An improved drop casting electrochemical strategy for furosemide quantification in natural waters exploiting chemically reduced graphene oxide on glassy carbon electrodes.

This work exploits the applicability of a chemically reduced graphene oxide (CRGO) modification on the electrochemical response of a glassy carbon electrode (GCE) for the first-time sensitive determination of furosemide in natural waters. The batch injection analysis (BIA) is proposed as an analytical method, where CRGO-GCE is coupled to a BIA cell for amperometric measurements. Acetate buffer (0.1 µmol L-1, pH 5.2) was used as the background electrolyte. The modification provided an increase in sensitivity (0.024 µA/µmol L-1), low limit of detection (0.7 µmol L-1), RSD (< 4%), and broad linear range (1-600 µmol L-1). Recovery tests performed in two different concentration ranges resulted in values between 89 and 99%. Recovery tests were performed and compared with high-performance liquid chromatography (HPLC) with UV-Vis detection using Student's t test at a 95% significance level, and no significant differences were found, confirming the accuracy of the method. The developed method is proven faster (169 h-1) compared with the HPLC analysis (5 h-1), also comparable with other flow procedures hereby described, offering a low-cost strategy suitable to quantify an emerging pharmaceutical pollutant. Graphical abstract.

Development of a flow-injection analysis system with fluorescence detection for gatifloxacin determination in organized medium.

This work reports the development and optimization of a flow injection analysis system with fluorescence detection (FIA-FLUO) for gatifloxacin (GFX) determination in organized medium. The analytical system was based on the enhanced fluorescence of gatifloxacin in micellar medium containing sodium dodecyl sulfate (SDS) at pH 6.0. The influence of physical (carrier flow rate, sample volume and volume of reaction coil) and chemical (pH, concentration of buffer and concentration of SDS) parameters that could affect the performance of the FIA system was evaluated in order to reach optimum conditions in terms of sensitivity and analytical throughput. Under optimized conditions, the FIA-FLUO system allowed the injection of 40 samples per hour with a limit of quantification of 72 µg/L and a RSD of 3.5% at 0.20 mg/L. Real samples of commercial pharmaceutical formulations containing GFX were analyzed, and no statistical difference was observed between the results obtained using the developed system and those obtained using the reference method based on high-performance liquid chromatography with UV detection.

3D-printed electrodes using graphite/carbon nitride/polylactic acid composite material: A greener platform for detection of amaranth dye in food samples.

The production of sustainable materials with properties aimed at the additive manufacturing of electrochemical sensors has gained prestige in the scientific scenario. Here, a novel lab-made composite material using graphite (G) and carbon nitride (C3N4) embedded into polylactic acid (PLA) biopolymer is proposed to produce 3D-printed electrodes. PLA offers printability and mechanical stability in this composition, while G and C3N4 provide electrical properties and electrocatalytic sites, respectively. Characterizations by Raman and infrared spectroscopies and Energy Dispersive X-rays indicated that the G/C3N4/PLA composite was successfully obtained, while electron microscopy images revealed non-homogeneous rough surfaces. Better electrochemical properties were achieved when the G/C3N4/PLA proportion (35:5:60) was used. As a proof of concept, amaranth (AMR), a synthetic dye, was selected as an analyte, and a fast method using square wave voltammetry was developed. Utilizing the 3D-printed G/C3N4/PLA electrode, a more comprehensive linear range (0.2 to 4.2 µmol/L), a 5-fold increase in sensitivity (9.83 µmol-1 L µA), and better limits of detection (LOD = 0.06 µmol/L) and quantification (LOQ = 0.18 µmol/L) were achieved compared to the G/PLA electrode. Samples of jelly, popsicles, isotonic drinks, and food flavoring samples were analyzed, and similar results to those obtained by UV-vis spectrometry confirmed the method's reliability. Therefore, the described sensor is a simple, cost-effective alternative for assessing AMR in routine food analysis.

Fluorescence determination of azithromycin in pharmaceutical formulations by using the synchronous scanning approach after its acid derivatization.

In this present work, a fluorescence method for azithromycin (9-deoxo-9a-aza-9a-methyl-9a-homoerythromycin) determination in pharmaceutical formulations is proposed. The method is based on the synchronous fluorescence (Δλ = 30 nm, 482 nm) produced when azithromycin is derivatized in strong acidic medium (9.0 mol L(-1) HCl). The influence of the derivatization conditions (acid concentration, reaction time and temperature) was studied. Also, the possible reaction mechanism was discussed. In the optimized conditions, the method presented a limit of detection of 0.23 mg L(-1) and a limit of quantification of 0.76 mg L(-1). The developed procedure was successfully applied in the determination of azithromycin in pharmaceutical formulations.

Determination of rosuvastatin in urine by spectrofluorimetry after liquid-liquid extraction and derivatization in acidic medium.

Statins are a class of drugs mostly used for treating hyperlipidemia, and rosuvastatin is the newest drug in the market belonging to this class. In this present work, a method was developed based on the molecular fluorescence technique, with the objective to quantify rosuvastatin in urine samples. For this purpose, the study of several parameters was made to achieve the maximum analytical signal (under reaction with sulfuric acid during 40 min). Also, a previous step to avoid matrix interference was carried out (liquid-liquid extraction). The limit of detection (LOD) and the limit of quantification (LOQ) were 0.38 and 1.28 mg L(-1), respectively. Linear relationship between rosuvastatin concentration and it's fluorescence intensity was found until 5.0 mg L(-1). The proposed method was tested in several samples spiked with rosuvastatin and recovery was found in the range of 90 ± 10%.

Direct determination of sitagliptin in pharmaceutical formulations and its determination in urine after solid-phase extraction by spectrofluorimetry.

The fluorescence characteristics of sitagliptin phosphate were used to develop a methodology that allowed its determination in pharmaceutical formulations and urine samples; under the studied conditions, limits of determination and quantification of 0.25 and, respectively, 0.85 mg/L were achieved. Linear correlation between fluorescence analytical signal and sitagliptin concentration was achieved up to 10.0 mg/L. The method was considered selective for sitagliptin determination in pharmaceutical formulations because no interferences due to excipients present in considered matrix were observed (as demonstrated by recovery tests comparing analytical and addition curves). When the method was applied to urine samples, Interferences related to the matrix were observed, which made a solid-phase extraction system necessary. The use of calibration was possible only by applying the standard addition method.

3D printed graphite-based electrode coupled with batch injection analysis: An affordable high-throughput strategy for atorvastatin determination.

This work integrated a lab-made conductive graphite/polylactic acid (Grp/PLA, 40:60% w/w) filament into a 3D pen to print customized electrodes (cylindrical design). Thermogravimetric analysis validated the incorporation of graphite into the PLA matrix, while Raman spectroscopy and scanning electron microscopy images indicated a graphitic structure with the presence of defects and highly porous, respectively. The electrochemical features of the 3D-printed Gpt/PLA electrode were systematically compared to that achieved using commercial carbon black/polylactic acid (CB/PLA, from Protopasta®) filament. The 3D printed Gpt/PLA electrode "in the native form" provided lower charge transfer resistance (Rct = 880 Ω) and a more kinetically favored reaction (K0 = 1.48 × 10-3 cm s-1) compared to the 3D printed CB/PLA electrode (chemically/electrochemically treated). Moreover, a method by batch injection analysis with amperometric detection (BIA-AD) was developed to determine atorvastatin (ATR) in pharmaceutical and water samples. Using the 3D printed Gpt/PLA electrode, a wider linear range (1-200 µmol L-1), sensitivity (3-times higher), and lower detection limit (LOD = 0.13 µmol L-1) were achieved when compared to the CB/PLA electrode. Repeatability studies (n = 15, RSD <7.3%) attested to the precision of the electrochemical measurements, and recovery percentages between 83 and 108% confirmed the accuracy of the method. Remarkably, this is the first time that ATR has been determined by the BIA-AD system and a low-cost 3D-printed device. This approach is promising to be implemented in research laboratories for quality control of pharmaceuticals and can also be useful for on-site environmental analysis.

Pre-concentration of rosuvastatin using solid-phase extraction in a molecularly imprinted polymer and analytical application in water supply.

In this work, it is shown the development and validation of innovative analytical methodology based on solid-phase extraction (SPE) with molecularly imprinted polymers (MIP) as a sorbent associated to UV-Vis spectroscopy to isolate and quantify, respectively, rosuvastatin (RSV) in water samples. For this purpose, porogenic solvent in MIP synthesis and SPE extraction parameters for MIP and non-imprinted polymers (NIP) were evaluated univariately for comparison purposes. The sorptive capacity and characterization studies by infrared spectroscopy and atomic force microscopy showed difference between MIP and NIP. The selectivity study of the MIP-RSV against other statins (simvastatin and atorvastatin) showed that the synthesized MIP can also be applied as a solid phase for isolation and quantitative pre-concentration of RSV and atorvastatin. The conjugation of SPE and UV-Vis spectroscopy in the determination of RSV in aqueous matrices led to large factor of pre-concentration (125 times), limit of detection (LOD) of 3 µg L-1, limit of quantification (LOQ) of 10 µg L-1, precision of 2.87% (n = 10), and accuracy of 83.1% (n = 4).

Synthesis and application of ion-imprinted polymer for the determination of mercury II in water samples.

In this study, an innovative analytical methodology capable of selectively identifying and quantifying mercury contamination by the association of solid-phase extraction using ion-imprinted polymers as a sorbent phase and differential pulse anodic stripping voltammetry is proposed. To this end, the ion-imprinted polymers were synthesized and characterized by infrared spectroscopy and atomic force microscopy. The sorption capacities and the selectivity of the ion-imprinted polymers were compared to the ones related to the non-imprinted ones. Next, the experimental parameters of this solid-phase extraction method (IIP-SPE) were evaluated univariately. The selectivity of this polymeric matrix against other cations (Cd II, Pb II, and Cu II) was also evaluated. Limits of detection (LOD) and quantification (LOQ) obtained for the here proposed methodology were 0.322 µg L-1 and 1.08 µg L-1, respectively. Also, the precision of 4.0% was achieved. The method was finally applied to three water samples from different sources: for the Piratininga and Itaipu Lagoon waters, Hg II concentrations were below the LOQ and for Vargem River waters a concentration equal to 1.35 ± 0.07 mg L-1 was determined. These results were confirmed by recovery tests, resulting in a recovery of 96.2 ± 4.0%, and by comparison with flame atomic absorption spectrometry, resulting in statistical conformity between the two methods at 95% confidence level.

Voltammetric determination of copper and lead in gasoline using sample preparation as microemulsions.

A voltammetric method for the determination of Cu(II) and Pb(II) in gasoline using sample preparation as three-component solutions (gasoline:propan-1-ol:water, 25:60:15 v/v/v) is proposed. HNO(3) was employed as a supporting electrolyte and to allow the use of aqueous inorganic standards for calibration, even if the analyte species originally in gasoline is present as a metallo-organic form. A square-wave anodic sequential determination was used by measuring the stripping current of Cu(II) (at +104 mV) using a glassy carbon electrode (GCE) and, in a second run, measuring the Pb(II) stripping current (at -470 mV) using a bismuth-film deposited on the surface of the GCE. The method allowed the quantification of 1.7 x 10(-9) mol L(-1) of Cu and 1.4 x 10(-10) mol L(-1) of Pb employing a 1500-s accumulation time. Recovery tests using analyte spiked three-component solutions prepared with commercial gasoline samples enabled recoveries of Cu and Pb from 97 +/- 8 to 102 +/- 5%.

Fluorimetric determination of cyclofenil using photochemical derivatization.

In this work, a fluorimetric approach for the determination of cyclofenil, 4-4'-(cyclohexylidenemethylene)bis(phenylacetate), is presented. The method was based on the intense fluorescence (250/410 nm) observed after a UV photochemical treatment of cyclofenil. The influence of the pH and solvent system and UV exposure time on the fluorescence magnitude was studied. Optimization of parameters was made using experimental design (factorial design and central composite design). Limit of detection (3S(b)/m) were estimated to be 1.1 x 10(-8)mol L(-1) with the linear dynamic range extending up to 8 x 10(-5)mol L(-1). This analytical approach was tested through the analysis of a commercial pharmaceutical formulation. In this case, tests enabled an average recovery of 98.3+/-3.9% (for n=9) using the analytical curve. The identification of the fluorescent derivative is proposed based on results achieved from GC-MS.

Use of hydrogen peroxide to achieve interference-free stripping voltammetric determination of copper at the bismuth-film electrode.

In this work, a new approach is presented to allow interference-free determination of Cu (II) by stripping voltammetry using the bismuth-film electrode. The addition of hydrogen peroxide to the electroanalytical cell has promoted complete resolution between re-dissolution peaks of Bi (III) and Cu (II). The absence of interference could be evaluated by the correlation coefficient (r>0.99) between Cu (II) concentration and its shifted current peak (at +212 mV) while achieving a slightly fluctuation of the bismuth current peak at -180 mV. Studies were performed aiming towards the optimum conditions for trace determination of Cu (II) using hydrogen peroxide. The methodology was applied to a real sample (sugarcane spirits) and the results were compared to those from graphite furnace atomic absorption spectrometry. The analytical parameters of merit and the results of the analysis indicated that the analytical methodology could be readily used for trace determination of Cu (II).