Supramolecular solvent microextraction of Sudan blue II in environmental samples prior to its spectrophotometric determination

A liquid phase microextraction method-based conformation of supramolecular assembly was developed for the separation and preconcentration of trace levels of Sudan blue II. Various analytical parameters such as pH, supramolecular solvent type and volume, sample volume and matrix effect etc. were optimised. Sudan blue II concentration in the extraction phase was determined by UV-visible spectrophotometer. Under the optimised conditions, detection limit and preconcentration factor was found as 2.16 µg L^?1 and 80, respectively. Relative standard deviation value was found 5%. The developed procedure was successfully applied for the determination of trace levels of Sudan blue II in environmental samples.     

Ion Chromatography with Pulsed Amperometric Detection for Determining Cyanide in Urine and Meconium Samples

The parents’ addictions and eating habits have a significant influence on the child’s growth. The first stool of a newborn baby provides a large amount of information about xenobiotics transmitted by the mother’s body. The analytical technique used in the study is ion chromatography with pulsed amperometric detection (IC-PAD). The biological samples, which were obtained from women staying in a maternity ward and their partners, revealed cyanide concentrations in urine samples spanning 1.30–25.3 μg L⁻¹. Meanwhile, the results of the meconium samples were in the range of 1.54 μg L⁻¹ to 24.9 μg L⁻¹. Under the optimized chromatographic conditions, the IC-PAD system exhibited satisfactory repeatability (R < 3%, n = 3) and good linearity in the range of 1–100 μg L⁻¹. Thus, it proved to be an effective tool for monitoring trace cyanide concentration in a series of human body fluid matrices, including meconium. Based on the literature review, this is the first application of the IC-PAD analytical technique for the determination of cyanide ions in meconium samples.     

Raffinose Capped Silver Nanoparticles: A New Localized Surface Plasmon Resonance Based Sensor for Selective Quantification of Cr(VI) in Waste Waters

In this study, a new method for selective determination of Cr(VI) in water samples at pH 4 is presented using raffinose capped silver nanoparticles (Ag/Raff NPs) as an optical sensor. The method is based on the variation of LSPR absorption band intensity as a result of electrostatic interaction between the negatively charged Ag/Raff NPs and positive Cr(III) ions, in-situ produced by chemical reduction of Cr(VI) with ascorbic acid, combined with the fast kinetics of Cr(III) coordination to the –OH groups of the capping agent on the nanoparticle surface, further causing the nanoparticle aggregation. The calibration curve for Cr(VI) is linear in the range 2.5–7.5 μmol L⁻¹, the limit of quantification achieved is 1.9 μmol L⁻¹, and values of relative standard deviation vary from 3 to 5% for concentration level 1.9–7.5 μmol L⁻¹. The interference studies performed in the presence of various metal ions show very good selectivity of Ag/Raff NPs toward Cr(VI) species. The added–found method is used to confirm the accuracy and precision of developed analytical approach.     

A Novel Glass Fiber Coated with Sol–Gel Poly-Diphenylsiloxane Sorbent for the On-Line Determination of Toxic Metals Using Flow Injection Column Preconcentration Platform Coupled with Flame Atomic Absorption Spectrometry

A novel simple and sensitive, time-based flow injection solid phase extraction system was developed for the automated determination of metals at low concentration. The potential of the proposed scheme, coupled with flame atomic absorption spectrometry (FAAS), was demonstrated for trace lead and chromium(VI) determination in environmental water samples. The method, which was based on a new sorptive extraction system, consisted of a microcolumn packed with glass fiber coated with sol–gel poly (diphenylsiloxane) (sol–gel PDPS), which is presented here for the first time. The analytical procedure involves the on-line chelate complex formation of target species with ammonium pyrrolidine dithiocarbamate (APDC), retention onto the hydrophobic sol–gel sorbent coated surface of glass fibers, and finally elution with methyl isobutyl ketone prior to atomization. All main chemical and hydrodynamic factors, which affect the complex formation, retention, and elution of the metal, were optimized thoroughly. Furthermore, the tolerance to potential interfering ions appearing in environmental samples was also explored. Enhancement factors of 215 and 70, detection limits (3 s) of 1.1 μg·L⁻¹ and 1.2 μg·L⁻¹, and relative standard deviations (RSD) of 3.0% (at 20.0 μg·L⁻¹) and 3.2% (at 20.0 μg·L⁻¹) were obtained for lead and chromium(VI), respec tively, for 120 s preconcentration time. The trueness of the developed method was estimated by analyzing certified reference materials and spiked environmental water samples.     

Hybrid Materials Formed with Green Metal-Organic Frameworks and Polystyrene as Sorbents in Dispersive Micro-Solid-Phase Extraction for Determining Personal Care Products in Micellar Cosmetics

Hybrid materials based on polystyrene (PS) and green metal-organic frameworks (MOFs) were synthesized, characterized, and evaluated as potential sorbents in dispersive micro-solid-phase extraction (µ-dSPE). Among the resulting materials, the hybrid PS/DUT-67(Zr) was selected as the adequate extraction material for the monitoring of six personal care products in micellar cosmetic samples, combining the µ-dSPE method with ultra-high performance liquid chromatography (UHPLC) coupled to ultraviolet/visible detection (UV/Vis). Univariate studies and a factorial design were performed in the optimization of the microextraction procedure. The compromise optimum extraction conditions included 20 mg of PS/DUT-67(Zr) for 10 mL of sample, 2 min of extraction time, and two desorption steps using 100 µL of acetonitrile and 5 min assisted by vortex in each one. The validated μ-dSPE-UHPLC-UV/Vis method presented limits of detection and quantification down to 3.00 and 10.0 μg·L⁻¹, respectively. The inter-day precision values were lower than 23.5 and 21.2% for concentration levels of 75 μg·L⁻¹ and 650 μg·L⁻¹, respectively. The hydrophobicity of the resulting PS/DUT-67(Zr) material was crucial for the improvement of its extraction capacity in comparison with its unitary components, showing the advantages of combining MOFs with other materials, getting new sorbents with interesting properties.     

Vortex-assisted magnetic solid phase extraction of Pb and Cu in some herb samples on magnetic multiwalled carbon nanotubes

This study is the development of a new solid phase extraction method based on using magnetic multiwalled carbon nanotubes impregnated with 1-(2-pyridylazo)2-naphthol (PAN) for separation, preconcentration, and flame atomic absorption spectrometric determination of Pb(II) and Cu(II). Optimization of the method was done by investigating pH effect, amount of magnetic multiwalled carbon nanotubes impregnated with PAN, eluent type and volume, matrix effects, and volume of the sample. The optimum adsorbent amount was found to be 75 mg and the optimum pH value was found as 5.5. The detection limits were 16.6 μg L^-1 for Pb(II) and 18.9 μg L^-1 for Cu(II). The relative standard deviations (RSD%) were less than 4%. Two certified reference materials: SPS-WW2 wastewater and NCS-DC73349 (bush branches and leaves) were used to test the validation of the method. The method was successfully applied to the analysis of Pb(II) and Cu(II) ions in daisy, mint, paprika, sage, rosemary, daphne leaves, heather, green tea, andViburnum opulussamples.     

Application of Bar Adsorptive Microextraction for the Determination of Levels of Tricyclic Antidepressants in Urine Samples

This work entailed the development, optimization, validation, and application of a novel analytical approach, using the bar adsorptive microextraction technique (BAμE), for the determination of the six most common tricyclic antidepressants (TCAs; amitriptyline, mianserin, trimipramine, imipramine, mirtazapine and dosulepin) in urine matrices. To achieve this goal, we employed, for the first time, new generation microextraction devices coated with convenient sorbent phases, polymers and novel activated carbons prepared from biomaterial waste, in combination with large-volume-injection gas chromatography-mass spectrometry operating in selected-ion monitoring mode (LVI-GC-MS(SIM)). Preliminary assays on sorbent coatings, showed that the polymeric phases present a much more effective performance, as the tested biosorbents exhibited low efficiency for application in microextraction techniques. By using BAμE coated with C₁₈ polymer, under optimized experimental conditions, the detection limits achieved for the six TCAs ranged from 0.2 to 1.6 μg L⁻¹ and, weighted linear regressions resulted in remarkable linearity (r² > 0.9960) between 10.0 and 1000.0 μg L⁻¹. The developed analytical methodology (BAμE(C18)/LVI-GC-MS(SIM)) provided suitable matrix effects (90.2–112.9%, RSD ≤ 13.9%), high recovery yields (92.3–111.5%, RSD ≤ 12.3%) and a remarkable overall process efficiency (ranging from 84.9% to 124.3%, RSD ≤ 13.9%). The developed and validated methodology was successfully applied for screening the six TCAs in real urine matrices. The proposed analytical methodology proved to be an eco-user-friendly approach to monitor trace levels of TCAs in complex urine matrices and an outstanding analytical alternative in comparison with other microextraction-based techniques.     

Multi-Element Analysis Based on an Automated On-Line Microcolumn Separation/Preconcentration System Using a Novel Sol-Gel Thiocyanatopropyl-Functionalized Silica Sorbent Prior to ICP-AES for Environmental Water Samples

A sol-gel thiocyanatopropyl-functionalized silica sorbent was synthesized and employed for an automated on-line microcolumn preconcentration platform as a front-end to inductively coupled plasma atomic emission spectroscopy (ICP-AES) for the simultaneous determination of Cd(II), Pb(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II), Mn(II), Hg(II), and V(II). The developed system is based on an easy-to-repack microcolumn construction integrated into a flow injection manifold coupled directly to ICP-AES’s nebulizer. After on-line extraction/preconcentration of the target analyte onto the surface of the sorbent, successive elution with 1.0 mol L⁻¹ HNO₃ was performed. All main chemical and hydrodynamic factors affecting the effectiveness of the system were thoroughly investigated and optimized. Under optimized experimental conditions, for 60 s preconcentration time, the enhancement factor achieved for the target analytes was between 31 to 53. The limits of detection varied in the range of 0.05 to 0.24 μg L⁻¹, while the limits of quantification ranged from 0.17 to 0.79 μg L⁻¹. The precision of the method was expressed in terms of relative standard deviation (RSD%) and was less than 7.9%. Furthermore, good method accuracy was observed by analyzing three certified reference materials. The proposed method was also successfully employed for the analysis of environmental water samples.     

A QuEChERS-HPLC-MS/MS Method with Matrix Matching Calibration Strategy for Determination of Imidacloprid and Its Metabolites in Procambarus clarkii (Crayfish) Tissues

We developed a method for determination of imidacloprid and its metabolites 5-hydroxy imidacloprid, olefin imidacloprid, imidacloprid urea and 6-chloronicotinic acid in Procambarus clarkii (crayfish) tissues using quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-triple quadrupole mass spectrometry. Samples (plasma, cephalothorax, hepatopancrea, gill, intestine, and muscle) were extracted with acetonitrile containing 0.1% acetic acid and cleaned up using a neutral alumina column containing a primary secondary amine. The prepared samples were separated using reverse phase chromatography and scanned in the positive and negative ion multiple reaction-monitoring modes. Under the optimum experimental conditions, spiked recoveries for these compounds in P. clarkii samples ranged from 80.6 to 112.7% with relative standard deviations of 4.2 to 12.6%. The limits of detection were 0.02–0.5 μg·L⁻¹, the limits of quantification were 0.05–2.0 μg·L⁻¹ and the method of quantification was 0.05–2.0 μg·kg⁻¹. The method is rapid, simple, sensitive and suitable for rapid determination and analysis of imidacloprid and its metabolites in P. clarkii tissues.     

Efficient Degradation of Iopromide by Using Sulfite Activated with Mackinawite

Iopromide (IOP), an iodinated X-ray contrast medium (ICM), is identified as a precursor to iodide disinfection byproducts that have high genotoxicity and cytotoxicity to mammals. ICM remains persistent through typical wastewater treatment processes and even through some hydroxyl radical-based advanced oxidation processes. The development of new technologies to remove ICMs is needed. In this work, mackinawite (FeS)-activated sulfite autoxidation was employed for the degradation of IOP-containing water. The experiment was performed in a 500 mL self-made temperature-controlled reactor with online monitoring pH and dissolved oxygen in the laboratory. The effects of various parameters, such as initial pH values, sulfite dosages, FeS dosages, dissolved oxygen, and inorganic anions on the performance of the treatment process have been investigated. Eighty percent of IOP could be degraded in 15 min with 1 g L⁻¹ FeS, 400 μmol L⁻¹ sulfite at pH 8, and high efficiency on the removal of total organic carbon (TOC) was achieved, which is 71.8% via a reaction for 1 h. The generated hydroxyl and oxysulfur radicals, which contributed to the oxidation process, were identified through radical quenching experiments. The dissolved oxygen was essential for the degradation of IOP. The presence of Cl⁻ could facilitate IOP degradation, while NO₃⁻ and CO₃²⁻ could inhibit the degradation process. The reaction pathway involving H-abstraction and oxidative decarboxylation was proposed, based on product identification. The current system shows good applicability for the degradation of IOP and may help in developing a new approach for the treatment of ICM-containing water.     

Synthesis of Fluorescent Carbon Dots and Their Application in Ascorbic Acid Detection

Water-soluble fluorescent carbon dots (CDs) were synthesized by a hydrothermal method using citric acid as the carbon source and ethylenediamine as the nitrogen source. The repeated and scale-up synthetic experiments were carried out to explore the feasibility of macroscopic preparation of CDs. The CDs/Fe³⁺ composite was prepared by the interaction of the CDs solution and Fe³⁺ solution. The optical properties, pH dependence and stability behavior of CDs or the CDs/Fe³⁺ composite were studied by ultraviolet spectroscopy and fluorescence spectroscopy. Following the principles of fluorescence quenching after the addition of Fe³⁺ and then the fluorescence recovery after the addition of asorbic acid, the fluorescence intensity of the carbon dots was measured at λex = 360 nm, λem = 460 nm. The content of ascorbic acid was calculated by quantitative analysis of the changing fluorescence intensity. The CDs/Fe³⁺ composite was applied to the determination of different active molecules, and it was found that the composite had specific recognition of ascorbic acid and showed an excellent linear relationship in 5.0–350.0 μmol·L⁻¹. Moreover, the detection limit was 3.11 μmol·L⁻¹. Satisfactory results were achieved when the method was applied to the ascorbic acid determination in jujube fruit. The fluorescent carbon dots composites prepared in this study may have broad application prospects in a rapid, sensitive and trace determination of ascorbic acid content during food processing.     

The Influence of Ripeness on the Phenolic Content,Antioxidant and Antimicrobial Activities of Pumpkins (Cucurbita moschata Duchesne)

Cucurbita moschata Duchesne (Cucurbitaceae) is a plant food highly appreciated for the content of nutrients and bioactive compounds, including polyphenols and carotenoids, which contribute to its antioxidant and antimicrobial capacities. The purpose of this study was to identify phenolic acids and flavonoids of Cucurbita moschata Duchesne using high-performance liquid chromatography–diode array detection–electrospray ionization tandem mass spectrometry (HPLC–DAD–ESI-MS) at different ripening stages (young, mature, ripened) and determine its antioxidant and antimicrobial activities. According to the results, phenolic acids and flavonoids were dependent on the maturity stage. The mature fruits contain the highest total phenolic and flavonoids contents (97.4 mg GAE. 100 g⁻¹ and 28.6 mg QE. 100 g⁻¹).A total of 33 compounds were identified. Syringic acid was the most abundant compound (37%), followed by cinnamic acid (12%) and protocatechuic acid (11%). Polyphenol extract of the mature fruits showed the highest antioxidant activity when measured by DPPH (0.065 μmol TE/g) and ABTS (0.074 μmol TE/g) assays. In the antimicrobial assay, the second stage of ripening had the highest antibacterial activity. Staphylococcus aureus was the most sensitive strain with an inhibition zone of 12 mm and a MIC of 0.75 mg L⁻¹. The lowest inhibition zone was obtained with Salmonella typhimurium (5 mm), and the MIC value was 10 mg L⁻¹.     

Phenolic compounds,essential oil composition,and antioxidant activity of Angelica purpurascens (Avé-Lall.) Gill

In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•⁺), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•⁺, DPPH•, and FRAP activities (IC₅₀: 0.05 ± 0.0001 mg/mL, IC₅₀: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC₅₀: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source.     

Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H₃L and H₅L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu₄(HL²⁻)₂(N₃)₄]·4CH₃OH·56H₂O (1) and [Cu₄(L³⁻)₂(OH)₂(H₂O)₂] (2), dinuclear [Cu₂(H₃L1²⁻)(N₃)(H₂O)(NO₃)] (3), polynuclear {[Cu₂(H₃L1²⁻)(H₂O)(BF₄)(N₃)]·H₂O}_n (4), heptanuclear [Cu₇(H₃L1²⁻)₂(O)₂(C₆H₅CO₂)₆]·6CH₃OH·44H₂O (5), and decanuclear [Cu₁₀(H₃L1²⁻)₄(O)₂(OH)₂(C₆H₅CO₂)₄] (C₆H₅CO₂)₂·20H₂O (6). X-ray studies have revealed that the basic building block in 1, 3, and 4 is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL²⁻ or H₃L1²⁻, and one μ-1,1-azido (N₃⁻) ion and in 2, 5, and 6 by μ-phenoxide oxygen of L³⁻ or H₃L1²⁻ and μ-O²⁻ or μ₃-O²⁻ ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (1 and 6), 2D-sheets (3), and 3D-structures (4). In 5, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In 1, 3, and 5, Cu(II) ions in [Cu₂] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm⁻¹.     

Determination of Aniline in Soil by ASE/GC-MS

In this study, a rapid and simple method based on accelerated solvent extraction (ASE) combined with gas chromatography-mass spectrometry (GC-MS) was established to determine the levels of aniline in soil. The matrix spike recovery rates of aniline were investigated by changing several experimental parameters such as vacuum freeze-drying, accelerated solvent extraction, sample transfer, nitrogen-blowing concentration and solvent exchange. Under optimized pretreatment conditions, the linearity of the method ranged from 0.5 to 20 μg mL⁻¹ for aniline, and the correlation coefficient was 0.999. Recoveries of aniline from quartz sand and soil ranged from 76% to 98%, while the precision was excellent with average inter-day and intraday values ranging (n = 6) from 3.1% to 7.5% and 2.0% to 6.9%, respectively. The limits of quantification of the method were 0.04 mg kg⁻¹. Notably, the results show that the method we developed is simple, fast, low cost and can meet the requirements for the determination of aniline in soil samples, sewage sludge, river and pond sediments.     

Light Intensity and Photoperiod Affect Growth and Nutritional Quality of Brassica Microgreens

We explored the effects of different light intensities and photoperiods on the growth, nutritional quality and antioxidant properties of two Brassicaceae microgreens (cabbage Brassica oleracea L. and Chinese kale Brassica alboglabra Bailey). There were two experiments: (1) four photosynthetic photon flux densities (PPFD) of 30, 50, 70 or 90 μmoL·m⁻²·s⁻¹ with red:blue:green = 1:1:1 light-emitting diodes (LEDs); (2) five photoperiods of 12, 14, 16, 18 or 20 h·d⁻¹. With the increase of light intensity, the hypocotyl length of cabbage and Chinese kale microgreens shortened. PPFD of 90 μmol·m⁻²·s⁻¹ was beneficial to improve the nutritional quality of cabbage microgreens, which had higher contents of chlorophyll, carotenoids, soluble sugar, soluble protein and vitamin C, as well as increased antioxidant capacity. The optimal PPFD for Chinese kale microgreens was 70 μmol·m⁻²·s⁻¹. Increasing light intensity could increase the antioxidant capacity of cabbage and Chinese kale microgreens, while not significantly affecting glucosinolate (GS) content. The dry and fresh weight of cabbage and Chinese kale microgreens were maximized with a 14-h·d⁻¹ photoperiod. The chlorophyll, carotenoid and soluble protein content in cabbage and Chinese kale microgreens were highest for a 16-h·d⁻¹ photoperiod. The lowest total GS content was found in cabbage microgreens under a 12-h·d⁻¹ photoperiod and in Chinese kale microgreens under 16-h·d⁻¹ photoperiod. In conclusion, the photoperiod of 14~16 h·d⁻¹, and 90 μmol·m⁻²·s⁻¹ and 70 μmol·m⁻²·s⁻¹ PPFD for cabbage and Chinese kale microgreens, respectively, were optimal for cultivation.     

Efficient Low-Cost Procedure for Microextraction of Estrogen from Environmental Water Using Magnetic Ionic Liquids

In this study, three magnetic ionic liquids (MILs) were investigated for extraction of four estrogens, i.e., estrone (E1), estradiol (E2), estriol (E3), and ethinylestradiol (EE2), from environmental water. The cation trihexyl(tetradecyl)phosphonium ([P₆₆₆₁₄]⁺), selected to confer hydrophobicity to the resulting MIL, was combined with tetrachloroferrate(III), ferricyanide, and dysprosium thiocyanate to yield ([P₆₆₆₁₄][FeCl₄]), ([P₆₆₆₁₄]₃[Fe(CN)₆]), and ([P₆₆₆₁₄]₅[Dy(SCN)₈]), respectively. After evaluation of various strategies to develop a liquid–liquid microextraction technique based on synthesized MILs, we placed the MILs onto a magnetic stir bar and used them as extracting solvents. After extraction, the MIL-enriched phase was dissolved in methanol and injected into an HPLC–UV for qualitative and quantitative analysis. An experimental design was used to simultaneously evaluate the effect of select variables and optimization of extraction conditions to maximize the recovery of the analytes. Under optimum conditions, limits of detection were in the range of 0.2 (for E3 and E2) and 0.5 μg L⁻¹ (for E1), and calibration curves exhibited linearity in the range of 1–1000 μg L⁻¹ with correlation coefficients higher than 0.998. The percent relative standard deviation (RSD) was below 5.0%. Finally, this method was used to determine concentration of estrogens in real lake and sewage water samples.     

Application of a Low Transition Temperature Mixture for the Dispersive Liquid–Liquid Microextraction of Illicit Drugs from Urine Samples

The use of psychoactive substances is a serious problem in today’s society and reliable methods of analysis are necessary to confirm their occurrence in biological matrices. In this work, a green sample preparation technique prior to HPLC-MS analysis was successfully applied to the extraction of 14 illicit drugs from urine samples. The isolation procedure was a dispersive liquid–liquid microextraction based on the use of a low transition temperature mixture (LTTM), composed of choline chloride and sesamol in a molar ratio 1:3 as the extracting solvent. This mixture was classified as LTTM after a thorough investigation carried out by FTIR and DSC, which recorded a glass transition temperature at −71 °C. The extraction procedure was optimized and validated according to the main Food and Drug Administration (FDA) guidelines for bioanalytical methods, obtaining good figures of merit for all parameters: the estimated lower limit of quantitation (LLOQ) values were between 0.01 µg L⁻¹ (bk-MMBDB) and 0.37 µg L⁻¹ (PMA); recoveries, evaluated at very low spike levels (in the ng-µg L⁻¹ range), spanned from 55% (MBDB) to 100% (bk-MMBDB and MDPV); finally, both within-run and between-run precisions were lower than 20% (LLOQ) and 15% (10xLLOQ).     

Single-Step Hydrolysis and Derivatization of Homocysteine Thiolactone Using Zone Fluidics: Simultaneous Analysis of Mixtures with Homocysteine Following Separation by Fluorosurfactant-Modified Gold Nanoparticles

Herein, we report a new automated flow method based on zone fluidics for the simultaneous determination of homocysteine and homocysteine thiolactone using fluorimetric detection (λ_ext = 370 nm/λ_em = 480 nm). Homocysteine thiolactone is hydrolyzed on-line in alkaline medium (1 mol L⁻¹ NaOH) to yield homocysteine, followed by reaction with o-phthalaldehyde in a single step. Derivatization is rapid without the need of elevated temperatures and stopped-flow steps, while specificity is achieved through a unique reaction mechanism in the absence of nucleophilic compounds. Mixtures of the analytes can be analyzed quantitatively after specific separation with fluorosurfactant-capped gold nanoparticles that are selectively aggregated by homocysteine, leaving the thiolactone analogue in solution. As low as 100 nmol L⁻¹ of the analyte(s) can be quantified in aqueous solutions, while concentrations > 2 μmol L⁻¹ can be analyzed in artificial and real urine matrix following 20-fold dilution. The percent recoveries ranged between 87 and 119%.     

A switchable sensor and scavenger: detection and removal of fluorinated chemical species by a luminescent metal–organic framework

Fluorosis has been regarded as a worldwide disease that seriously diminishes the quality of life through skeletal embrittlement and hepatic damage. Effective detection and removal of fluorinated chemical species such as fluoride ions (F⁻) and perfluorooctanoic acid (PFOA) from drinking water are of great importance for the sake of human health. Aiming to develop water-stable, highly selective and sensitive fluorine sensors, we have designed a new luminescent MOF In(tcpp) using a chromophore ligand 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H₄tcpp). In(tcpp) exhibits high sensitivity and selectivity for turn-on detection of F⁻ and turn-off detection of PFOA with a detection limit of 1.3 μg L⁻¹ and 19 μg L⁻¹, respectively. In(tcpp) also shows high recyclability and can be reused multiple times for F⁻ detection. The mechanisms of interaction between In(tcpp) and the analytes are investigated by several experiments and DFT calculations. These studies reveal insightful information concerning the nature of F⁻ and PFOA binding within the MOF structure. In addition, In(tcpp) also acts as an efficient adsorbent for the removal of F⁻ (36.7 mg g⁻¹) and PFOA (980.0 mg g⁻¹). It is the first material that is not only capable of switchable sensing of F⁻ and PFOA but also competent for removing the pollutants via different functional groups.

A robust In-MOF, In(tcpp), demonstrates sensitive detection of the fluorinated chemical species F⁻ and PFOA via distinctly different luminescence signal change, and effective adsorption and removal of both species from aqueous solution.