Binary Solvents Dispersive Liquid-Liquid Microextraction (BS-DLLME) Method for Determination of Tramadol in Urine Using High-Performance Liquid Chromatography.

BACKGROUND: Tramadol is an opioid, synthetic analog of codeine and has been used for the treatment of acute or chronic pain may be abused. In this work, a developed Dispersive liquid liquid microextraction (DLLME) as binary solvents-based dispersive liquid-liquid microextraction (BS-DLLME) combined with high performance liquid chromatography (HPLC) with fluorescence detection (FD) was employed for determination of tramadol in the urine samples. This procedure involves the use of an appropriate mixture of binary extraction solvents (70 µL CHCl3 and 30 µL ethyl acetate) and disperser solvent (600 µL acetone) for the formation of cloudy solution in 5 ml urine sample comprising tramadol and NaCl (7.5%, w/v). After centrifuging, the small droplets of extraction solvents were precipitated. In the final step, the HPLC with fluorescence detection was used for determination of tramadol in the precipitated phase. RESULTS: Various factors on the efficiency of the proposed procedure were investigated and optimized. The detection limit (S/N = 3) and quantification limit (S/N = 10) were found 0.2 and 0.9 µg/L, respectively. The relative standard deviations (RSD) for the extraction of 30 µg L of tramadol was found 4.1% (n = 6). The relative recoveries of tramadol from urine samples at spiking levels of 10, 30 and 60 µg/L were in the range of 95.6 - 99.6%. CONCLUSIONS: Compared with other methods, this method provides good figures of merit such as good repeatability, high extraction efficiency, short analysis time, simple procedure and can be used as microextraction technique for routine analysis in clinical laboratories.

Stirring-controlled solidified floating solid-liquid drop microextraction as a new solid phase-enhanced liquid-phase microextraction method by exploiting magnetic carbon nanotube-nickel hybrid.

A specific technique is introduced to overcome limitations of classical solidification of floating organic drop microextraction, such as tedious and time-consuming centrifuge step and using disperser solvent, by facile and efficient participation of solid and liquid phases. In this proposed method of stirring-controlled solidified floating solid-liquid drop microextraction (SC-SF-SLDME), magnetic carbon nanotube-nickel hybrid (MNi-CNT) as a solid part of the extractors are dispersed ultrasonically in sample solution, and the procedure followed by dispersion of liquid phase (1-undecanol) through high-rate stirring and easily recollection of MNi-CNT in organic solvent droplets through hydrophobic force. With the reduction in speed of stirring, one solid-liquid drop is formed on top of the solution. MNi-CNT acts as both extractor and the coalescence helper between organic droplets for a facile recollection. MNi-CNT was prepared by spray pyrolysis of nickel oleate/toluene mixture at 1000 °C. Four tyrosine kinase inhibitors were selected as model analytes and the effecting parameters were investigated. The results confirmed that magnetic nanoadsorbent has an important role in the procedure and complete collection of dispersed solvent is not achieved in the absence of the solid phase. Also, short extraction time exhibited success of the proposed method and effect of dispersed solid/liquid phases. The limits of quantification (LOQs) for imatinib, sunitinib, erlotinib, and nilotinib were determined to be as low as 0.7, 1.7, 0.6, and 1.0 µg L-1, respectively. The intra-day precisions (RSDs) were lower than 4.5%. Method performance was investigated by determination of mentioned tyrosine kinase inhibitors (TKIs) in human serum and cerebrospinal fluid samples with good recoveries in the range of 93-98%.

Chromium speciation in human blood samples based on acetyl cysteine by dispersive liquid-liquid biomicroextraction and in-vitro evaluation of acetyl cysteine/cysteine for decreasing of hexavalent chromium concentration.

A rapid and efficient method based on ionic liquid dispersive liquid-liquid biomicroextraction (IL-DLLBME) was used for speciation and preconcentration of Chromium (III, VI) in human blood samples before determination by electro-thermal atomic absorption spectrometer (ET-AAS). In this method, 1-hexyl-3-methylimidazolium hexafluorophosphate as a ionic liquid was dissolved in acetone as a dispersant solvent and then the binary solution was rapidly injected by a syringe into the blood samples containing Cr(III), which have already complexed by acetyl cysteine (NAC) at optimized pH. Under the optimal conditions, the linear range (LR), limit of detection (LOD) and preconcentration factor (PF) were obtained 0.03-4.4 µg L(-1), 0.005 µg L(-1) and 10 respectively (RSD <5%). In vitro study show us, the cysteine (Cys) as a prodrug of NAC can decrease the concentration of Cr(VI) in blood samples and human body. Validation of methodology was confirmed by standard reference material (SRM).

Graphene-silica hybrid in efficient preconcentration of heavy metal ions via novel single-step method of moderate centrifugation-assisted dispersive micro solid phase extraction.

Novel nanoadsorbent of graphene-silica hybrid was synthesized via chemical vapor deposition (CVD) method. Graphene sheets were catalytically grown on a silica-based substrate and after being characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), their high efficacy in adsorption of metal ions (lead, cadmium, and chromium) was examined. It was found that the presence of silica within the G-SiO2 structure imparts an amphiphilic property to the hybrid that enables it to interact with both free and bounded metal ions present in the biological samples. Utilization of the innovative method of moderate centrifugation-assisted dispersive micro solid phase extraction (MCDµSPE) coupled with electrothermal atomic absorption spectrometry (ETAAS), not only facilitated absolute separation of the fabricated nanoadsorbent from the solvent, but also helped complete recovering of the scant volume of desorbed supernatant. Thus, microliter amount of desorption solvent can be regained completely by MCDµSPE method without sorbent loss. Various parameters affecting the extraction efficiency were investigated and admirable linearity from 0.012 to 12.5 µg L(-1) and favorable detection limits (LOD) could be recorded. Intra day precision (RSD, n=10) ranged from 3.1 to 3.8%, whereas inter day precision (RSD, n=5) ranged from 6.3 to 7.2%.

Innovative separation and preconcentration technique of coagulating homogenous dispersive micro solid phase extraction exploiting graphene oxide nanosheets.

A uniquely novel, fast, and facile technique is introduced for the first time in which a scant amount of graphene oxide (GO), without modification, has been utilized in dispersive mode of solid phase extraction (SPE) for an efficient yet simple separation. The proposed method of coagulating homogenous dispersive micro solid phase extraction (CHD-µSPE) is based on coagulation of homogeneous GO solution with the aid of polyetheneimine (PEI). CHD-µSPE use full adsorption capacity of GO because in this method was used GO solution obtained from synthesis process without drying step and stacking nanosheets. In optimized condition, 30 µL GO solution (7 mg mL(-1)), obtained in synthesis process, was injected into 1.5 mL the sample solution followed by immediate injection of 53 µL PEI solution (1 mg mL(-1)). After inserting PEI, GO sheets aggregate and can be readily separated by centrifugation. PEI not only cause aggregation of GO, but also form three-dimensional network of GO with easy handling in following separation steps. Lead, cadmium, and chromium were selected as model analytes and the effecting parameters including the amount of GO, concentration of PEI, sample pH, extraction time, and type of desorption solvent were investigated and optimized. The results indicate that the proposed CHD-µSPE method can be successfully applied GO in dispersive mode of SPE without effecting on good capability adsorption of GO. The novel method was applied in determination of lead, cadmium, and chromium in water, human saliva, and urine samples by electrothermal atomic absorption spectrometry. The detection limits are as low as 0.035, 0.005, and 0.012 µg L(-1) for Pb, Cd, and Cr respectively. The intra-day precisions (RSDs) were lower than 3.8%. CHD-µSPE method showed a good linear ranges of 0.24-15.6, 0.015-0.95 and 0.039-2.33 µg L(-1) for Pb, Cd and Cr respectively. Method performance was investigated by determination of mentioned metal ions in river water, human urine and saliva sample with good recoveries in range of 94.2-103.0%. The accuracy of the method was underpinned by correct analysis of a standard reference material (SRM: 2668 level I, Urine).