Tuning the selectivity of polymeric ionic liquid sorbent coatings for the extraction of polycyclic aromatic hydrocarbons using solid-phase microextraction

A new generation polymeric ionic liquid (PIL), poly(1-4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (poly(VBHDIm⁺ NTf₂⁻)), was synthesized and is shown to exhibit impressive selectivity towards the extraction of 12 polycyclic aromatic hydrocarbons (PAHs) from aqueous samples when used as a sorbent coating in direct-immersion solid-phase microextraction (SPME) coupled to gas chromatography (GC). The PIL was imparted with aromatic character to enhance π–π interactions between the analytes and the sorbent coating. For comparison purposes, a PIL with similar structure but lacking the π–π interaction capability, poly(1-vinyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) (poly(HDIm⁺ NTf₂⁻)), as well as a commercial polydimethylsiloxane (PDMS) sorbent coating were evaluated and exhibited much lower extraction efficiencies. Extraction parameters, including stir rate and extraction time, were studied and optimized. The detection limits of poly(VBHDIm⁺ NTf₂⁻), poly(HDIm⁺ NTf₂⁻), and PDMS coatings varied between 0.003–0.07 μg L⁻¹, 0.02–0.6 μg L⁻¹, and 0.1–6 μg L⁻¹, respectively. The partition coefficients (log K_fs) of eight PAHs to the three studied fiber coatings were estimated using a static SPME approach. This study represents the first report of analyte partition coefficients to any PIL-based material.     

Determination of water pollutants by direct-immersion solid-phase microextraction using polymeric ionic liquid coatings

The determination of a group of eighteen pollutants in waters, including polycyclic aromatic hydrocarbons and substituted phenols, is conducted in direct-immersion solid-phase microextraction (SPME) using the polymeric ionic liquid (PIL) poly(1-vinyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl]imide as a novel coating material. The performance of the PIL fiber coating in the developed IL-SPME-gas chromatography (GC)–mass spectrometry (MS) method is characterized by average relative recoveries of 92.5% for deionized waters and 90.8% for well waters, average precision values (as relative standard deviations, RSD%) of 11% for deionized waters and 12% for well waters, using a spiked level of 5 ng mL⁻¹. The detection limits oscillate from 0.005 ng mL⁻¹ for fluoranthene to 4.4 ng mL⁻¹ for 4-chloro-3-methylphenol, when using an extraction time of 60 min with 20 mL of aqueous sample. The extraction capabilities of the PIL fiber have been compared with the commercial SPME coatings: polydimethylsyloxane (PDMS) 30 μm, PDMS 100 μm and polyacrylate (PA) 85 μm. The PIL fiber is superior to the PDMS 30 μm for all analytes studied. A qualitative study was also carried out to compare among the nature of the coating materials by normalizing the coating thickness. The PIL material was shown to be more efficient than the PDMS material for all analytes studied. The PIL coating was also adequate for nonpolar analytes whereas the PA material was more sensitive for polar compounds.     

Role of counteranions in polymeric ionic liquid-based solid-phase microextraction coatings for the selective extraction of polar compounds

A polymeric ionic liquid (PIL) poly(1-vinyl-3-hexylimidazolium chloride) (poly(ViHIm⁺Cl⁻)) was designed as a coating material for solid phase microextraction (SPME) to extract polar compounds including volatile fatty acids (VFAs) and alcohols. The extracted analytes were analyzed by using gas chromatography (GC) coupled with flame ionization detection (FID). Extraction parameters of the HS–SPME–GC–FID method, such as ionic strength, extraction temperature, pH and extraction time were optimized. Calibration studies were carried out under the optimized conditions to further evaluate the performance of the PIL-based SPME coating. For comparison purposes, the PIL poly(1-vinyl-3-hexylimidazolium bis[(trifluoromethyl)sulfonyl]imide) (poly(ViHIm⁺NTf₂⁻)) was also used as the SPME coating to extract the same analytes. The results showed that the poly(ViHIm⁺Cl⁻) PIL coating had higher selectivity towards more polar analytes due to the presence of the Cl⁻ anion which provides higher hydrogen bond basicity than the NTf₂⁻ anion. The limits of detection (LODs) determined by the designed poly(ViHIm⁺Cl⁻) PIL coating ranged from 0.02 μg L⁻¹ for octanoic acid and decanoic acid and 7.5 μg L⁻¹ for 2-nitrophenol, with precision values (as relative standard deviation) lower than 14%. The observed performance of the poly(ViHIm⁺Cl⁻) PIL coating was comparable to previously reported work in which commercial or novel materials were used as SPME coatings. The selectivity of the developed PIL coatings was also evaluated using heptane as the matrix solvent. This work demonstrates that the selectivity of PIL-based SPME coatings can be simply tuned by incorporating different counteranions to the sorbent coating.     

Chemical immobilization of crosslinked polymeric ionic liquids on nitinol wires produces highly robust sorbent coatings for solid-phase microextraction

Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30% w/w) H₂O₂ solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix.     

Utilization of a benzyl functionalized polymeric ionic liquid for the sensitive determination of polycyclic aromatic hydrocarbons; parabens and alkylphenols in waters using solid-phase microextraction coupled to gas chromatography-flame ionization detection

The functionalized polymeric ionic liquid poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (poly(VBHDIm(+)NTf(2)(-))) has been used as successful coating in solid-phase microextraction (SPME) to determine a group of fourteen endocrine disrupting chemicals (ECDs), including polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and parabens, in several water samples. The performance of the PIL fiber in direct immersion mode SPME followed by gas chromatography (GC) with flame-ionization detection (FID) is characterized with average relative recoveries higher than 96.1% from deionized waters and higher than 76.7% from drinking bottled waters, with precision values (RSD) lower than 13% for deionized waters and lower than 14% for drinking bottled waters (spiked level of 1 ng mL(-1)), when using an extraction time of 60 min with 20 mL of aqueous sample. Detection limits varied between 9 ng L(-1) and 7 ng mL(-1). A group of real water samples, including drinking waters, well waters, and swimming pool waters, have been analyzed under the optimized conditions. A comparison has also been carried out with the commercial SPME coatings: polydimethylsyloxane (PDMS) 30 μm, and polyacrylate (PA) 85 μm. The functionalized PIL fiber (～12 μm) demonstrated to be superior to both commercial fibers for the overall group of analytes studied, in spite of its lower coating thickness. A normalized sensitivity parameter is proposed as a qualitative tool to compare among fiber materials, being higher for the poly(VBHDIm(+)NTf(2)(-)) coating. Furthermore, the partition coefficients of the studied analytes to the coating materials have been determined. A quantitative comparison among the partition coefficients also demonstrates the superior extraction capability of the functionalized PIL sorbent coating.     

Sorbent coatings for solid-phase microextraction based on mixtures of polymeric ionic liquids

Four polymeric ionic liquids based on two different cations, poly(1‐vinyl‐3‐hexylimidazolium) and poly(1‐vinyl‐3‐hexadecylimidazolium), combined with two different anions, bis[(trifluoromethyl)sulfonyl]imide (NTf) and chloride (Cl^?), were combined in various weight percentages and used as sorbent coatings for solid‐phase microextraction gas chromatography (SPME‐GC). The selectivity of the fiber coatings for 12 test analytes was examined. The extraction efficiency of n‐alcohols increased with an increase in the weight percentage of chloride ion in the sorbent coating. The ability to tune the interactions between the coating material and the analytes was exploited and resulted in distinct changes in the limits of detection for hydrogen‐bonding analytes with varying chloride ion content in the sorbent coating.     

Preparation and characterization of novel crown ether functionalized ionic liquid-based solid-phase microextraction coatings by sol-gel technology

A novel crown ether functionalized ionic liquid (IL), 1-allyl-3-(6'-oxo-benzo-15-crown-5 hexyl) imidazolium hexafluorophosphate was synthesized and used as selective stationary phase to prepare task-specific IL-based solid phase microextraction (SPME) fibers by sol-gel method and free radical cross-linking technology. The underlying mechanism of the sol-gel reaction was proposed and the successful chemical bonding of the crown ether functionalized IL to the formed hybrid organic-inorganic copolymer coating was confirmed by FT-IR spectroscopy. The performance of this in situ created crown ether functionalized IL-based SPME fibers, was investigated in detail. The coating has porous surface structure, stable performance in high temperature (to 340 °C) and in different solutions (water, organic solvent, acid and alkali), and good coating preparation reproducibility. In contrast to the sol-gel derived 1-allyl-3-methyl imidazolium hexafluorophosphate-based coating prepared in our previous work with the identical procedure, the extraction performance of this newly developed sol-gel crown ether functionalized IL-based coating was superior for alcohols, phthalate esters, phenolic environmental estrogens, fatty acids and aromatic amines due to the introduction of benzo-15-crown-5 functional group in IL structure. Moreover, it was shown to provide higher or comparable extraction efficiencies for most analytes studied than did the commercial PDMS, PDMS/DVB and PA fibers.     

Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction

Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf₂]^-) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C₆MIm][NTf₂]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME.     

Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water

A novel microextraction method making use of commercial polymer fiber as sorbent, coupled with high-performance liquid chromatography-fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) in water has been developed. In this technique, the extraction device was simply a length (8 cm) of a strand of commercial polymer fiber, Kevlar (each strand consisted of 1000 filaments, each of diameter ca. 9.23 μm), that was allowed to tumble freely in the aqueous sample solution during extraction. The extracted analytes were desorbed ultrasonically before the extract was injected into HPLC system for analysis. Extraction parameters such as extraction time, desorption time, type of desorption solvent and sample volume were optimized. Each fiber could be used for up to 50 extractions and the method showed good precision, reproducibility and linear response within a concentration range 0.05–5.00 μg L⁻¹ with correlation coefficients of up to 0.9998. Limits of detection between 0.4 and 4.4 ng L⁻¹ for seven PAHs could be achieved. The relative standard deviations (n = 3) of this technique were between 2.9% and 12.1%.     

Graphene oxide reinforced polymeric ionic liquid monolith solid‐phase microextraction sorbent for high‐performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples

A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1‐(3‐aminopropyl)‐3‐(4‐vinylbenzyl)imidazolium 4‐styrenesulfonate monomer and 1,6‐di‐(3‐vinylimidazolium) hexane bihexafluorophosphate cross‐linking agent. Coupled to high‐performance liquid chromatography, the monolith was used as a solid‐phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5–400 μg/L for 3‐nitrophenol, 2‐nitrophenol, and 2,5‐dichlorophenol and 2–400 μg/L for 4‐chlorophenol, 2‐methylphenol, and 2,4,6‐trichlorophenol (R² = 0.9973–0.9988). The limits of detection were 0.5 μg/L for 3‐nitrophenol and 2‐nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5–113%.     

Preparation of a polymeric ionic liquid-coated solid-phase microextraction fiber by surface radical chain-transfer polymerization with stainless steel wire as support

Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%.     

Insitu growth of IRMOF-3 combined with ionic liquids to prepare solid-phase microextraction fibers

A superior solid-phase microextraction (SPME) fiber-coating material, IRMOF-3@ILs/PDMS, was prepared by the in situ growth of IRMOF-3 onto stainless-steel wires and protection with ionic liquids (ILs) and polydimethylsiloxane (PDMS). The ILs can efficiently prevent the substantial cracking of IRMOF-3 caused by moisture, and a thin PDMS film can protect the IRMOF-3@ILs material to achieve a much better extraction efficiency as well as excellent resistance to high temperature and high humidity. This IRMOF-3@ILs/PDMS coating possessed a porous structure, a rough surface and an increased lifespan (by at least 100 times) compared with that of IRMOF-3. The coating was evaluated by analyzing four polycyclic aromatic hydrocarbons (PAHs) in water, and good precision (<7.7%), low detection limits (12.0–15.4 ng L⁻¹), and wide linearity (50–20,000 ng L⁻¹) were achieved under the optimized conditions. The fiber was successfully applied to the sensitive analysis of PAHs in rainwater by coupling it with gas chromatography–mass spectrometry (GC–MS).     

A novel poly(3,4-ethylenedioxythiophene)-ionic liquid composite coating for the headspace solid-phase microextraction and gas chromatography determination of several alcohols in soft drinks

A novel poly(3,4-ethylenedioxythiophene)-ionic liquid (i.e., 1-hydroxyethyl-3-methyl imidazolium-bis[(trifluoromethyl)sulfonyl]imide) composite film was electrodeposited on a Pt wire for headspace solid-phase microextraction. The film showed nodular structure and had large specific surface. In addition, it displayed high thermal stability (up to 300 °C) and durable property (could be used for more than 200 times). Coupled with gas chromatography-flame ionization detection, the resulting fiber was applied to the headspace solid-phase microextraction and determination of several alcohols (i.e., linalool, nonanol, terpineol, geraniol, decanol and dodecanol). It presented higher extraction capability in comparison with the poly(3,4-ethylenedioxythiophene) and commercial polydimethylsiloxane/divinylbenzene fiber. Under the optimized conditions, the linear ranges exceeded three magnitudes with correlation coefficients above 0.9952 and the low limits of detection were 34.2–81.3 ng L⁻¹. For different alcohols the repeatabilities (defined as RSD) were <5.8% and <7.8% for single fiber (n = 5) and fiber-to-fiber (n = 4), respectively. The proposed method was applied to the determination of these alcohols in real samples with acceptable recoveries from 81.1% to 106.6%.     

A new disposable ionic liquid based coating for headspace solid-phase microextraction of methyl tert-butyl ether in a gasoline sample followed by gas chromatography-flame ionization detection

A new ionic liquid (IL) based solid-phase microextraction (SPME) fiber was investigated and used for headspace (HS) extraction of methyl tert-butyl ether (MTBE) in a gasoline sample. Using the new IL coated HS-SPME fiber with the combination of gas chromatography-flame ionization detection (GC-FID); sub-to-low μg L⁻¹ concentrations of MTBE were detected. Four different ILs including 1-butyl-3-methylimidazolium tetraflouroborate ([C₄C₁IM] [BF₄]), 1-octyl-3-methylimidazolium tetraflouroborate ([C₈C₁IM] [BF₄]), 1-octyl-3-methylimidazolium hexaflourophosphate ([C₈C₁IM] [PF₆]) and 1-ethyl-3-methylimidazolium ethylsulphate ([C₂C₁IM] [ETSO₄]) were synthesized and examined for extraction, preconcentration and determination of MTBE. It was observed that [C₈C₁IM] [BF₄] showed the highest extraction efficiency and possessed the best extractability for MTBE. The fiber coating takes up the compounds from the sample by absorption in the case of liquid coatings. The calibration graph was linear in a concentration range of 1-120 μg L⁻¹ (R² > 0.994) with the detection limit of 0.09 μg L⁻¹ level. The new IL-coated fiber was applied successfully for the determination of MTBE in a gasoline sample with good recoveries between 90 and 95%.     

Developing qualitative extraction profiles of coffee aromas utilizing polymeric ionic liquid sorbent coatings in headspace solid-phase microextraction gas chromatography-mass spectrometry

Two solid-phase microextraction (SPME) sorbent coatings based on polymeric ionic liquids (PILs) have been utilized for the analysis of complex coffee aroma samples. The PIL-based SPME coatings examined, namely, poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) [poly(VBHDIm⁺ NTf₂⁻)], with ∼14-μm thickness, and poly(1-vinyl-3-hexylimidazolium chloride) [poly(ViHIm⁺ Cl⁻)], with ∼8-μm thickness, were employed for the headspace determination of up to 49 analytes from four different coffee beans: two French roast coffees of different brands, Sumatra coffee, and decaffeinated Sumatra coffee. The analysis was conducted using gas chromatography coupled to mass spectrometry. For comparative purposes, the commercial polyacrylate (PA, 85-μm film thickness) SPME coating was utilized under the same extraction conditions. The three SPME coatings tested behaved quite differently as a function of the families of compounds extracted. Thus, the poly(VBHDIm⁺ NTf₂⁻) coating was extremely selective for aldehydes while also exhibiting good extraction efficiencies for acids. The poly-(ViHIm⁺ Cl⁻) coating exhibited superior performance for aromatic alcohols, and the PA coating worked better for heterocyclic aromatics. Both PIL-based SPME sorbent coatings demonstrated exceptional selectivity and extraction efficiency when dealing with complex coffee aromas in spite of their small film thicknesses.     

Preparation of ionic liquid based solid-phase microextraction fiber and its application to forensic determination of methamphetamine and amphetamine in human urine

A new solid-phase microextraction (SPME) procedure using an ionic liquid (IL) has been developed. Reusable IL-based SPME fiber was prepared for the first time by fixing IL through cross-linkage of IL impregnated silicone elastomer on the surface of a fused silica fiber. 1-Ethoxyethyl-3-methylimidazloium bis(trifluoromethane) sulfonylimide ([EeMim][NTf₂]) ionic liquid was employed as a demonstration and the prepared fiber was applied to the forensic headspace determination of methamphetamine (MAP) and amphetamine (AP) in human urine samples. Important extraction parameters including the concentration of salt and base in sample matrix, extraction temperature and extraction time were investigated and optimized. Combined with gas chromatography/mass spectrometry (GC/MS) working in selected ion monitoring (SIM) mode, the new method showed good linearity in the range of 20–1500 μg L⁻¹, good repeatability (RSD < 7.5% for MAP, and <11.5% for AP, n = 6), and low detection limits (0.1 μg L⁻¹ for MAP and 0.5 μg L⁻¹ for AP). Feasibility of the method was evaluated by analyzing human urine samples. Although IL-based SPME is still at the beginning of its development stage, the results obtained by this work showed that it is a promising simple, fast and sensitive sample preparation method.     

Hydroxyl-functionalized ionic liquid: a novel efficient catalyst for chemical fixation of CO2 to cyclic carbonate

A series of hydroxyl-functionalized ionic liquids (HFILs) were synthesized and characterized. They showed efficient reactivity and reusability toward the coupling of epoxide and CO₂ without any additional co-catalyst and organic solvent. Highest activity and selectivity were achieved in the presence of 1-(2-hydroxyl-ethyl)-3-methylimidazolium bromide (HEMIMB) in comparison with other similar catalysts investigated. The relationship between the higher catalytic reactivity and OH-functional group was proposed.     

Multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid with high‐performance liquid chromatography for the determination of steroid sex hormones in water and urine

The development of a simple and sensitive analytical approach that combines multiple monolithic fiber solid‐phase microextraction with liquid desorption followed by high‐performance liquid chromatography with diode array detection is proposed for the determination of trace levels of seven steroid sex hormones (estriol, 17β‐estradiol, testosterone, ethinylestradiol, estrone, progesterone and mestranol) in water and urine matrices. To extract the target analytes effectively, multiple monolithic fiber solid‐phase microextraction based on a polymeric ionic liquid was used to concentrate hormones. Several key extraction parameters including desorption solvent, extraction and desorption time, pH value and ionic strength in sample matrix were investigated in detail. Under the optimal experimental conditions, the limits of detection were found to be in the range of 0.027–0.12 μg/L. The linear range was 0.10–200 μg/L for 17β‐estradiol, 0.25–200 μg/L estriol, ethinylestradiol and estrone, and 0.50–200 μg/L for the other hormones. Satisfactory linearities were achieved for analytes with the correlation coefficients above 0.99. Acceptable method reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations of both less than 8%. The enrichment factors ranged from 54‐ to 74‐fold. Finally, the proposed method was successfully applied to the analysis of steroid sex hormones in environmental water samples and human urines with spiking recoveries ranged from 75.6 to 116%.     

Extraction and determination of hormones in cosmetics by homogeneous ionic liquid microextraction high-performance liquid chromatography

The homogeneous ionic liquid microextraction was applied to the extraction of hormones from cosmetics and the hormones were determined by high-performance liquid chromatography. 1-Hexyl-3-methylimidazolium tetrafluoroborate was used as extraction solvent. Ammonium hexafluorophosphate as used as ion-pairing agent. Several experimental parameters, including the volume of 1-hexyl-3-methylimidazolium tetrafluoroborate, amount of ammonium hexafluorophosphate and sodium chloride, extraction and centrifuge time, and the pH value, were optimized. The limits of detection and quantification for the analytes ranged from 0.03 to 0.24 ng/mL and from 0.10 to 0.79 ng/mL, respectively. The precision for determining the hormones was lower than 5.2%. The proposed method was successfully developed for the determination of hormones in real cosmetic samples.