Photocatalytic Cellulose-Paper: Deepening in the Sustainable and Synergic Combination of Sorption and Photodegradation.

Clean water is one of the sustainable development goals set by the United Nations for 2030. The development of effective but worldwide affordable strategies is essential to guarantee this achievement. Photocatalysis technology fulfills these criteria whenever the photocatalyst is sustainable and nontoxic. In this article, a cellulose-paper modified with a polyamide-titanium dioxide (TiO2) nanocomposite by dip-coating is evaluated to degrade estrogens efficiently under solar light. The study deepens on the synergic combination of the sorptive capacity of the polyamide and the activity of TiO2. The photocatalytic performance was studied under artificial and sunlight in a miniaturized experimental setup (batch of six reactors). Also, the effects of the dispersed/immobilized catalyst, irradiation time, and adsorption evaluation were studied under kinetic conditions. The photocatalyst composition, considering the polyamide (nylon-6) and TiO2 amounts and the dipping cycles, was studied by a response surface methodology, and the reusability of the photocatalytic cellulose-paper was investigated. The LED source provided removal efficiencies of 65, 62, and 52% (for estrone, 17ß-estradiol, and estriol, respectively) after 420 min of light exposure. Under sunlight, the efficiency increased up to 99.5% for estrone and 17ß-estradiol and 98.5% for estriol after 180 min of irradiation. The sustainable character of the cellulosic substrate, the low toxicity of the nanocomposite ingredients, and its performance under sunlight make the material attractive for in-field application.

A straightforward and semiautomated membrane-based method as efficient tool for the determination of cocaine and its metabolites in urine samples using liquid chromatography coupled to quadrupole time-of-flight-mass spectrometry.

In this study, a novel and straightforward analytical methodology was proposed for the determination of cocaine (COC) and its main metabolites benzoylecgonine (BZE) cocaethylene (CE) and hydroxy­cocaine (COCOH) in urine samples. This approach consisted of a high-throughput and semiautomated configuration based on hollow-fiber renewal liquid membrane extraction (HFRLM) coupled to a 96-well plate system, which was proposed for the first time to analyze complex biological samples such as urine. The analytical determinations were performed using ultra-high performance liquid chromatography coupled to quadrupole time-of-flight-mass spectrometry (LC-ESI-QTOF-MS). The analytical methodology was fully optimized through Doehlert and simplex-centroid designs, and univariate approaches. Polypropylene membranes of 1 cm length were inserted in the pins of an extraction blade combined with a 96-well plate system and its pores were filled with hexane:dichloromethane:ethyl acetate (1:1:1 v/v/v) for 180 s; moreover, 20 µL of this mixture was added to the sample to allow for a renewable liquid membrane. The extraction step was carried out by keeping the blades immersed in vials containing 1.5 mL of diluted urine adjusted at pH 10 with 10% (w/v) of Na2CO3 during 20 min, followed by liquid desorption with 100 µL of acetonitrile. Finally, the extract was dried under N2 stream and resuspended with 20 µL of ultrapure water. Satisfactory analytical performance was obtained with coefficients of determination ranging from 0.9875 for BZE to 0.9986 for CE; intra-day precision ranged from 1.6 to 13.5%, and inter-day precision varied from 2.2 to 17.5%. Limits of detection ranged from 1.5 to 15.1 ng mL-1, and limits of quantification varied from 5 to 50 ng mL-1, with relative recoveries varied from 70.7 to 124.1%.

A high throughput approach to rotating-disk sorptive extraction (RDSE) using laminar cork for the simultaneous determination of multiclass organic micro-pollutants in aqueous sample by GC-MS.

In this study, a high throughput approach to rotating-disk sorptive extraction (RDSE) using laminar cork as extraction phase is demonstrated for the first time in the determination of 20 multiclass organic micro-pollutants including pesticides, PAHs and UV filters compounds from aqueous samples with gas chromatography mass spectrometry (GC-MS). The influencing parameters (desorption solvent, volume and time, extraction time and sample pH and ionic strength) were carefully optimized using multivariate designs. The optimal conditions were 10 min for extraction using 35 mL of water samples and a liquid desorption using 1 mL of MeOH:AcOEt (50:50% v/v) for 20 min. A low-cost apparatus that allows six extractions simultaneously, providing a high throughput of 5 min per sample turnaround times, considering the sample preparation step was used for the first time in this modified RDSE methodology. Satisfactory analytical performance was achieved with limits of detection (LOD) between 0.08 and 1.5 µg L-1 and limits of quantification (LOQ) between 0.3 and 4.8 µg L-1. The relative recoveries for the analytes were determined using river and lake water samples spiked at different concentrations and ranging from 80% to 119% for all analytes, with relative standard deviations (RSD) lower than 20%. The extraction efficiency obtained for the proposed configuration with laminar cork was significantly superior to powdered cork, demonstrating an interesting new configuration for new applications.

Expanding the applicability of cork as extraction phase for disposable pipette extraction in multiresidue analysis of pharmaceuticals in urine samples.

In this paper, cork is proposed as a natural and renewable material for the extraction phase in disposable pipette extraction to be applied in the multiresidue determination of pharmaceuticals in human urine by HPLC with diode array detection. The compounds carbamazepine, losartan, ketoprofen, 17­ß­estradiol, naproxen, diazepam, 17­α­ethinylestradiol, estrone, diclofenac and ibuprofen were studied. A known amount (5 mg) of cork, with a size of 200 mesh, was inserted into a pipette tip. The method optimization was carried out with univariate and multivariate approaches. The optimized conditions were sample pH adjusted to 3, urine dilution factor of 40 (158 µL of urine diluted in 6.142 mL of ultrapure water), 9 extraction cycles each performed with 700 µL of sample, and extraction time of 10 s per cycle. Desorption was performed with 85 µL of methanol applying 6 cycles of 10 s each using the same solvent aliquot. For the clean-up step, 4 cycles were carried out each with 200 µL of methanol. The limits of quantification varied from 5 to 10 µg L-1 with determination coefficients higher than 0.9919 for the calibration curves for all the analytes. Intra-day and inter-day precision and relative recovery from urine samples donated by two volunteers were assessed based on three spiked concentrations. The analyte relative recoveries ranged from 65 to 117% (n = 3) for the two samples. Intra-day precision ranged from 1.2 to 17% (n = 3) and inter-day precision varied from 11 to 21% (n = 9).