Development of a new continuous homogenous liquid phase microextraction procedure based on in-situ preparation of deep eutectic solvent; application in the analysis of aliphatic amines in urine samples by GC-MS.

In the present work, a new microextraction procedure combined with gas chromatography-mass spectrometry has been developed for the analysis of several aliphatic amines from urine sample. The sample preparation method was a continuous homogenous liquid phase microextraction that was based on in-situ preparation of 4-chlorophenol: choline chloride deep eutectic solvent. The deep eutectic solvent was prepared by passing the mixture of related compounds through a syringe barrel filled with exothermic salts (calcium chloride and potassium bromide). The released heat by dissolving the salts and increasing the solution ionic strength assists the formation of the deep eutectic solvent. The influence of various factors on the efficiency of the proposed procedure including salts amount, flow rate, pH, salting-out effect, and extraction solvent volume was studied. The calibration curves were linear broadly over the concentration range of 1.2-250 ng mL-1 with coefficient of determinations ≥0.996. The enrichment factors were in the range of 188-246 and the limits of detection and quantification were 0.16-0.37 and 0.56-1.2 ng mL-1, respectively. Based on the results, the offered method was sensitive, rapid, eco-friendly, and efficient for extracting and determining aliphatic amines in urine samples.

In situ formation of chloroform for dispersive liquid-liquid microextraction of some aromatic amines from aqueous samples optimized by central composite design prior to GC-MS analysis.

In the current research, an in situ solvent formation-liquid phase microextraction method based on chloroform has been introduced as an efficient sample preparation procedure and applied for the extraction and preconcentration of some aromatic amines from wastewaters. In this method, chloral hydrate (2,2,2-trichloroethane-1,1-diol) was added to an alkaline solution of the samples in order to form chloroform as an extraction solvent in the sample solution. Thus, the selected analytes were transferred from the aqueous solution into the tiny droplets of the produced chloroform. Following this, the extracted and enriched analytes were quantified using a gas chromatograph-mass spectrometer. Experimental conditions of the proposed method including the chloral hydrate amount, salt effect, extraction time, and sodium hydroxide concentration were studied and optimized by a central composite design approach. By the offered method, high enrichment factors (292-324) with satisfactory extraction recoveries (82-91%), low limits of detection (0.26-0.39 ng mL-1), and proper repeatability (relative standard deviations ≤6.3% for intra- and inter-day precisions) were achieved under optimum conditions. Eventually, the suggested method was assessed through the quantification of aromatic amines in aqueous samples.