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Screen-printed electrodes (SPEs) are reliable, portable, affordable, and versatile electrochemical platforms for the real-time analytical monitoring of emerging analytes in the environmental, clinical, and agricultural fields. The aim of this study was to evaluate the electrochemical behavior of gold screen-printed electrodes (SPGEs) modified with molecules containing amino (Tr-N) or α-aminophosphonate (Tr-P) groups for the selective and sensitive detection of the toxic metal ions Pb2+ and Hg2+ in aqueous samples. After optimizing the analytical parameters (conditioning potential and time, deposition potential and time, pH and concentration of the supporting electrolyte), anodic square wave stripping voltammetry (SWASV) was used to evaluate and compare the electrochemical performance of bare or modified electrodes for the detection of Hg2+ and Pb2+, either alone or in their mixtures in the concentration range between 1 nM and 10 nM. A significative improvement in the detection ability of Pb2+ ions was recorded for the amino-functionalized gold sensor SPGE-N, while the presence of a phosphonate moiety in SPGE-P led to greater sensitivity towards Hg2+ ions. The developed sensors allow the detection of Pb2+ and Hg2+ with a limit of detection (LOD) of 0.41 nM and 35 pM, respectively, below the legal limits for these heavy metal ions in drinking water or food, while the sensitivity was 5.84 µA nM−1cm−2 and 10 µA nM−1cm−2, respectively, for Pb2+ and Hg2+. The reported results are promising for the development of advanced devices for the in situ and cost-effective monitoring of heavy metals, even in trace amounts, in water resources. [ABSTRACT FROM AUTHOR]

Palladium nanoparticles find extensive applications in catalysis in both homogeneously and heterogeneously catalyzed processes. Supporting metal nanoparticles enhances their stability as compared to their unsupported counterparts. The role of catalytic support is increasingly recognized as crucial in determining the behaviour of these materials. However, controlling the deposition and anchoring of palladium nanoparticles remains a significant challenge. This contribution discusses the preparation of straight lines of palladium particles on zinc oxide by wet impregnation. This phenomenon is attributed to the highly stepped morphology of the employed ZnO that created steric anchoring sites to stabilize the metal particles. Palladium-based catalysts were evaluated for the valuable Suzuki–Miyaura cross-coupling reaction. The dispersed Pd/ZnO catalyst achieved a conversion rate of 86% with 100% selectivity, remarkably superior to that of the Pd/Al2O3 and Pd/TiO2 counterparts. [ABSTRACT FROM AUTHOR]

Seaweeds are considered a biomass for third-generation biofuel, and hydrothermal carbonization (HTC) is a valuable process for efficiently disposing of the excess of macroalgae biomass for conversion into multiple value-added products. However, the HTC process produces a liquid phase to be disposed of. The present study aims to investigate the effects of seed-priming treatment with three HTC-discarded liquid phases (namely AHL180, AHL240, and AHL300), obtained from different experimental procedures, on seed germination and plant growth and productivity of Phaseolus vulgaris L. To disentangle the osmotic effects from the use of AHL, isotonic solutions of polyethylene glycol (PEG) 6000 have also been tested. Seed germination was not affected by AHL seed-priming treatment. In contrast, PEG-treated samples showed significantly lower seed germination success. AHL-treated samples showed changes in plant biomass: higher shoot biomass was recorded especially in AHL180 samples. Conversely, AHL240 and AHL300 samples showed higher root biomass. The higher plant biomass values recorded in AHL-treated samples were the consequence of higher values of photosynthesis rate and water use efficiency, which, in turn, were related to higher stomatal density. Recorded data strongly support the hypothesis of the AHL solution reuse in agriculture in the framework of resource management and circular green economy. [ABSTRACT FROM AUTHOR]

Carbon dots (CDs) samples were synthesized from orange peel waste (OPW) via a simple and eco‐friendly hydrothermal carbonization (HTC) and electrochemical (EC) bottom‐up synthesis integrated approach. The comprehensive chemical‐physical characterization of CDs samples, carried out by various techniques such as TEM, EDX, XRD, FT‐IR, underlined their morphological and microstructural features. The CDs exhibited attractive electrochemical properties, and thus an electrochemical sensor by modifying a screen printed carbon electrode (CDs/SPCE) for the detection of nitrobenzene (NB) in water was developed. Electroanalytical performances of CDs/SPCE sensor using differential pulse voltammetry (DPV) demonstrated its high sensitivity (9.36 μA μM−1 cm−2) towards NB in a wide linear dynamic range (0.1–2000 μM) and a low limit of detection (LOD=13 nM). The electrochemical sensor also shown high selectivity, long‐term stability, and repeatability. This paper might open the way to a new synergistic HTC‐EC approach for the synthesis of CDs from waste biomass material and their advanced application in highly efficient electrochemical sensors. [ABSTRACT FROM AUTHOR]

In the present work, a study was carried out with the aim of enhancing the performance of electrochemical biosensors based on Co3O4:Fe2O3 heterojunctions. Specifically, the redox behavior of screen–printed carbon electrodes (SPCEs) modified with Co3O4:Fe2O3 (0.5 wt%:x wt%) nanocomposites, where x ranged from 0.1 to 0.5 wt%, was examined in detail. The hybrid nanocomposites were synthesized using the sol-gel auto-combustion method. Several characterization methods were performed to investigate the morphology, microstructure, and surface area of the pure Co3O4, pure Fe2O3, and the synthesized Co3O4:Fe2O3 nanocomposites. Using cyclic voltammetry (CV) tests, the electrochemical behavior of the modified electrodes toward the dopamine (DA) molecules was investigated. The modified Co3O4:Fe2O3, (0.5 wt%, x = 0.4 wt%)/SPCE resulted in a sensor with the best electrochemical performance toward DA. A high linear relationship between DA concentrations and the faradic current variation (ipa (μA) = 0.0736 + 0.1031 CDA (μA) and R2 = 0.99) was found in the range of 10–100 μM. The sensitivity value was computed to be 0.604 µA µM−1cm−2 and the limit of detection (LOD) 0.24 µM. Based on the characterization and electrochemical results, it can be suggested that the formation of Co3O4:Fe2O3 heterostructures provides a large specific surface area, an increased number of electroactive sites at the metal oxide interface and a p–n heterojunction, thus ensuring a remarkable enhancement in the electrochemical response towards DA. [ABSTRACT FROM AUTHOR]

Hybrid hydrogels composed of chitosan (CS) have shown great potential in bone tissue engineering and regeneration. The introduction of polyhedral oligomeric silsesquioxanes (POSS) in the biopolymeric matrix has been demonstrated to improve the rheological and biological properties of the hybrid composites. In this work, we have integrated the favourable features of chitosan (CS) and POSS nanoparticles to design new nanocomposites for bone tissue regeneration, focusing our attention on the effect of POSS concentration within the CS matrix (0.5, 1, and 1.5 equivalents in weight of POSS with respect to CS) on the chemical, physical, rheological, and in vitro biological properties of the final composites. The drug release ability of the synthesized hydrogel scaffolds were also investigated using, as the model drug, ketoprofen, that was included in the scaffold during the gelling procedure, showing a more controlled release for the hybrids with respect to CS (86–91% of drug released after two weeks). The results of the in vitro biological tests performed on human fetal osteoblastic cells (hFOB 1.19) culture demonstrated the great biocompatibility of the hybrid materials. The hybrids, at the different POSS concentrations, showed values of cell mortality superimposable with control cells (11.1 vs. 9.8%), thus revealing the CS/POSS hydrogels as possible candidates for bone tissue engineering applications. [ABSTRACT FROM AUTHOR]

The total annual production of agricultural biomass such as wood, corn cobs, leaves, and citrus peels, is estimated at 956 million tons (Mt). Since crop residues are by-products of agricultural production, crop residue collection does not compete with food crops for acreage and therefore, it does not negatively impact food prices. Moreover, it has the advantage of reducing the amount of waste, the disposal of which often becomes a serious problem despite natural sources. Biomass conversion becomes a very valid alternative to diversify energy sources and reduce global warming. Thermochemical treatment of biomass is a promising way to convert biomass into bio-oil, biochar, and gas. In recent years, interest in the conversion of plant biomass into biochar has increased because this carbonaceous material has interesting properties that guarantee applications in wastewater treatment, soil improvement, solid fuels, and energy. The processes performed to convert biomass into biochar are different and the most used are thermochemical processes: pyrolysis, torrefaction, hydrothermal treatment, and gasification. The studies of the thermokinetic parameters that control these processes are carried out using different methods that provide the necessary information for the applicability of the processes on an industrial scale. One of the objectives of the present review is to compare kinetic models in order to clarify the role of the conversion process and the effects of the process parameters on the final product. A comprehensive investigation of the thermokinetic parameters controlling the conversion of crop residues to biochar was conducted. The mathematical description of kinetic processes is usually performed using the Arrhenius equation and its derivatives to obtain the activation energies (Ea), the pre-exponential parameter, and the process mechanisms. While isothermal processes can be described using the model fitting method, isoconversional processes can be studied using both the model fitting method and model-free methods. The high complexity and diversity of the reactions involved could lead to the use of approximations. In this paper, an overview of the kinetic parameters determined for biochar production processes and the model used to determine them is given. [ABSTRACT FROM AUTHOR]

Cancer-targeted drug delivery systems (DDS) based on carbon nanostructures have shown great promise in cancer therapy due to their ability to selectively recognize specific receptors overexpressed in cancer cells. In this paper, we have explored a green route to synthesize nanobiochar (NBC) endowed with graphene structure from the hydrothermal carbonization (HTC) of orange peels and evaluated the suitability of this nanomaterial as a nanoplatform for cancer therapy. In order to compare the cancer-targeting ability of different widely used targeting ligands (TL), we have conjugated NBC with biotin, riboflavin, folic acid and hyaluronic acid and have tested, in vitro, their biocompatibility and uptake ability towards a human alveolar cancer cell line (A549 cells). The nanosystems which showed the best biological performances—namely, the biotin- and riboflavin- conjugated systems—have been loaded with the poorly water-soluble drug DHF (5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one) and tested for their anticancer activity. The in vitro biological tests demonstrated the ability of both systems to internalize the drug in A549 cells. In particular, the biotin-functionalized NBC caused cell death percentages to more than double with respect to the drug alone. The reported results also highlight the positive effect of the presence of oxygen-containing functional groups, present on the NBC surface, to improve the water dispersion stability of the DDS and thus make the approach of using this nanomaterial as nanocarrier for poorly water-soluble drugs effective. [ABSTRACT FROM AUTHOR]

Pure titanium and titanium alloys are widely used in dentistry and orthopedics. However, despite their outstanding mechanical and biological properties, implant failure mainly due to post-operative infection still remains a significant concern. The possibility to develop inherent antibacterial medical devices was here investigated by covalently inserting bioactive ammonium salts onto the surface of titanium metal substrates. Titanium discs have been functionalized with quaternary ammonium salts (QASs) and with oleic acid (OA), affording the Ti-AEMAC Ti-GTMAC, Ti-AUTEAB, and Ti-OA samples, which were characterized by ATR-FTIR and SEM-EDX analyses and investigated for the roughness and hydrophilic behavior. The chemical modifications were shown to deeply affect the surface properties of the metal substrates and, as a consequence, their bio-interaction. The bacterial adhesion tests against the Gram-negative Escherichia Coli and Gram-positive Staphylococcus aureus, at 1.5 and 24 h of bacterial contact, showed good anti-adhesion activity for Ti-AUTEAB and Ti-OA samples, containing a long alkyl chain between the silicon atom and the ammonium functionality. In particular, the Ti-AUTEAB sample showed inhibition of bacteria adhesion against Escherichia Coli of about one log with respect to the other samples, after 1.5 h. The results of this study highlight the importance of chemical functionalization in addressing the antimicrobial activity of metal surfaces and could open new perspectives in the development of inherent antibacterial medical devices. [ABSTRACT FROM AUTHOR]

Featured Application: Hydrothermal carbonization process can be efficiently used for the simultaneous production of value-added chemicals, including furans and levulinates, and carbon-based materials. In this study, a simple and green protocol to obtain hydrochar and high-added value products, mainly 5-hydroxymethylfurfural (5-HMF), furfural (FU), levulinic acid (LA) and alkyl levulinates, by using the hydrothermal carbonization (HTC) of orange peel waste (OPW) is presented. Process variables, such as reaction temperature (180–300 °C), reaction time (60–300 min), biomass:water ratio and initial pH were investigated in order to find the optimum conditions that maximize both the yields of solid hydrochar and 5-HMF and levulinates in the bio-oil. Data obtained evidence that the highest yield of hydrochar is obtained at a 210 °C reaction temperature, 180 min residence time, 6/1 w/w orange peel waste to water ratio and a 3.6 initial pH. The bio-products distribution strongly depends on the applied reaction conditions. Overall, 180 °C was found to be the best reaction temperature that maximizes the production of furfural and 5-HMF in the presence of pure water as a reaction medium. [ABSTRACT FROM AUTHOR]

The aim of this tutorial review is to provide a general overview of processes, technologies and challenges in the production of pharmaceutical and bioactive compounds from food waste and lignocellulosic residues. Particular attention is given to benign-by-design processes instinctively devoted to environmental sustainability for the recovery of bioactive compounds from food waste as well as for the production of alcohols, acids, polyols, furans and aromatic compounds from lignocellulosic residues. At the same time, novel green synthetic routes for the production of active pharmaceutical ingredients and the development of novel bioactive compounds are discussed. Recent success industrial stories on the use of food waste and lignocellulosic residues for pharmaceutical and nutraceutical applications are also discussed. [ABSTRACT FROM AUTHOR]

Electrochemical sensors for monitoring biochemical substances are attracting considerable attention. These devices are usually based on enzymes that are sensitive and very specific. Still, the activity of those enzymes is lost with changes in temperature or pH. Non-enzymatic electrochemical sensors – fabricated via the modification of the electrode surface with metal oxide nanoparticles – are an ideal answer to address that problem. In this study, we investigated the photo-electrochemical properties of CuO–TiO2 heterojunctions for glucose sensing in alkaline media. A combination of high-resolution (scanning) transmission electron microscopy, spatially resolved electron energy-loss spectroscopy, energy-dispersive X-ray spectroscopy and X-ray powder diffraction, was used to study in detail the microstructures of the prepared specimens. These results highlighted the strong intertwining between the TiO2 nanoparticles and the Cu-based nanoparticles, which present a metallic core with a CuO rich surface. In addition, we showed that CuO, joint to TiO2, has smaller size compared to pure CuO, which entails larger specific surface area available for the glucose electro-oxidation, which consequently enhanced the electrochemical features. The influence of Cu loading over the sensing performance of TiO2 was examined in detail carrying out electrochemical sensing tests under dark, laboratory and halogen lamp irradiation conditions. Results demonstrated that, under halogen lamp irradiation, modified CuO–TiO2 electrodes showed a specific response signal that is four times higher than that of pure CuO. Those increased photo-electrochemical properties in CuO–TiO2 heterojunctions are likely due to a synergistic effect between the microstructural characteristics and effective separation of photo-generated excitons created at the heterojunction interface. Results of this study offer applicable guidelines for designing photo-electrochemical screen-printed electrodes based on nano-sized CuO on titania for efficient detection of glucose. [ABSTRACT FROM AUTHOR]

The effects of cerium addition on the physical-chemical properties and CO oxidation activity of nanocomposite MnCeOx catalysts (0 ≤ χCe ≤ 1) have been assessed. The kinetics of the CO oxidation on a typical nanocomposite MnCeOx catalyst (M5C1) were probed by temperature programmed catalytic reaction tests in the range of 293-533K. A systematic study of the interaction pattern of the catalyst with reagent and product molecules shows easy reactivity of surface oxygen to CO, low mobility of lattice oxygen and weak surface affinity to CO2. Systematic evidences on mechanism and intermediates signal an extrafacial redox path, triggered by the abstraction of oxygen atoms in the neighbouring of surface-active MnIV sites, and sustained by O2 species adsorbed on the resulting O-vacancies. A Langmuir-Hinshelwood (L-H) type reaction mechanism leads to a formal kinetic model fully predicting the CO oxidation functionality of the MnCeOx catalysts. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomasses have a tremendous potential to cover the future demand of bio-based chemicals and materials, breaking down our historical dependence on petroleum resources. The development of green chemical technologies, together with the appropriate eco-politics, can make a decisive contribution to a cheap and effective conversion of lignocellulosic feedstocks into sustainable and renewable chemical building blocks. In this regard, the use of an indirect H-source for reducing the oxygen content in lignocellulosic biomasses and in their derived platform molecules is receiving increasing attention. In this contribution we highlight recent advances in the transfer hydrogenolysis of cellulose, hemicellulose, lignin, and of their derived model molecules promoted by heterogeneous catalysts for the sustainable production of biofuels and biochemicals. [ABSTRACT FROM AUTHOR]

Abstract: Nickel/carbon composites (Ni−C) have been synthesized by a pyrolysis treatment carried out at the temperature of 675 °C, of NiO incorporated into a pyrogallol‐formaldehyde organic wet gel. Structural and morphological characterizations of the Ni−C samples were performed by XRD and SEM analysis, respectively. Electrochemical non‐enzymatic glucose sensors were fabricated modifying the working electrode surface of screen printed carbon electrodes. Cyclic voltammetry and amperometric tests were performed in order to investigate the electrocatalytic activity of differently Ni loaded carbon towards the oxidation of glucose in alkaline 0.1 M KOH solution. The sensor based on 30 % Ni/carbon showed the best sensing performance towards glucose monitoring with a sensitivity of 670 μA/mM cm−1 in the a liner range from 20 to 500 μM, and a detection limit lower than 8 μM at S/N=3. [ABSTRACT FROM AUTHOR]

Cover Feature: Voltammetric Sensor Based on Waste-Derived Carbon Nanodots for Enhanced Detection of Nitrobenzene (ChemElectroChem 13/2023) Carbon nanodots, electrochemical sensor, electrochemical bottom-up synthesis, waste valorization, nitrobenzene Keywords: carbon nanodots; electrochemical sensor; electrochemical bottom-up synthesis; waste valorization; nitrobenzene EN carbon nanodots electrochemical sensor electrochemical bottom-up synthesis waste valorization nitrobenzene 1 1 1 07/05/23 20230703 NES 230703 B The Cover Feature b shows groundwater contaminated by environmental pollutants and how a sensor modified by an improved waste is helpful to estimate the presence of contaminants in it. [Extracted from the article]