A hybrid sensing system combining simultaneous optical and electrochemical measurements: application to beer discriminations

A hybrid sensing system, which combines simultaneous cyclic voltammetric (CV) and UV-vis absorbance measurements using a commercial carbon screen-printed electrode and a set of optical fibres in disposable cuvettes, is proposed. The hybrid system approach was applied to 27 samples of recognized beer brands, improving the classification power as compared to only voltammetric or only spectrophotometric measurements. The developed partial least squares discriminant analysis (PLS-DA) model was able to discriminate between five types of beer (lager, marzen, black/stout, alcohol-free and white/ale). The model was also successfully applied to 28 beer samples of white-label brands sold in local supermarkets, demonstrating their similarity to recognized brand beers

Authentication of soothing herbs by UV-vis spectroscopic and chromatographic data fusion strategy

A data fusion approach combining chromatographic and spectroscopic profiles is proposed for the discrimination and classification of soothing herbs in different types of herbal preparations. Particularly, chamomile, lavender, passionflower, and valerian were considered. The proposed data fusion approach revealed a higher clusterization ability than each analytical technique in a separate way, which was assessed through an exploratory analysis based on Principal Component Analysis (PCA) coupled to Silhouette analysis: percentage of samples with a negative Silhouette width were 19, 15 and 10 for chromatography, spectroscopy and data fusion, respectively. Furthermore, a Partial Least Squares - Discriminant Analysis (PLS-DA) model developed based on data fusion was able to perfectly discriminate samples of chamomile, passionflower, and valerian in a set of 20 samples, overcoming the difficulties related to dealing with different types of herbal preparations including pure herbs, infusions, tablets, capsules and herbal drops

New discrimination tools for harvest year and varieties of white wines based on hydrophilic interaction liquid chromatography with amperometric detection

A simple HPLC-EC method based on hydrophilic interaction liquid chromatography with amperometric detection through gold screen-printed electrodes has been developed and applied for the first time to the determination of aminothiols in white wines. Moreover, the coupling of the method with partial least squares discriminant analysis (PLS-DA) using the analysed aminothiols as biomarkers provides wine discrimination in terms of harvest year. White wine samples were directly injected and chromatographic areas, together with pH and redox potential values, allowed a successful discrimination of wines from different harvest years with a global classification rate of 97.8%. The developed HPLC-EC method also generated characteristic fingerprints that were combined with PLS-DA to classify wines according to three wine varieties, with a global classification rate of 95.3%

Simultaneous determination of iron and copper using screen-printed carbon electrodes by adsorptive stripping voltammetry with o-phenanthroline.

The simultaneous voltammetric determination of iron and copper was accomplished by an unmodified screen-printed carbon electrode based on the complexation with o-phenanthroline assisted by the reducing agent ferrocyanide. The detection limits were 3.74 and 0.34 µg L−1 for iron and copper, respectively, and a linear response was observed from 12.5 to 400 µg L−1 for iron and from 1.14 to 400 µg L−1 for copper. This method successfully avoids interferences between iron and copper while allowing the simultaneous determination of both low and high metal concentrations usually found in the environment. Finally, a certified wastewater reference material was successfully analyzed, confirming the precision and accuracy of the proposed method

Synthesis and characterization of a new norfloxacin/resorcinol cocrystal with enhanced solubility and dissolution profile

A new cocrystal of Norfloxacin, a poorly soluble fluoroquinolone antibiotic, has been synthetized by a solvent-mediated transformation experiment in toluene, using resorcinol as a coformer. The new cocrystal exists in both anhydrous and monohydrate forms with the same (1:1) Norfloxacin/resorcinol stoichiometry. The solubility of Norfloxacin and the hydrated cocrystal were determined by the shake-flask method. While Norfloxacin has a solubility of 0.32 ± 0.02 mg/mL, the cocrystal has a solubility of 2.64 ± 0.39 mg/mL, approximately 10-fold higher. The dissolution rate was tested at four biorelevant pH levels of the gastrointestinal tract: 2.0, 4.0, 5.5, and 7.4. In a first set of comparative tests, the dissolution rate of Norfloxacin and the cocrystal was determined separately at each pH value. Both solid forms showed the highest dissolution rate at pH 2.0, where Norfloxacin is totally protonated. Then, the dissolution rate decreases as pH increases. In a second set of experiments, the dissolution of the cocrystal was evaluated by a unique dissolution test, in which the pH dynamically changed from 2.0 to 7.4, stepping 30 min at each of the four biorelevant pH values. Results were quite different in this case, since dissolution at pH 2 affects the behavior of Norfloxacin at the rest of the pH values

The Mean Metal-line Absorption Spectrum of DLAs in BOSS

We study the mean absorption spectrum of the Damped Lyman alpha population at $z\sim 2.6$ by stacking normalized, rest-frame shifted spectra of $\sim 27\,000$ DLAs from the DR12 of BOSS/SDSS-III. We measure the equivalent widths of 50 individual metal absorption lines in 5 intervals of DLA hydrogen column density, 5 intervals of DLA redshift, and overall mean equivalent widths for an additional 13 absorption features from groups of strongly blended lines. The mean equivalent width of low-ionization lines increases with $N_{\rm HI}$, whereas for high-ionization lines the increase is much weaker. The mean metal line equivalent widths decrease by a factor $\sim 1.1-1.5$ from $z\sim2.1$ to $z \sim 3.5$, with small or no differences between low- and high-ionization species. We develop a theoretical model, inspired by the presence of multiple absorption components observed in high-resolution spectra, to infer mean metal column densities from the equivalent widths of partially saturated metal lines. We apply this model to 14 low-ionization species and to AlIII, SIII, SiIII, CIV, SiIV, NV and OVI. We use an approximate derivation for separating the equivalent width contributions of several lines to blended absorption features, and infer mean equivalent widths and column densities from lines of the additional species NI, ZnII, CII${}^{*}$, FeIII, and SIV. Several of these mean column densities of metal lines in DLAs are obtained for the first time; their values generally agree with measurements of individual DLAs from high-resolution, high signal-to-noise ratio spectra when they are available.Comment: Resubmitted after referee revision. Added evolution of metal-line equivalent widths with redshift (Section 5). Added assessment of result dependencies on sample and methodology. Comparison of relative abundances of DLAs vs Milky Way ISM and halo (Figure 16). Publicly available videos of composite quasar and DLA spectra realizations here: https://github.com/lluism

Mercury films on commercial carbon screen-printed devices for the analysis of heavy metal ions: a critical evaluation

The suitability of mercury films on commercial screen-printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)-ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L-1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen-printed devices

A chemically-bound glutathione sensor bioinspired by the defense of organisms against heavy metal contamination: Optimization of the immobilization conditions

The influence of the experimental conditions (glutathione concentration and incubation time and temperature) concerning the covalent immobilization of glutathione via carbodiimide coupling on the behavior of a glutathione modified screen-printed carbon electrode obtained by electrografting is evaluated. The optimized parameters fasten the modification process and improve the performance of the sensor as compared to the usual procedure. This suggests the convenience of a tailored preparation of metal sensors based on metal-binding biomolecules such as glutathione

Glutathione modified screen-printed carbon nanofiber electrode for the voltammetric determination of metal ions in natural samples

This work reports the development of a glutathione modified electrode via electrografting on a screen-printed carbon nanofiber substrate (GSH-SPCNFE). GSH-SPCNFE was compared to a classical screen-printed carbon electrode modified with glutathione (GSH-SPCE) for the simultaneous voltammetric determination of Cd(II) and Pb(II). Their electrochemical characterization and analytical performance suggest that SPCNFE could be a much better support for GSH immobilization. The applicability of GSH-SPCNFE for the determination of low concentration levels of Pb(II) and Cd(II) ions in environmental samples was successfully tested in a certified wastewater reference material by means of stripping voltammetry with a very high reproducibility and good trueness

Penicillamine-modified sensor for the voltammetric determination of Cd(II) and Pb(II) ions in natural samples

A new penicillamine-GCE was developed based on the immobilization of D-penicillamine on aryl diazonium salt monolayers anchored to the glassy carbon electrode (GCE) surface and it was applied for the first time to the simultaneous determination of Cd(II) and Pb(II) ions by stripping voltammetric techniques. The detection and quantification limits at levels of µg L-1 suggest that the penicillamine-GCE could be fully suitable for the determination of the considered ions in natural samples