethylsiloxane (DVB-PDMS), pH 2, 20 min, and 70 °C, respectively. The optimization and automation of the method led to low method detection limits (9-437 ng L-1) and high selectivity. Evaluation of the method on real samples was done by analyzing the aqueous phase of a bioreactor, whereby the matrix effect could be greatly reduced due to dilution and headspace sampling. The rapid, sensitive, selective, and matrix-reduced approach is found to be not only a novel method for water analysis but is promising for further applications, e.g., with solid and gaseous samples containing FAMEs.

Improving greenness and sustainability of standard analytical methods by microextraction techniques: A critical review.

Since environmental awareness has increased in analytical chemistry, the demand for green sample preparation methods continues to grow. Microextractions such as solid-phase microextraction (SPME) and liquid-phase microextraction (LPME) miniaturize the pre-concentration step and are a more sustainable alternative to conventional large-scale extractions. However, the integration of microextractions in standard and routine analysis methods is rare, although these applications are used most frequently and have a role model function. Therefore, it is important to highlight that microextractions are capable to replace large-scale extractions in standard and routine methods. This review discusses the greenness, benefits, and drawbacks of the most common LPME and SPME variants compatible with gas chromatography based on the following key evaluation principles: Automation, solvent consumption, hazards, reusability, energy consumption, time efficiency, and handling. Furthermore, the need to integrate microextractions into standard and routine analytical methods is presented by using method greenness evaluation metrics AGREE, AGREEprep, and GAPI applied to USEPA methods and their replacements.

Ultrafast cold-brewing of coffee by picosecond-pulsed laser extraction.

Coffee is typically brewed by extracting roasted and milled beans with hot water, but alternative methods such as cold brewing became increasingly popular over the past years. Cold-brewed coffee is attributed to health benefits, fewer acids, and bitter substances. But the preparation of cold brew typically needs several hours or even days. To create a cold-brew coffee within a few minutes, we present an approach in which an ultrashort-pulsed laser system is applied at the brewing entity without heating the powder suspension in water, efficiently extracting caffeine and aromatic substances from the powder. Already 3 min irradiation at room temperature leads to a caffeine concentration of 25 mg caffeine per 100 ml, comparable to the concentrations achieved by traditional hot brewing methods but comes without heating the suspension. Furthermore, the liquid phase's alkaloid content, analyzed by reversed-phase liquid chromatography coupled to high-resolution mass spectrometry, is dominated by caffeine and trigonelline and is comparable to traditional cold-brewed coffee rather than hot-brewed coffee. Furthermore, analyzing the head-space of the prepared coffee variants, using in-tube extraction dynamic head-space followed by gas chromatography coupled to mass spectrometry, gives evidence that the lack of heating leads to the preservation of more (semi-)volatile substances like pyridine, which provide cold-brew coffee its unique taste. This pioneering study may give the impetus to investigate further the possibility of cold-brewing coffee, accelerated by more than one order of magnitude, using ultrafast laser systems.