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 C 6 solvents complemented by n-pentane and n-heptane during the nano-second 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, ΔH vap , 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.
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.
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.
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