Fabrication of a new electrochemiluminescent sensor for fentanyl citrate based on glassy carbon microspheres and ionic liquid composite paste electrode

Due to the high performance of glassy carbon in the aspects of mechanical strength, electrical conductivity and high corrosion resistance, etc., glassy carbon has been widely used in the electrochemistry. A new form of glassy carbon, glassy carbon microsphere, was utilized to couple with ionic liquid in preparing a new electrochemiluminescent platform for Ru(bpy)₃Cl₂. Room temperature ionic liquid has been proposed to be very interesting and efficient pasting binder to replace the non conductive organic binders for the fabrication of composite paste electrode. Attributed to the special characteristics of glassy carbon microspheres and room temperature ionic liquid [N-octylpyridium tetrafluoroborate (OPFP)], this new electrochemiluminescent sensor exhibited excellent electrochemiluminescent performance in Ru(bpy)₃²⁺ solution. We first found that fentanyl citrate could increase the ECL of Ru(bpy)₃²⁺, hence an ECL approach was developed for the determination of fentanyl citrate based on this glassy carbon microspheres based electrochemiluminescent platform with high sensitivity. Under the optimized conditions, the enhanced electrochemiluminescent intensity versus fentanyl citrate concentration was linear in the range of 1.0 × 10⁻⁸ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 8.5 × 10⁻⁹ mol L⁻¹, and the relative standard deviation for 1.0 × 10⁻⁶ mol L⁻¹ fentanyl citrate was 1.90% (n = 10). This protocol has extended the application scopes of glassy carbon material and promoted the application of glassy carbon microspheres in electroanalysis.     

Extraction and mechanism investigation of trace roxithromycin in real water samples by use of ionic liquid-salt aqueous two-phase system

The ionic liquid, as a green solvent, has several advantages over the organic solvents in traditional liquid-liquid extraction. Aqueous two-phase system (ATPS) consisting of a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoraborate, [Bmim]BF₄) and Na₂CO₃, which is a novel, simple, non-toxic and effective sample pretreatment technique coupled with molecular fluorescence spectrophotometry, was developed for the simultaneous separation, enrichment and rapid analysis of roxithromycin. The extraction yield of roxithromycin in [Bmim]BF₄-Na₂CO₃ aqueous two-phase system is influenced by the types of salts, concentrations of Na₂CO₃ and [Bmim]BF₄, as well as the extracting temperature. Under the optimum conditions, the average extraction efficiency is up to 90.7%. The mechanism of ionic liquid-salt ATPS formation was discussed by hydration theory, and the extraction mechanism of the [Bmim]BF₄-salt ATPS was investigated by FT-IR spectroscopy and UV-vis spectroscopy. The results demonstrate that no chemical (bonding) interactions are observed between ionic liquid and roxithromycin, while the nature properties of the roxithromycin are not altered. This method was practical when applied to the analysis of roxithromycin in real water samples with the detection limit of 0.03 μg mL⁻¹, relative standard deviation (RSD) of 1.9% (n = 13), and linear ranges of 1.00-20.00 μg mL⁻¹. The proposed extraction technique will be promising in the separation of other small biomolecules.     

Determination of water-soluble inorganic and organic species in atmospheric fine particulate matter

The use of ion chromatography (IC) in conjunction with ultrasonic extraction is described for the routine analysis of water-soluble major inorganic ions and organic acids in atmospheric fine particles (PM_2.5). Both the extraction method and the IC analysis were validated using NIST SRM 1648 (urban particulate matter). In addition, the reliability of the IC method was established by intercomparison of results obtained with those from suitable alternative analytical techniques (atomic absorption spectrometry (AAS), proton-induced X-ray emission (PIXE) spectrometry, and UV-Visible spectrophotometry). The validated IC method was successfully applied for field monitoring of PM_2.5 particles collected in Singapore over an extended period of time. The IC analysis revealed that the concentrations of individual ions were in the order, SO₄²⁻ > NH₄⁺ > NO₃⁻ > Na⁺ > K⁺ > Cl⁻, respectively. Among the major ionic components, SO₄²⁻ contributed 50% to the measured water-soluble aerosol mass followed by NH₄⁺ (16.5%) and NO₃⁻ (9.0%). The cations Na⁺, K⁺, Mg²⁺, and Ca²⁺ accounted for 24% of the total water-soluble mass. The IC analysis was performed to quantify the organic acids, which typically account for a small fraction of water-soluble organic compounds in PM_2.5. Oxalate was found to be the dominant species among the organic acids measured in this work.     

Electrochemical behavior of hexafluoroniobate, heptafluorotungstate, and oxotetrafluorovanadate anions in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide room temperature ionic liquid

Electrochemical behavior of hexafluoroniobate (Nb(V)F₆⁻), heptafluorotungstate (W(VI)F₇⁻), and oxotetrafluorovanadate (V(V)OF₄⁻) anions has been investigated in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPyrTFSA) ionic liquid at 298 K by means of cyclic voltammetry and chronoamperometry. Cyclic voltammograms at a Pt electrode showed that Nb(V)F₆⁻ anion is reduced to Nb(IV)F₆²⁻ by a one-electron reversible reaction. Electrochemical reductions of W(VI)F₇⁻ and V(V)OF₄⁻ anions at a Pt electrode are quasi-reversible and irreversible reactions, respectively, according to cyclic voltammetry. The diffusion coefficients of Nb(V)F₆⁻, W(VI)F₇⁻ and V(V)OF₄⁻ determined by chronoamperometry are 1.34 × 10⁻⁷, 7.45 × 10⁻⁸ and 2.49 × 10⁻⁷ cm² s⁻¹, respectively. The Stokes radii of Nb(V)F₆⁻, W(VI)F₇⁻, and V(V)OF₄⁻ in BMPyrTFSA have been calculated to be 0.23, 0.38, and 0.12 nm, from the diffusion coefficients and viscosities obtained.     

A new room temperature ionic liquid of oxyfluorometallate anion: 1-Ethyl-3-methylimidazolium oxypentafluorotungstate (EMImWOF5)

The first room temperature ionic liquid (room temperature molten salt) containing oxyfluorometallate anion, 1-ethyl-3-methylimidazolium oxypentafluorotungstate (EMImWOF₅), has been synthesized and characterized compared to other known EMIm fluorocomplex salts. EMImWOF₅ is synthesized by two routes: one is the hydrolysis of EMImWF₇ and the other is the fluoroacid-base reaction of EMIm(HF)_2.3F and WOF₄. EMImWOF₅ is a hydrophilic room temperature ionic liquid but is stable in aqueous solution. From the result of DSC analysis, EMImWOF₅ exhibits a glass transition at 182 K and melts at 253 K. The density, conductivity and viscosity at 298 K are 2.25 g cm⁻³, 3.0 mS cm⁻¹ and 105.1 cP, respectively.     

Ionic liquid of [Bmim]Cl for the preparation of hierarchical nanostructured rutile titania

The rutile titania with hierarchical nanostructure was conveniently prepared in a room temperature ionic liquid (RTIL) of [Bmim]⁺Cl⁻ system. The obtained materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ adsorption-desorption analysis. XRD patterns revealed that only rutile phase was formed in the ionic liquid of [Bmim]⁺Cl⁻. The SEM and TEM micrographs as well as N₂ adsorption-desorption measurements showed that the nanorods of rutile titania were interaggregated to fabricate a large mesoporous structure and the voids packed in the nanorods formed a small mesostructure. It was proposed that the formation of rutile crystal phase was due to high acidity and high Cl⁻ content in the special reaction media, and also the combination of ionic liquid-templated effects with so-called reaction limited aggregation resulted in the hierarchical nanostructure.     

Cesium fluorohydrogenate, Cs(FH)2.3F

Cs(FH)_2.3F is a liquid salt exhibiting a low viscosity of 20.1 cP and a high conductivity of 86.3 mS cm⁻¹ at 25 °C, in spite of the relatively high melting point (16.9 °C). The high density of 2.82 g cm⁻³ at the liquid state is due to the heavy atomic weight and small size of cesium atom compared to the organic cations of general ionic liquids. The infrared spectroscopy indicates that this salt contains (FH)₂F⁻ as a main anionic species. The other anionic species such as (FH)₃F⁻ found in the cases of other M⁺(HF)_2.3F (M = a univalent organic cation) ionic liquid salts is not detected, suggesting its small abundance as well as the presence of neutral HF in the form of molecular and/or oligomers. The result of ¹H NMR also suggests that the anions exchange HF between them. These observations coincide with the experimental result that Cs(FH)_2.3F acts as an acid against general ionic liquid fluorohydrogenates such as EMIm(FH)_2.3F (EMIm = 1-ethyl-3-methylimidazolium) to lose HF and give Cs(FH)₂F precipitate.     

A sensitive and highly stable electrochemical impedance immunosensor based on the formation of silica gel-ionic liquid biocompatible film on the glassy carbon electrode for the determination of aflatoxin B1 in bee pollen

The paper describes a sensitive and highly stable label-free electrochemical impedance immunosensor for the determination of aflatoxin B₁ (AFB₁), which is based on the formation of silica gel-ionic liquid biocompatible film on the glassy carbon electrode. The electrochemical performances of the sensor were investigated by electrochemical impedance spectroscopy using a Fe(CN)₆^3−/4− phosphate buffer solution as base solution for test. As new ionic liquid, 1-amyl-2,3-dimethylimidazolium hexafluorophosphate, offers a very biocompatible microenvironment for AFB₁ antibody, the sensor exhibits good repeatability (RSD = 1.2%), sensitive electrochemical impedance response to AFB₁ in the range of 0.1-10 ng ml⁻¹ and lowers the detection limit of AFB₁ (0.01 ng ml⁻¹)_. The electron-transfer resistance change of the sensor after and before incubation with AFB₁ of 2.0 ng ml⁻¹ can retain 95% over a 180-day storage period at 4 °C. The results present a remarkable improvement of sensitivity (2-fold) and long-term stability (190-fold) when compared to classical silica gel sensor. Moreover, proposed sensor has a high selectivity to AFB₁ alone with no significant response to AFB₂, AFG₁, AFG₂ and AFM₁ as single substrates, it has been successfully applied to the determination of trace AFB₁ in bee pollen samples with a spiked recovery in the range of 96.0-102.5%.     

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

An overview of recent structural studies on alkylimidazolium-based salts containing fluoroanions is presented. Alkylimidazolium cations have been most extensively used for syntheses of ionic liquids (room temperature molten salts) because they usually exhibit low melting points, low viscosities and high conductivities. This review mainly focuses on structures of alkylimidazolium-based salts combined with a fluorocomplex anion ((FH)_nF⁻, BF₄⁻, PF₆⁻, AsF₆⁻, SbF₆⁻, NbF₆⁻, TaF₆⁻), N(SO₂CF₃)₂⁻ (TFSI⁻) and OSO₂CF₃⁻. The first part describes crystal structures of these salts and the second part describes computational, spectroscopic and diffraction studies on their liquid structures. Related studies on ionic liquids of non-alkylimidazolium cation and non-fluoroanion are also briefly summarized.     

Layer by layer assembly of catalase and amine-terminated ionic liquid onto titanium nitride nanoparticles modified glassy carbon electrode: Study of direct voltammetry and bioelectrocatalytic activity

A novel, simple and facile layer by layer (LBL) approach is used for modification of glassy carbon (GC) electrode with multilayer of catalase and nanocomposite containing 1-(3-Aminopropyl)-3-methylimidazolium bromide (amine terminated ionic liquid (NH₂-IL)) and titanium nitride nanoparticles (TiNnp). First a thin layer of NH₂-IL is covalently attached to GC/TiNnp electrode using electro-oxidation method. Then, with alternative self assemble positively charged NH₂-IL and negatively charged catalase a sensitive H₂O₂ biosensor is constructed, whose response is directly correlated to the number of bilayers. The surface coverage of active catalase per bilayer, heterogeneous electron transfer rate constant (k_s) and Michaelis–Menten constant (K_M) of immobilized catalase were 3.32 × 10⁻¹² mol cm⁻², 5.28 s⁻¹ and 1.1 mM, respectively. The biosensor shows good stability, high reproducibility, long life-time, and fast amperometric response with the high sensitivity of 380 μA mM⁻¹ cm⁻² and low detection limit of 100 nM at concentration range up to 2.1 mM.     

Chemistry in heterocyclic ammonium fluorohydrogenate room-temperature ionic liquid

Investigation on alkali fluoride-HF system has been initiated in the 19th century. The technique is currently utilized in fluorine-chemical industry. But, the problem is that this system readily releases hazardous HF. Although organic base, e.g., amine, with HF, which is mainly applied to fluorination treatment for organic compound, reduces the HF release, the solution still requires careful handling because of limited amount of free HF. Recently family of fluorohydrogenate room-temperature ionic liquid, XF(HF)_2.3, that consists of heterocyclic ammonium cation (X⁺), F(HF)₂⁻, and F(HF)₃⁻, has gotten a lot of attentions due to the interesting physicochemical properties such as negligible vapor pressure (<7.5 × 10⁻³ Torr (=1 Pa) at 298 K), high conductivity, and low corrosiveness. This novel solvent will greatly contribute to development of fluorine chemistry. In this article, fundamental techniques and physicochemical data on the fluorohydrogenate RTIL are summarized, and molecular science in the dialkylimidazolium fluorohydrogenates leading to the understanding of the unusual properties is reviewed based on recent experimental and theoretical considerations.     

Ionic liquids accelerate access to N-substituted-1,8-naphthalimides

The synthesis of N-substituted-1,8-naphthalimides is accelerated in the presence of the room temperature ionic liquid [BMIM][NO₃]. Reaction times are reduced from 18 h in volatile organic compounds (VOCs) (PhCH₃, EtOH and THF) to 20 min in the ionic liquid [BMIM][NO₃]. The reaction yields are typically increased to >85% and the products are isolated by ethanol-mediated precipitation direct from the ionic liquid, requiring no further purification.     

Ultrasonication-assisted extraction and preconcentration of medicinal products from herb by ionic liquids

Ionic liquid-based extraction of medicinal or useful compounds from plants was investigated as an alternative to supercritical fluid, cloud point and conventional organic solvent extractions. The method integrated extraction and preconcentration. Medicinal products were first extracted by an ionic liquid solution, part of which was then converted to a hydrophobic form by anion metathesis for preconcentration. The remaining soluble ionic liquid acted as a dispersive agent to enhance the efficiency of preconcentration. Protein in the extract was precipitated spontaneously without addition of further solvents. Ultrasonication assisted this method for extraction and preconcentration of cryptotanshinone, tanshinone I and tanshinone II A from Salvia Miltiorrhiza Bunge. 0.233 mg g⁻¹, 0.695 mg g⁻¹ and 0.682 mg g⁻¹ of each, respectively, were extracted using [OMIM][Cl], and preconcentrated in a [OMIM][PF₆] phase at respective concentrations of 148.1, 507.1 and 486.1 μg mL⁻¹. The method exhibited potential applicability with other medicinal products.     

Enrichment and sensitive determination of dichlorodiphenyltrichloroethane and its metabolites with temperature controlled ionic liquid dispersive liquid phase microextraction prior to high performance liquid phase chromatography

Dichlorodiphenyltrichloroethane (DDT) and its main metabolites are important environmental pollutants and have been in the focusing center. It is of great value to develop simple, rapid, sensitive and easy to operate method for monitoring them. Present work established a novel temperature controlled ionic liquid dispersive liquid phase microextraction method in combination with high performance liquid chromatography for the enrichment and determination of DDT and its metabolites. Proposed method used only ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]) for the enrichment and overcame the demerits of conventional single drop liquid phase microextraction and dispersive liquid-liquid microextraction. Temperature has two functions here, one is to promote the dispersing of ionic liquid into the solution and forming infinitesimal micro-drop and increasing the chance of the analytes extracted into ionic liquid phase, and the other one is to perform phase-separation. A series of factors that would affect the extraction performance was systematically investigated and optimized. The experimental results indicated that the detection limits obtained for p,p′-DDD, p,p′-DDT, o,p′-DDT and p,p′-DDE were 0.24, 0.24, 0.45, 0.24 ng mL⁻¹, respectively. The linear ranges for them were from 1.0 to 100 ng mL⁻¹, and the precisions were between 3.8% and 6.7% (n = 6). The proposed method was validated with four real-world samples and excellent results were achieved.     

The room temperature preparation of metastable fluorides and potent oxidizers

The low electronegativity of an oxidation state in an anion enables high oxidation states, e.g. Ni^IV, and Ag^III, to be easily attained in liquid anhydrous HF (aHF), made basic with fluoride-ion donors. The oxidation state can be enhanced if elemental fluorine is photo-dissociated. Teflon^® valves and lines, especially transparent and kinetically stable fluorocarbon containers for the aHF solutions, provide for this. Binary fluorides that are of low solubility in aHF, can be displaced by stronger F⁻ acceptors from their high oxidation-state anions. NiF₄, NiF₃, and AgF₃, which can be made in this manner, are thermodynamically unstable with respect to loss of fluorine. The electronegativity of the oxidation state in the binary fluoride is higher than in the anion (hence the metastability) and when a strong F⁻ acceptor converts the binary fluoride into a cationic species, the electronegativity is further enhanced. Thus cationic Ag^III and Ni^IV are superior to KrF⁺, as one-electron oxidizers and are the most potent oxidizers known thus far. They are able to remove the electron from all platinum-metal hexafluoro-anions, MF₆⁻, to liberate the hexafluorides. All of this chemistry can be achieved at or below room temperature.     

Potentiometric sensor using sub-micron Cu2O-doped RuO2 sensing electrode with improved antifouling resistance

A Cu₂O-doped RuO₂ sensing electrode (SE) for potentiometric detection of dissolved oxygen (DO) was prepared and its structure and electrochemical properties were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS) and energy-dispersive spectroscopy (EDS) techniques. Cu₂O-RuO₂-SE displayed a linear DO response from 0.5 to 8.0 ppm (log[O₂], −4.73 to −3.59) within a temperature range of 9-30 °C. The maximum sensitivity of −47.4 mV/decade at 7.27 pH was achieved at 10 mol% Cu₂O. Experimental evaluation of the Cu₂O-doped RuO₂-SE demonstrated that the doping of RuO₂ not only improves its structure but also enhances both sensor's selectivity and antifouling properties. Selectivity measurements revealed that 10 mol% Cu₂O-doped RuO₂-SE is insensitive to the presence of Na⁺, Mg²⁺, K⁺, Ca²⁺, NO₃⁻, PO₄²⁻ and SO₄²⁻ ions in the solution in the concentration range of 10⁻⁷-10⁻¹ mol/l.     

Development of an extraction method for the determination of prostaglandins in biological tissue samples using liquid chromatography–tandem mass spectrometry: Application to gonads of Atlantic cod (Gadus morhua)

A simple extraction method for the analysis of PGE₂ and PGF_2α in gonad samples from Atlantic cod and further quantification by using liquid chromatography–tandem mass spectrometry is proposed. The evaluation of the best solvent extraction conditions and the analytical performance parameters are reported. The method was highly selective for both prostaglandins and the calibration curves, based on the internal standard method, were linear between 5 and 1000 ng mL⁻¹ for PGE₂ and PGF_2α, with limits of detection of 1 ng mL⁻¹ and 1.5 ng mL⁻¹ and recovery values of 99.999 ± 0.002 and 99.967 ± 0.023 respectively. The homogenization of samples using liquid nitrogen combined with the developed extraction protocol can be implemented in different types of biological tissues.     

Hydrolysis of dioxouranium(VI): a calorimetric study in NaClaq and NaClO4 aq, at 25 °C

We report the results of a calorimetric study on the hydrolysis of UO₂²⁺ in different ionic media (NaClO_4 aq, NaCl_aq) at 25 °C. Experiments in NaCl were performed at different ionic strength, at I≤1 mol l⁻¹. The species considered in both ionic media were UO₂(OH)⁺, (UO₂)₂(OH)₂²⁺ and (UO₂)₃(OH)₅⁺, and in addition (UO₂)₃(OH)₄²⁺ and (UO₂)₃(OH)₇⁻ in NaCl_aq. The dependence on ionic strength of enthalpy changes in NaCl_aq was expressed by the simple linear equation ΔH_pq=ΔH°_pq+aI^1/2 (a, empirical parameter). Comparison with literature findings is given and some recommended values are reported.     

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P₆₆₆₁₄⁺) and tetrakis(pentafluorophenyl)borate anion (TB⁻) was employed within a water|P₆₆₆₁₄TB (w|P₆₆₆₁₄TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. ¹³⁷Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N′-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6 × 10¹¹ at the w|P₆₆₆₁₄TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ_α, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ_α of 2 and 8.2 × 10⁷, respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water–organic solvent mixture into an electron spray ionization mass spectrometer.     

Assessment of single extractions for the determination of mobile forms of metals in highly polluted soils and sediments--analytical and thermodynamic approaches

Highly polluted forest/tilled soils and stream sediments from a mining and smelting area were subjected to single-extraction procedures to determine the extractable contents of Cd, Cu, Pb, and Zn. The results obtained from four widely used operationally defined single extraction tests were compared: deionised water, 0.01 mol L⁻¹ CaCl₂, 1 mol L⁻¹ NH₄NO₃ and 0.005 mol L⁻¹ DTPA. The analytical data were coupled with measurement of the pH and Eh in extracts, mineralogical investigations and thermodynamic modelling using the PHREEQC-2 code. The changes in the pH of the equilibrated suspensions significantly influenced the metal extractabilities, with higher values in the lower pH regions. Although the DTPA procedure generally extracted the highest amounts of metals, it was found to be unsuitable for highly organic acidic forest soils, where anionic metal-DTPA complexes are assumed to be re-adsorbed on the positively charged surfaces of soil organic matter and oxides. The NH₄NO₃ extraction was also unsuitable due to the high ionic strength (1 mol L⁻¹), limiting the use of the thermodynamic speciation model and the formation of the Cu(NH₃)²⁺ complex, leading to acidification of the suspension. 0.01 mol L⁻¹ CaCl₂ can be proposed as the most appropriate extraction medium, suitable for speciation modelling and analytical determinations using ICP-techniques and having an ionic strength similar to that of the soil solution. The metals are present in free ionic forms or chlorocomplexes in the CaCl₂ extracts, preventing their re-adsorption on the positively charged surfaces of soil solids (organic matter, Fe- and Mn-oxides) in acidic and circum-neutral conditions.