Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Using ionic liquid combined with HPLC-DAD to analyze semi-permanent hair dyes in commercial formulations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Controlling the formation of ionic-liquid-based aqueous biphasic systems by changing the hydrogen-bonding ability of polyethylene glycol end groups

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Novel polymer electrolytes based on gelatin and ionic liquids

This study describes the results of the characterization of polymer electrolytes using gelatin matrix doped with europium triflate and/or different ionic liquids. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. Electrolyte samples are thermally stable up to approximately 220 degrees C. All the materials synthesized are totally amorphous. The room temperature conductivity maximum of this electrolyte system is based on ionic liquid 1-ethyl-3-methylimidazolium acetate, (C(2)mim)(OAc) (1.18 x 10(-4) S cm(-1) at 30 degrees C). The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. This new series of materials represents a promising alternative in polymer electrolytes research field. The preliminary studies carried out with electrochromic devices (ECDs) incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of "smart windows". This new materials, will open a land of promising applications in many areas: optics, energy, medicine for example as membranes and separation devices, ECD-based devices, sensors, etc. (C) 2012 Elsevier B.V. All rights reserved.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid���liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid���liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid���liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid���liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Organic reactions in ionic liquids: ionic liquid-accelerated facile synthesis of 3-alkyl-2,4-thiazolidinediones

The room temperature ionic liquid [bmim]PF6 is a new green solvent for the N-alkylation of 2,4-thiazolidinones. Significant rate enhancement and improved yields have been observed.

Organic reactions in ionic liquids:Ionic liquid promoted Knoevenagel condensation of aromatic aldehydes with (2-thio)barbituric acid

The Knoevenagel condensation of aromatic aldehydes with (2-thio)barbituric acid proceeded efficiently in reusable ionic liquids, EAN, BmimBF4, and BmimPF6 at room temperature in the absence of any catalyst with high yields.

Ionic liquid-accelerated N-arylation of benzoazoles with diaryliodonium salts, an efficient method for the synthesis of N-aryl azoles

N-Arylation of benzoazoles with diaryliodonium salts can be performed in good yields in the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4), which provides an efficient method for the synthesis of N-arylbenzoazoles. The ionic liquid can be recycled and reused.

Ionic liquid-accelerated arylation of sodium arenesulfinates with diaryliodonium salts used for the synthesis of diaryl sulfones

Arylation of sodium arenesulfinates with diaryliodonium salts can be performed with good yields in the room-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMim]BF4), which provides an efficient method for the synthesis of diaryl sulfones; the ionic liquid can be recycled and reused.

Organic reactions in ionic liquids: ionic liquid-accelerated nucleophilic substitution reaction of alpha-tosyloxyketones with potassium salts of aromatic acids

The room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) is used as a ‘green' recyclable alternative to classical molecular solvents for the nucleophilic substitution reaction of a-tosyloxy ketones with potassium salts of aromatic acids. Significant rate enhancement and improved yields have been observed.

Organic reactions in ionic liquids; Ionic liquid-accelerated three-component reaction: a rapid one-pot synthesis of 3-alkyl-5-[(Z)-arylmethylidene]-1,3-thiazolidine-2,4-diones

A rapid one-pot synthesis of 3-alkyl-5-[(Z)-arylme­thylidene]-1,3-thiazolidine-2,4-dionesis described that occurs in recyclable ionic liquid [bmim]PF6 (1-butyl-3-methylimidazolium hexafluorophosphate).Significant rate enhancement and good selectivity have been observed.

Organic reactions in ionic liquids: ionic liquid-accelerated cyclocondensation of alpha-tosyloxyketones with 2-aminopyridine

The room temperature ionic liquid it-butylpyridinium tetrafluoroborate (BPyBF4) is used as a `green' recyclable alternative to classical molecular solvents for the cyclocondensation of alpha-tosyloxyketones with 2-aminopyridine. Significant rate enhancements and improved yields have been observed.

Analysis of bio-derived platform chemicals in ionic liquid media by desorption/ionization mass spectrometry

In this work, desorption/ionization mass spectrometry was employed for the analysis of sugars and small platform chemicals that are common intermediates in biomass transformation reactions. Specifically, matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) mass spectrometric techniques were employed as alternatives to traditional chromatographic methods. Ionic liquid matrices (ILMs) were designed based on traditional solid MALDI matrices (2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (CHCA)) and 1,3-dialkylimidazolium ionic liquids ([BMIM]Cl, [EMIM]Cl, and [EMIM]OAc) that have been employed as reaction media for biomass transformation reactions such as the conversion of carbohydrates to valuable platform chemicals. Although two new ILMs were synthesized ([EMIM][DHB] and [EMIM][CHCA] from [EMIM]OAc), chloride-containing ILs did not react with matrices and resulted in mixtures of IL and matrix in solution. Compared to the parent solid matrices, much less matrix interference was observed in the low mass region of the mass spectrum (< 500 Da) using each of the IL-matrices. Furthermore, the formation of a true ILM (i.e. a new ion pair) does not appear to be necessary for analyte ionization. MALDI sample preparation techniques were optimized based on the compatibility with analyte, IL and matrix. ILMs and IL-matrix mixtures of DHB allowed for qualitative analysis of glucose, fructose, sucrose and N-acetyl-D-glucosamine. Analogous CHCA-containing ILMs did not result in appreciable analyte signals under similar conditions. Small platform compounds such as 5-hydroxymethylfurfural (HMF) and levulinic acid were not detected by direct analysis using MALDI-MS. Furthermore, sugar analyte signals were only detected at relatively high matrix:IL:analyte ratios (1:1:1) due to significant matrix and analyte suppression by the IL ions. Therefore, chemical modification of analytes with glycidyltrimethylammonium chloride (GTMA) was employed to extend this method to quantitative applications. Derivatization was accomplished in aqueous IL solutions with fair reaction efficiencies (36.9 – 48.4 % glucose conversion). Calibration curves of derivatized glucose-GTMA yielded good linearity in all solvent systems tested, with decreased % RSDs of analyte ion signals in IL solutions as compared to purely aqueous systems (1.2 – 7.2 % and 4.2 – 8.7 %, respectively). Derivatization resulted in a substantial increase in sensitivity for MALDI-MS analyses: glucose was reliably detected at IL:analyte ratios of 100:1 (as compared to 1:1 prior to derivatization). Screening of all test analytes resulted in appreciable analyte signals in MALDI-MS spectra, including both HMF and levulinic acid. Using appropriate internal standards, calibration curves were constructed and this method was employed for monitoring a model dehydration reaction of fructose to HMF in [BMIM]Cl. Calibration curves showed wide dynamic ranges (LOD – 100 ng fructose/μg [BMIM]Cl, LOD – 75 ng HMF/μg [BMIM]Cl) with correlation coefficients of 0.9973 (fructose) and 0.9931 (HMF). LODs were estimated from the calibration data to be 7.2 ng fructose/μg [BMIM]Cl and 7.5 ng HMF/μg [BMIM]Cl, however relatively high S/N ratios at these concentrations indicate that these values are likely overestimated. Application of this method allowed for the rapid acquisition of quantitative data without the need for prior separation of analyte and IL. Finally, small molecule platform chemicals HMF and levulinic acid were qualitatively analyzed by DESI-MS. Both HMF and levulinic acid were easily ionized and the corresponding molecular ions were easily detected in the presence of 10 – 100 times IL, without the need for chemical modification prior to analysis. DESI-MS analysis of ILs in positive and negative ion modes resulted in few ions in the low mass region, showing great potential for the analysis of small molecules in IL media.