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Rice husk ash is an important waste of agricultural industry that, within the framework of the circular economy, has been easily converted into a sustainable sorbent material. This was tested in this work for the pre-concentration of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), representative perfluoroalkyl substances as probe environmental pollutants of waters, with HPLC-MS/MS quantification. The preparation involves a rapid microwave-assisted oxidation followed by a hydrothermal treatment, which was studied using a 22 design of experiments. The final material was thoroughly characterized and tested for its affinity to the target analytes by solid-phase extraction in environmental waters and wastewaters. Recoveries in the range 67–113 % (RSD < 11 %, n = 3) were achieved at environmentally relevant concentrations (10, 50, and 100 ng L-1) and the sorbent was reusable for at least ten consecutive extractions. Good linearity (R2 = 0.9997) was observed, with a method quantification limit in the water sample of 10 ng L-1 that allows the analysis of PFOA and PFOS below the established limits. The method was evaluated for greenness using AGREEprep and SPMS metrics, and it was then applied to the analysis of actual water samples from Northern Italy.

This work showcases a novel application of biochar for analytical sample treatment. The carbonaceous material, obtained by pyrolysis of orange peel waste (550°C) without any post-synthesis treatment or functionalization, was thoroughly characterized and easily immobilized on the inner wall of sampling tubes in order to perform a sort of “in-vial” solid-phase extraction (SPE). The as-obtained device was tested for the extraction of seven sexual steroids, as probe water pollutants, from tap, lake, river water and wastewater treatment plant effluent samples spiked with 0.2-5 µg L−1 of each compound. The sorption kinetics profiles showed quantitative uptake from the sample (25 mL) in 20 min contact time, followed by complete elution in pure ethanol (2 mL, 15 min), thanks to the proper balance between sorption affinity and ease of elution. Under the selected conditions, recovery was in the range 60-123 %, with good inter-day precision (RSD 10-18 %, n=3). As evidence of the excellent reproducibility, an overall RSD below 15 % was observed from inter-day inter-batch recovery tests on three individually prepared sampling tubes. The procedure, carried out on a roller mixer, allows 10 samples to be extracted simultaneously, improving the sample throughput. Moreover, reusability tests showed that the same device maintains its efficiency for 10 consecutive sorption/desorption cycles. The greenness assessment, carried out by two dedicated software, further supported the sustainability of this biochar-based sample preparation as an alternative SPE.

Photocatalytically active heterojunctions based on metal halide perovskites (MHPs) are drawing significant interest for their chameleon ability to foster several redox reactions. The lack of mechanistic insights into their performance, however, limits the ability of engineering novel and optimized materials. Herein, a report is made on a composite system including a double perovskite, Cs2AgBiCl6/g‐C3N4, used in parallel for solar‐driven hydrogen generation and nitrogen reduction, quantified by a rigorous analytical approach. The composite efficiently promotes the two reactions, but its activity strongly depends on the perovskite/carbon nitride relative amounts. Through advanced spectroscopic investigation and density function theory (DFT) modeling the H2 and NH3 production reaction mechanisms are studied, finding perovskite halide vacancies as the primary reactive sites for hydrogen generation together with a positive contribution of low loaded g‐C3N4 in reducing carrier recombination. For nitrogen reduction, instead, the active sites are g‐C3N4 nitrogen vacancies, and the heterojunction best performs at low perovskites loadings where the composites maximize light absorption and reduce carrier losses. It is believed that these insights are important add‐ons toward universal exploitation of MHPs in contemporary photocatalysis.

Aim of this study stands in the evaluation of a carbon nanotubes-based polymerized high internal phase emulsion composite (CNT/polyHIPE) as sorptive phase in biological sample preparation. A micro-solid-phase extraction procedure (µSPE) was developed for trace fluoroquinolone (FQ) antimicrobials, namely Ciprofloxacin, Levofloxacin, Lomefloxacin, Moxifloxacin, Norfloxacin and Sparfloxacin, in human urine samples. PolyHIPEs modified by incorporation of different concentrations of nanotubes (0.2–0.8 wt %) were one-pot synthesized and applied in the packed-cartridge setting. The sorption affinity for the drugs was investigated in tap water and buffered aqueous solutions, demonstrating the key role of the nanotubes embedded in the polymer. The 0.5 wt % CNT composite was selected to develop a straightforward µSPE procedure directly in raw urine (1 mL sample), followed by HPLC-MS/MS. Targets were retained on the sorbent at near neutral pH and, after an aqueous washing (0.1 % v/v formic acid), eluted in a single-step with 4 % v/v ammonia aqueous solution (15 % v/v acetonitrile), thus combining extraction and clean-up. The method allowed accurate quantification of FQs, as evidenced by the recoveries (74–116 %, n = 3) obtained on blank pooled urine samples spiked with 40, 75, 150 µg L−1, accompanied by good inter-day precision (RSD

Recently, as the interest in cannabidiol (CBD) has grown due to its therapeutic potential, e-cigarette liquids containing CBD have proliferated on the market. Typically, e-liquids contain variable concentrations of CBD (from 2 mg∙mL−1 to 20 mg∙mL−1) in propylene glycol or 70:30 propylene glycol:glycerol mixture and are eventually flavored with food-grade flavors. In this work, carried out by a GC-MS analysis of the condensed smoke produced by a real e-cig, we have demonstrated the actual amount of CBD that can survive the smoking process, and we found that negligible amounts of THCs are formed during the smoking process (i.e., the amount formed was 9-THC is around 2.5 mg (smoked or ingested per os), it is reasonable to conclude that accidental THC intoxication is unlikely, which is a very important issue from a forensic point of view, as in some court cases the use of e-cig liquids containing CBD has been argued as being the source of THC intoxication. Furthermore, all the other cannabinoids considered in this study and potentially derived from CBD thermal degradation have concentrations below the instrumental LOD.

A microextraction procedure was developed for the determination of fluoroquinolone (FQ) drugs, namely Ciprofloxacin, Levofloxacin, Lomefloxacin, Moxifloxacin, Norfloxacin and Sparfloxacin, in human urine. The new natural waste-derived material consisting of silica-supported carbon nanoparticle aggregates from rice husk ash (nC-RHA@SiO2) was used as sorbent for setting up a straightforward pipette-tip micro-solid-phase extraction (PT-µSPE) prior to HPLC-MS/MS quantification. The analytes were adsorbed on the solid phase (25 mg) through multi-type interactions and, after a washing step (0.1 % v/v formic acid, 5 % v/v ethanol), eluted in alkaline aqueous solution (15 % v/v acetonitrile), thus achieving simultaneous extraction and clean-up. The PT-µSPE coupled with MS2 detection provided satisfactory recovery (67–118 %, n = 3) in 1:1 v/v diluted urine samples (formate buffer, pH 3), good inter-day precision (RSD < 12 %), good matrix-matched linearity in the concentration range 3–80 μg L −1 (R2 > 0.9956), and limited matrix effect. The experimental method quantification limit was 5 µg L −1, suitable for trace determination of such drugs in urine. Compared to the actual microextraction procedures, the PT-µSPE described here is attractive in terms of extraction efficiency, sample throughput, energy consumption, limited use of organic solvents and ease of operation, as evidenced by a greenness evaluation through the AGREEprep software. The final method was applied to FQs determination in blind urine samples.

A method for multiclass determination of β-lactam antibiotics in human urine by solid-phase extraction (SPE) prior to quantification by hydrophilic interaction liquid chromatography (HILIC) was developed. Four cephalosporins, one carbapenem and four penicillins were selected among the most prescribed β-lactam drugs. A HILIC column – silica-linked zwitterionic sulfobetaine groups – proved to be valuable for analysis of these three classes of highly hydrophilic compounds, with suitable capacity factors, peak shape and resolution gained by proper selection of the chromatographic conditions. Sample extraction has been performed on Strata™-X. The quick SPE procedure entirely developed in urine successfully combined sample clean-up, avoiding protein precipitation before extraction, with recovery higher than 66% (interday RSD < 15%, n = 5), and method quantification limits in urine in the range 1–4 µg mL−1. Selectivity has been proven on blank urine samples, also in presence of several non-target pharmaceuticals, and the method was applied to the analysis of samples from four patients under β-lactams therapy.

This study is focused on the development of a multiclass analytical method for sensitive determination of steroid hormones (progestins, oestrogens, androgens and glucocorticoids) in fruits and vegetables. The herein considered analytes present a wide logP range, thus they tend to accumulate differently in edible parts. Therefore, a berry fruit (strawberry), a root vegetable (carrot), and a leafy vegetable (spinach) were chosen as probes to develop the extraction procedure. This, optimized by a chemometric approach (23 experimental design) on lyophilized samples (0.25 g, spike 100 ng g − 1), entails a rapid ultrasonic extraction (3 × 1 min cycles) with low consumption (3 × 2 mL) of MeOH, selected as extraction solvent by a preliminary screening. The clean-up step, necessary due to the complexity of the matrices, was performed by a simple solid-phase extraction procedure on the Supelclean™ LC-NH2 sorbent afore the selective quantification by HPLC–ESI-MS/MS (MRM mode). The final analytical method was successfully applied to multianalyte extraction at lower concentrations (10–50 ng g−1) with good recoveries and repeatability, and it was successfully extended to raspberry, radish and arugula, further supporting applicability to this kind of samples. The results from the analysis of fruits and vegetables purchased from local markets, where some steroids have been quantified at the low ng g−1 levels, are consistent with literature data about concentration of these emerging pollutants in edible plants, also according to their LogP values.

The stability of cannabidiol (CBD) under thermal (heating, microwave irradiation, presence of Bronsted and Lewis acids) and photochemical conditions has been tested in organic solvents, including glycerol and propylene glycol that are traditionally employed in the preparation of CBD-containing formulation (e-liquid) for e-cigarettes.The results obtained in the present investigation point out the instability of CBD in the realistic scenario of pharmaceutical preparations and commercial products (e.g., e-liquids). In simulated e-liquid, among the by-products, the psychotropic THCs were found in negligible amounts (

In the present work, we describe the electrochemical behaviour of two opioids structurally related to aroyl amides of forensic interest, namely U-47700 and AH-7921. The data obtained allowed for the mise-au-point of a voltammetric determination protocol, that relies on differential pulse voltammetry (DPV) at a glassy carbon electrode in ethanol/0.1 M lithium perchlorate/0.10 M 2,6-lutidine. To apply the method to the analysis of real samples (urines), a clean-up and a preconcentration strategy by solid phase extraction (SPE) using the adsorbent Florisil have been developed. LOQ of 0.2 μg·mL−1 in urine samples with an enrichment factor of 20 and linear range from 5 to 150 μg·mL−1 were obtained.

Rice husk (RH) in the rice industry is often air-burnt to obtain energy in the form of heat and RH ash (RHA) residue. In this work, RHA was applied as a starting material to obtain silica-supported carbon nanomaterials, resulting in a new reuse of a globally produced industrial waste product, in a circular economy approach. The preparation involves ultrasound-assisted one-pot oxidation with a sulfonitric mixture followed by wet oven treatment in a closed vessel. A study of oxidation times and RHA amount/acid volume ratio led to a solid material (nC-RHA@SiO2) and a solution containing silica-supported carbon quantum dots (CQD-RHA@SiO2). TEM analyses evidenced that nC-RHA@SiO2 consists of nanoparticle aggregates, while CQD-RHA@SiO2 are carbon-coated spherical silica nanoparticles. The presence of oxygenated carbon functional groups, highlighted by XPS analyses, makes these materials suitable for a wide range of analytical applications. As the main product, nC-RHA@SiO2 was tested for its affinity towards steroid hormones. Solid-phase extractions were carried out on environmental waters for the determination of target analytes at different concentrations (10, 50, and 200 ng L−1), achieving quantitative adsorption and recoveries (RSD < 20%, n = 3). The method was successfully employed for monitoring lake, river, and wastewater treatment plant water samples collected in Northern Italy.

Heterojunctions based on metal halide perovskites (MHPs) are promising systems for the photocatalytic hydrogen evolution reaction (HER). In this work, we coupled Cs3Bi2Br9 nanocrystals (NCs), obtained by wet ball milling synthesis, with g-C3N4 nanosheets (NSs), produced by thermal oxidation of bulk g-C3N4, in air. These methods are reproducible, inexpensive and easy to scale up. Heterojunctions with different loadings of Cs3Bi2Br9 NCs were fully characterised and tested for the HER. A relevant improvement of H2 production with respect to pristine carbon nitride was achieved at low NCs levels reaching values up to about 4600 µmol g−1 h−1. This work aims to provide insights into the synthesis of inexpensive and high-performing heterojunctions using MHP for photocatalytic applications.

Identifying the composition and the physical characteristics of the bullet that generated a specific hole in the victim's clothes or skin may be crucial in shooting incident reconstructions. In forensics, chemographic tests are routinely conducted to visualize lead, copper, or nitrite deposits around entrance holes with the aim of confirming a projectile impact or estimating the shooting distance. A quantitative chemical analysis of the particles collected from the periphery of an entrance hole is required for identifying the type of passing bullet. In real cases, such analysis would be affected by the possible cross-contributions of both inorganic residue from the discharged ammunition primer and metallic fragments from previous rounds projected from the gun barrel. The actual contribution of the sole bullet to the composition of the inorganic residue deposited on target is then hardly distinguishable. In the present study, the deposits left by three different copper/zinc jacketed bullets on targets were analysed by inductively coupled plasma optical emission spectrometry and by X-ray fluorescence spectrometry. To reduce any possible source of contamination, a heavy metal free primer mixture and a brand new pistol were used. Elements of interest were quantified varying the shooting distances with the aim of identifying different bullet contributions to the inorganic residue on targets.

In this study, a sensitive and multiclass method has been developed for analysis of three families of steroid hormones, i.e. progestins, oestrogens, androgens, by SPE-HPLC-ESI-MS/MS. The extraction efficiency of thermally condensed humic acids onto silica sorbent (HA-C@silica), here for the first time studied for multiclass enrichment of these sex hormones, was tested in different environmental waters (tap and river water, urban wastewater treatment plant effluent) spiked at the nanograms per litre levels (5–1000 ng L−1). Quantitative adsorption was achieved using 200 mg sorbent for preconcentration of 250–1000 mL sample, at the native pH (pH = 6.5–7.7). Elution was performed by two sequential fractions (methanol followed by acetonitrile), obtaining in all the matrices investigated satisfactory recoveries (71% to 124% for river waters and 71–113% for urban wastewater treatment plant effluent) and RSDs below 15% (n = 3). The high enrichment factors (up to 4000) coupled with high-performance liquid chromatography tandem mass spectrometry quantification (MRM mode) provided low limits of detection and quantification (a few ng L−1), that are suitable for environmental monitoring. Most of the analytes were detected in river water and in wastewater effluent samples (in the ng L−1 concentration range), attesting their environmental diffusion. The proposed method was extended to a fourth class, Glucocorticoids, achieving good results in river samples, by the same SPE cartridge and chromatographic run. Keywords: Environmental waters, Steroid hormones, Multiclass determination, HPLC-MS, Pollutants, Solid-phase extraction

Nanosized titanium dioxide immobilized on silica gel was synthesized and used as fixed-bed phase for V(V) pre-concentration, followed by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. Three different sorbents were prepared by sol–gel method starting from a mixture of titanium isopropoxide, 2-propanol and water, and characterized by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and BET analysis. V(V), the most stable and toxic oxidation state of the element, present in water and beverages samples, was selectively sorbed, pre-concentrated, quantitatively eluted by 0.1 M HCl and analyzed by ICP-OES. The effectiveness of the procedure was first assessed on tap water enriched with 1 μg L−1 of V(V) obtaining recoveries up to 92% (n = 4). The pre-concentration step was then optimized for complex matrices such as tea infusions and red and white wines. The reliability of the procedure was assessed on the same beverages samples spiked with 20–250 μg L−1. Quantitative recoveries (82–95%, n = 4) were assured avoiding any sample pre-treatment, generally essential in such complex matrices, obtaining good precision (RSD

Purified multi-walled carbon nanotubes (MWCNTs) grafted onto silica microspheres by gamma-radiation were applied as a HPLC stationary phase for investigating the intermolecular interactions between MWCNTs and substituted benzenes. The synthetic route, simple and not requiring CNTs derivatization, involved no alteration of the nanotube original morphology and physical–chemical properties. The affinity of a set of substituted benzenes for the MWCNTs was studied by correlating the capacity factor (k′) of each probe to its physico-chemical characteristics (calculated by Density Functional Theory). The correlation was found through a theoretical approach based on feedforward neural networks. This strategy was adopted because today these calculations are easily affordable for small molecules (like the analytes), and many critical parameters needed are not known. This might increase the applicability of the proposed method to other cases of study. Moreover, it was seen that the normal linear fit does not provide a good model. The interaction on the MWCNT phase was compared to that of an octadecyl (C18) reversed phase, under the same elution conditions. Results from trained neural networks indicated that the main role in the interactions between the analytes and the stationary phases is due to dipole moment, polarizability and LUMO energy. As expected for the C18 stationary phase correlation, is due to dipole moment and polarizability, while for the MWCNT stationary phase primarily to LUMO energy followed by polarizability, evidence for a specific interaction between MWCNTs and analytes. The CNT-based hybrid material proved to be not only a chromatographic phase but also a useful tool to investigate the MWCNT-molecular interactions with variously substituted benzenes. Keywords: Carbon nanotubes, Feedforward neural networks, Intermolecular interaction, Liquid chromatography

Aim of this work was to explore the possibility of retention and selectivity tuning in reversed-phase liquid chromatography by means of chemically modified multi-walled carbon nanotubes (MWCNTs). These were synthesized by derivatizing pristine MWCNTs with amino-terminated alkyl chains containing polar embedded groups. A novel hybrid material based on functionalized MWCNTs (MWCNTs-R-NH2) was prepared, characterized and tested. The idea was to design a mixed-mode separation medium basing its sorption properties on the peculiar characteristics of MWCNTs combined with the chemical interactions provided by the functional chains introduced on the nanotube skeleton. MWCNTs-R-NH2 were easily grafted to silica microspheres by gamma radiation (using a 60Co source) in the presence of polybutadiene as the linking agent. The composite was characterized by scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) analysis in terms of structural morphology, surface area and porosity. The MWCNTs-R-NH2 sorbent was tested as stationary phase. The reversed-phase behaviour was first proved by analysis of alkylbenzenes, while the key role of CNT derivatization in addressing the selectivity/affinity towards the solutes was evidenced by testing three classes of analytes, viz. barbiturates, steroid hormones and alkaloids. These compounds, with different molecular structure and polarity, were here analysed for the first time on CNT-based LC stationary phases. The behaviour of the novel sorbent was compared in terms of retention capability and resolution with that observed using unmodified MWCNTs, pointing out the mixed-mode characteristics of the MWCNTs-R-NH2 material. The same test mixtures were analysed also on a conventional mono-modal separation sorbent (C18) to highlight the particular behaviour of the (derivatized)MWCNTs-based stationary phases. The novel material showed better performance in separation of polar compounds, i.e. barbiturates and alkaloids, than the unmodified MWCNTs and than the C18 column. Results showed that MWCNT functionalization is powerful to modulate retention/selectivity in reversed-phase liquid chromatography. Keywords: Functionalized carbon nanotubes, Liquid chromatography, Mixed-mode stationary phases

In this work, a simple, quick and efficient analytical method for determination of human and veterinary fluoroquinolone antimicrobial residues in lettuce, cucumber and spinach is developed. The procedure entails a 6 min ultrasound-assisted extraction (UAE, 3 × 2 min) in an alkaline (2% v/v NH3) aqueous solution containing Mg2+ ions (3 × 6 mL), with no need for organic solvents. The extract is submitted to cleanup on the HLB™ cartridge and the fluoroquinolones are separated and quantified by HPLC-MS/MS in a 10 min chromatographic run, using a small amount of acetonitrile in the mobile phase. The method, entirely developed in real matrices, is validated according to the updated analytical guidelines and provided suitable recoveries in the range of 67–116% and precision (RSD ≤ 20%, n = 3) at different concentrations (15, 70 and 150 ng g−1), with method quantification limits of 2–10 ng g−1. Fluoroquinolones were detected and quantified at concentrations from few to hundreds of nanograms per gram in vegetables from supermarkets, demonstrating the applicability of the method for monitoring residues of these pharmaceuticals.

This study relies on the ability of six different fabrics to retain gunshot residues on their surfaces, and their capability to let them pass through. The fabrics were cotton, linen, elastane, polyester, silk and viscose, each of them placed above a filter paper sheet. This last was used to retain residues passing through fabric. Microscopic structures of the chosen textiles were characterized by optical microscopy, and their surface morphology was characterized by stylus profilometry. A semi-automatic Sig Sauer P228 pistol, calibre 9 × 21 mm IMI, was exploited and two shooting distances were considered, 10 cm and 40 cm. Preliminary, inorganic residue (IGSR) deposition patterns were visualized by X-ray fluorescence spectroscopy. Scanning electron microscopy was also used to describe morphology and composition of IGSR generated by discharging the selected gun. Concentration of IGSR on targets was then quantitatively determined by inductively coupled plasma optical emission spectrometry, while nitrites and nitrates, originated by nitrocellulose content of smokeless powders, were identified by ion chromatography. As expected, the amount of metallic residues, nitrites and nitrates decreases inversely with the shooting distance. In addition, considering the same distance, concentration of these elements changes significantly depending on the analyzed cloth. Therefore, when evaluating shooting distance in a forensic case, the habit to use a cotton textile to construct a calibration curve, despite of the actual nature of the target, could not be quantitatively accurate. It was evidenced that a significant amount of GSR passed through target fabrics, making their identification possible even on underneath tissues.

Lysyl hydroxylase 3 (LH3) catalyzes collagen lysine hydroxylation and their subsequent O-linked glycosylation. Here the authors provide mechanistic insights into the lysyl hydroxylase and glycosyltransferase activities of LH3 by determining the crystal structures of full-length human LH3 bound to cofactors and donor substrates.

A simple not solvent and time consuming Fe3O4@MIL-100(Fe), synthesized in the presence of a small amount of magnetite (Fe3O4) nanoparticles (27.3 wt%), is here presented and discussed. Layer-by-layer alone (20 shell), and combined layer-by-layer (5 shell)/reflux or /hydrothermal synthetic procedures were compared. The last approach (Fe3O4@MIL-100_H sample) is suitable (i) to obtain rounded-shaped nanoparticles (200–400 nm diameter) of magnetite core and MIL-100(Fe) shell; (ii) to reduce the solvent and time consumption (the layer-by-layer procedure is applied only 5 times); (iii) to give the highest MIL-100(Fe) amount in the composite (72.7 vs. 18.5 wt% in the layer-by-layer alone); (iv) to obtain a high surface area of 3546 m2 g−1. The MIL-100(Fe) sample was also synthesized and both materials were tested for the absorption of Ofloxacin antibiotic (OFL). Langmuir model well describes OFL adsorption on Fe3O4@MIL-100_H, indicating an even higher adsorption capacity (218 ± 7 mg g−1) with respect to MIL-100 (123 ± 5 mg g−1). Chemisorption regulates the kinetic process on both the composite materials. Fe3O4@MIL-100_H performance was then verified for OFL removal at µg per liter in tap and river waters, and compared with MIL-100. Its relevant and higher adsorption efficiency and the magnetic behavior make it an excellent candidate for environmental depollution.

A micron-sized sorbent, Magn-Humic, has been prepared by humic acids pyrolysis onto silica-coated magnetite. The material was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), and Brunauer, Emmett, and Teller (BET) surface area measurements and applied for simultaneous magnetic solid-phase extraction (MSPE) of glucocorticoids, estrogens, progestogens, and androgens at ng mL−1 levels from human plasma followed by high-performance liquid chromatography coupled with mass spectrometry (HPLC–MS/MS). Due to the low affinity for proteins, steroids extraction was done with no need for proteins precipitation/centrifugation. As highlighted by a design of experiments, MSPE was performed on 250 µL plasma (after 1:4 dilution) by 50 mg Magn-Humic (reusable for eight extractions) achieving quantitative recovery and satisfying clean-up. This was improved by washing (2 mL 2% v/v formic acid) prior to analytes elution by 0.5 mL 1:1 v/v methanol-acetonitrile followed by 0.5 mL methanol; eluate reduction to 0.25 mL compensated the initial sample dilution. The accuracy was assessed in certified blank fetal bovine serum and in human plasma, gaining satisfactory recovery in the range 65–122%, detection limits in the range 0.02–0.3 ng mL−1 (0.8 ng mL−1 for 17-β-estradiol) and suitable inter-day precision (relative standard deviation (RSD) n = 3). The method was evaluated in terms of selectivity, sensitivity, matrix-effect, instrumental carry-over, and it was applied to human plasma samples.

Two sensors for the detection of the metal ion Cu(II), based on the same sensing layer, are compared. They rely on different transduction methods, i.e., electrochemistry and surface plasmon resonance (SPR). D,L-penicillamine was used as the specific receptor since it is a strong ligand for copper(II). Moreover it is easily immobilized on a gold layer by a self assembling procedure by contacting the gold layer overnight with water/EtOH (80/20) containing D,L-penicillamine, taking advantage of the spontaneous interaction of thiols with gold surfaces. Both the electrochemical and SPR platforms were derivatized in the same way. In the first case a gold disc was used as working electrode, and in the second one a thin gold layer (60 nm thick) was deposited by sputtering over the exposed core of a plastic optical fiber (POF), after removing the cladding along half circumference.

A robust voltammetric method has been developed and validated for the determination of Fe(II) and Fe(III) in pharmaceutical iron polysaccharidic complexes. Undesirable low molecular weight iron complexes, at concentration about 3% in the pharmaceutical formulation, can be easily determined with good accuracy and precision. This methodology can be proposed as a viable, environmentally sustainable substitute for the conventional Normal Pulse Polarographic method in US Pharmacopeia, with better analytical figures of merit, and reduced Hg consumption. A deeper insight in Fe(II) and Fe(III) composition can be gained by the combined use of a new potentiometric technique after chemical decomposition of the complex. Keywords: Sodium ferric gluconate complex, Iron sucrose complex, Iron polysaccharides, Voltammetry

The previously published version of this Article contained an error in Figure 3. In panel a, the residues His667 and Asp669 were incorrectly labelled as His627 and Asp629. The error has been corrected in both the PDF and HTML versions of the Article.

The aim of this work was to couple physical-chemical approaches with photocatalysis to reduce by a simple, inexpensive way the organic load of olive mill wastewater (OMW), mandatorily prior to the final discharge. Before irradiation, different sorbents were tested to remove part of the organic fraction, monitored by measuring chemical oxygen demand (COD) and polyphenols (PP). Different low-cost, safe materials were tested, that is, Y zeolite (ZY), montmorillonite, and sepiolite. Considerable decrease of organic load was obtained, with the highest abatement (40%) provided by ZY (10 g L−1 in 1 : 10 OMW). Use of the three sorbents, in particular ZY, was convenient compared to commercial activated carbons. UV light photocatalytic tests, performed using P25 TiO2 on ZY-treated OMW, yielded quantitative remediation (ca. 90%). Also solar light provided significative results, PP being lowered by 74% and COD by 56%. Sol-gel anatase TiO2 and N-doped anatase TiO2 were also tested, obtaining good results, around -80% PP and -40% COD. Finally, an integrated approach was experimented by ZY-supported anatase TiO2 (TiO2@ZY). This photoreactive sorbent allowed one-pot treatment of OMW significative abatements of PP (-77%) and COD (-39%) with only 1 g L−1 material, under solar light.

Prolidase is the only human enzyme responsible for the digestion of iminodipeptides containing proline or hydroxyproline at their C-terminal end, being a key player in extracellular matrix remodeling. Prolidase deficiency (PD) is an intractable loss of function disease, characterized by mutations in the prolidase gene. The exact causes of activity impairment in mutant prolidase are still unknown. We generated three recombinant prolidase forms, hRecProl-231delY, hRecProl-E412K and hRecProl-G448R, reproducing three mutations identified in homozygous PD patients. The enzymes showed very low catalytic efficiency, thermal instability and changes in protein conformation. No variation of Mn(II) cofactor affinity was detected for hRecProl-E412K; a compromised ability to bind the cofactor was found in hRecProl-231delY and Mn(II) was totally absent in hRecProl-G448R. Furthermore, local structure perturbations for all three mutants were predicted by in silico analysis. Our biochemical investigation of the three causative alleles identified in perturbed folding/instability, and in consequent partial prolidase degradation, the main reasons for enzyme inactivity. Based on the above considerations we were able to rescue part of the prolidase activity in patients' fibroblasts through the induction of Heath Shock Proteins expression, hinting at new promising avenues for PD treatment.

Cytotoxicity of cadmium-containing silica nanoparticles Cd-SiO2NPs (0.05–100 µg/mL) versus SiO2NPs and CdCl2 was evaluated by an in vitro test battery in A549 by assessing (i) mitochondrial function, (ii) membrane integrity/cell morphology, (iii) cell growth/proliferation, (iv) apoptotic pathway, (v) oxidative stress, after short- (24–48 h) and long-term (10 days) exposure. Both Cd-SiO2NPs and CdCl2 produced dose-dependent cytotoxic effects: (i) MTT-assay: similar cytotoxicity pattern was observed at both 24 and 48 h, with a more Cd-SiO2NPs pronounced effect than CdCl2. Cd-SiO2NPs induced mortality (about 50%) at 1 μg/mL, CdCl2 at 25 μg/mL; (ii) calcein-AM/PI staining: decrease in cell viability, noticeable at 25 μg/mL, enhanced markedly at 50 and 100 μg/mL, after 24 h. Cd-SiO2NPs induced higher mortality than CdCl2 (25% versus 4%, resp., at 25 μg/mL) with further exacerbation after 48h; (iii) clonogenic assay: exposure for longer period (10 days) compromised the A549 proliferative capacity at very low dose (0.05 μg/mL); (iv) a progressive activation of caspase-3 immunolabelling was detected already at 1 μg/mL; (v) GSH intracellular level was modified by all compounds. In summary, in vitro data demonstrated that both Cd-SiO2NPs and CdCl2 affected all investigated endpoints, more markedly after Cd-SiO2NPs, while SiO2NPs influenced GSH only.