Synthesis and characterization of p-n junction ternary mixed oxides for photocatalytic coprocessing of CO2 and H2O

In the present paper, we report the synthesis and characterization of both binary (Cu2 O, Fe2 O3, and In2 O3 ) and ternary (Cu2 O-Fe2 O3 and Cu2 O-In2 O3 ) transition metal mixed-oxides that may find application as photocatalysts for solar driven CO2 conversion into energy rich species. Two different preparation techniques (High Energy Milling (HEM) and Co-Precipitation (CP)) are compared and materials properties are studied by means of a variety of characterization and analytical techniques UV-Visible Diffuse Reflectance Spectroscopy (UV-VIS DRS), X-ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Energy Dispersive X-Ray spectrometry (EDX). Appropriate data elaboration methods are used to extract materials bandgap for Cu2 O@Fe2 O3 and Cu2 O@In2 O3 prepared by HEM and CP, and foresee whether the newly prepared semiconductor mixed oxides pairs are useful for application in CO2-H2 O coprocessing. The experimental results show that the synthetic technique influences the photoactivity of the materials that can correctly be foreseen on the basis of bandgap experimentally derived. Of the mixed oxides prepared and described in this work, only Cu2 O@In2 O3 shows positive results in CO2-H2 O photo-co-processing. Preliminary results show that the composition and synthetic methodologies of mixed-oxides, the reactor geometry, the way of dispersing the photocatalyst sample, play a key role in the light driven reaction of CO2 –H2 O. This work is a rare case of full characterization of photo-materials, using UV-Visible DRS, XPS, XRD, TEM, EDX for the surface and bulk analytical characterization. Surface composition may not be the same of the bulk composition and plays a key role in photocatalysts behavior. We show that a full material knowledge is necessary for the correct forecast of their photocatalytic behavior, inferred from experimentally determined bandgaps

Ag-based synergistic antimicrobial composites. A critical review

The emerging problem of the antibiotic resistance development and the consequences that the health, food and other sectors face stimulate researchers to find safe and effective alternative methods to fight antimicrobial resistance (AMR) and biofilm formation. One of the most promising and efficient groups of materials known for robust antimicrobial performance is noble metal nanoparticles. Notably, silver nanoparticles (AgNPs) have been already widely investigated and applied as antimicrobial agents. However, it has been proposed to create synergistic composites, because pathogens can find their way to develop resistance against metal nanophases; therefore, it could be important to strengthen and secure their antipathogen potency. These complex materials are comprised of individual components with intrinsic antimicrobial action against a wide range of pathogens. One part consists of inorganic AgNPs, and the other, of active organic molecules with pronounced germicidal effects: both phases complement each other, and the effect might just be the sum of the individual effects, or it can be reinforced by the simultaneous application. Many organic molecules have been proposed as potential candidates and successfully united with inorganic counterparts: polysaccharides, with chitosan being the most used component; phenols and organic acids; and peptides and other agents of animal and synthetic origin. In this review, we overview the available literature and critically discuss the findings, including the mechanisms of action, efficacy and application of the silver-based synergistic antimicrobial composites. Hence, we provide a structured summary of the current state of the research direction and give an opinion on perspectives on the development of hybrid Ag-based nanoantimicrobials (NAMs)

Opto‐Electronic Characterization of Photocatalysts Based on p,n‐Junction Ternary and Quaternary Mixed Oxides Semiconductors (Cu2O‐In2O3 and Cu2O‐In2O3‐TiO2)

Semiconductor materials are the basis of electronic devices employed in the communication and media industry. In the present work, we report the synthesis and characterization of mixed metal oxides (MOs) as p,n‐junction photocatalysts, and demonstrate the correlation between the preparation technique and the properties of the materials. Solid‐state UV-visible diffuse reflectance spectroscopy (UV‐VIS DRS) allowed for the determination of the light absorption properties and the optical energy gap. X‐ray photoelectron spectroscopy (XPS) allowed for the determination of the surface speciation and composition and for the determination of the valence band edge. The opto‐electronic behavior was evaluated measuring the photocurrent generated after absorption of chopped visible light in a 3‐electrode cell. Scanning electron microscopy (SEM) measurements allowed for auxiliary characterization of size and morphology, showing the formation of composites for the ternary Cu2O‐In2O3 p,n‐mixed oxide, and even more for the quaternary Cu2O‐In2O3‐TiO2 MO. Light absorption spectra and photocurrent‐time curves mainly depend upon the composition of MOs, while the optical energy gap and defective absorption tail are closely related to the preparation methodology, time and thermal treatment. Qualitative electronic band structures of semiconductors are also presented

Cu nanoparticle-loaded nanovesicles with antibiofilm properties. Part i: Synthesis of new hybrid nanostructures

Copper nanoparticles (CuNPs) stabilized by quaternary ammonium salts are well known as antimicrobial agents. The aim of this work was to study the feasibility of the inclusion of CuNPs in nanovesicular systems. Liposomes are nanovesicles (NVs) made with phospholipids and are traditionally used as delivery vehicles because phospholipids favor cellular uptake. Their capacity for hydrophilic/hydrophobic balance and carrier capacity could be advantageous to prepare novel hybrid nanostructures based on metal NPs (Me-NPs). In this work, NVs were loaded with CuNPs, which have been reported to have a biofilm inhibition effect. These hybrid materials could improve the effect of conventional antibacterial agents. CuNPs were electro-synthesized by the sacrificial anode electrolysis technique in organic media and characterized in terms of morphology through transmission electron microscopy (TEM). The NVs were prepared by the thin film hydration method in aqueous media, using phosphatidylcholine (PC) and cholesterol as a membrane stabilizer. The nanohybrid systems were purified to remove non-encapsulated NPs. The size distribution, morphology and stability of the NV systems were studied. Different quaternary ammonium salts in vesicular systems made of PC were tested as stabilizing surfactants for the synthesis and inclusion of CuNPs. The entrapment of charged metal NPs was demonstrated. NPs attached preferably to the membrane, probably due to the attraction of their hydrophobic shell to the phospholipid bilayers. The high affinity between benzyl-dimethyl-hexadecyl-ammonium chloride (BDHAC) and PC allowed us to obtain stable hybrid NVs c.a. 700 nm in diameter. The stability of liposomes increased with NP loading, suggesting a charge-stabilization effect in a novel antibiofilm nanohybrid material

Platinum(IV) complexes of trans-1,2-diamino-4-cyclohexene: Prodrugs affording an oxaliplatin analogue that overcomes cancer resistance

Six platinum(IV) compounds derived from an oxaliplatin analogue containing the unsaturated cyclic diamine trans-1,2-diamino-4-cyclohexene (DACHEX), in place of the 1,2-diaminocyclohexane, and a range of axial ligands, were synthesized and characterized. The derivatives with at least one axial chlorido ligand demonstrated solvent-assisted photoreduction. The electrochemical redox behavior was investigated by cyclic voltammetry; all compounds showed reduction potentials suitable for activation in vivo. X-ray photoelectron spectroscopy (XPS) data indicated an X-ray-induced surface reduction of the Pt(IV) substrates, which correlates with the reduction potentials measured by cyclic voltammetry. The cytotoxic activity was assessed in vitro on a panel of human cancer cell lines, also including oxaliplatin-resistant cancer cells, and compared with that of the reference compounds cisplatin and oxaliplatin; all IC50 values were remarkably lower than those elicited by cisplatin and somewhat lower than those of oxaliplatin. Compared to the other Pt(IV) compounds of the series, the bis-benzoate derivative was by far (5–8 times) the most cytotoxic showing that low reduction potential and high lipophilicity are essential for good cytotoxicity. Interestingly, all the complexes proved to be more active than cisplatin and oxaliplatin even in three-dimensional spheroids of A431 human cervical cancer cells

Reverse Micelle Strategy for the Synthesis of MnOx-TiO2Active Catalysts for NH3-Selective Catalytic Reduction of NOxat Both Low Temperature and Low Mn Content

MnOx-TiO2catalysts (0, 1, 5, and 10 wt % Mn nominal content) for NH3-SCR (selective catalytic reduction) of NOxhave been synthesized by the reverse micelle-assisted sol-gel procedure, with the aim of improving the dispersion of the active phase, usually poor when obtained by other synthesis methods (e.g., impregnation) and thereby lowering its amount. For comparison, a sample at nominal 10 wt % Mn was obtained by impregnation of the (undoped) TiO2sample. The catalysts were characterized by using an integrated multitechnique approach, encompassing X-ray diffraction followed by Rietveld refinement, micro-Raman spectroscopy, N2isotherm measurement at −196 °C, energy-dispersive X-ray analysis, diffuse reflectance UV-vis spectroscopy, temperature-programmed reduction technique, and X-ray photoelectron spectroscopy. The obtained results prove that the reverse micelle sol-gel approach allowed for enhancing the catalytic activity, in that the catalysts were active in a broad temperature range at a substantially low Mn loading, as compared to the impregnated catalyst. Particularly, the 5 wt % Mn catalyst showed the best NH3-SCR activity in terms of both NOxconversion (ca. 90%) and the amount of produced N2O (ca. 50 ppm) in the 200-250 °C temperature range

Oxidized alginate dopamine conjugate: In vitro characterization for nose-to-brain delivery application

Background: The blood–brain barrier (BBB) bypass of dopamine (DA) is still a challenge for supplying it to the neurons of Substantia Nigra mainly affected by Parkinson disease. DA prodrugs have been studied to cross the BBB, overcoming the limitations of DA hydrophilicity. Therefore, the aim of this work is the synthesis and preliminary characterization of an oxidized alginatedopamine (AlgOX-DA) conjugate conceived for DA nose-to-brain delivery. Methods: A Schiff base was designed to connect oxidized polymeric backbone to DA and both AlgOX and AlgOX-DA were characterized in terms of Raman, XPS, FT-IR, and1H-NMR spectroscopies, as well as in vitro mucoadhesive and release tests. Results: Data demonstrated that AlgOX-DA was the most mucoadhesive material among the tested ones and it released the neurotransmitter in simulated nasal fluid and in low amounts in phosphate buffer saline. Results also demonstrated the capability of scanning near-field optical microscopy to study the structural and fluorescence properties of AlgOX, fluorescently labeled with fluorescein isothiocyanate microstructures. Interestingly, in SH-SY5Y neuroblastoma cell line up to 100 µg/mL, no toxic effect was derived from AlgOX and AlgOX-DA in 24 h. Conclusions: Overall, the in vitro performances of AlgOX and AlgOX-DA conjugates seem to encourage further ex vivo and in vivo studies in view of nose-to-brain administration

Circulating miR-184 is a potential predictive biomarker of cardiac damage in Anderson–Fabry disease

open21noFunding: This work was supported by the Italian Ministry of Health (PE-2013-02356818) to GCEnzyme replacement therapy (ERT) is a mainstay of treatment for Anderson–Fabry disease (AFD), a pathology with negative effects on the heart and kidneys. However, no reliable biomarkers are available to monitor its efficacy. Therefore, we tested a panel of four microRNAs linked with cardiac and renal damage in order to identify a novel biomarker associated with AFD and modulated by ERT. To this end, 60 patients with a definite diagnosis of AFD and on chronic ERT, and 29 age- and sex-matched healthy individuals, were enrolled by two Italian university hospitals. Only miR-184 met both conditions: its level discriminated untreated AFD patients from healthy individuals (c-statistic = 0.7522), and it was upregulated upon ERT (P < 0.001). On multivariable analysis, miR-184 was independently and inversely associated with a higher risk of cardiac damage (odds ratio = 0.86; 95% confidence interval [CI] = 0.76–0.98; P = 0.026). Adding miR-184 to a comprehensive clinical model improved the prediction of cardiac damage in terms of global model fit, calibration, discrimination, and classification accuracy (continuous net reclassification improvement = 0.917, P < 0.001; integrated discrimination improvement [IDI] = 0.105, P = 0.017; relative IDI = 0.221, 95% CI = 0.002–0.356). Thus, miR-184 is a circulating biomarker of AFD that changes after ERT. Assessment of its level in plasma could be clinically valuable in improving the prediction of cardiac damage in AFD patients.openSalamon I.; Biagini E.; Kunderfranco P.; Roncarati R.; Ferracin M.; Taglieri N.; Nardi E.; Laprovitera N.; Tomasi L.; Santostefano M.; Ditaranto R.; Vitale G.; Cavarretta E.; Pisani A.; Riccio E.; Aiello V.; Capelli I.; La Manna G.; Galie N.; Spinelli L.; Condorelli G.Salamon I.; Biagini E.; Kunderfranco P.; Roncarati R.; Ferracin M.; Taglieri N.; Nardi E.; Laprovitera N.; Tomasi L.; Santostefano M.; Ditaranto R.; Vitale G.; Cavarretta E.; Pisani A.; Riccio E.; Aiello V.; Capelli I.; La Manna G.; Galie N.; Spinelli L.; Condorelli G

Impact of CO₂-enriched combustion air on micro-gas turbine performance for carbon capture

Power generation is one of the largest anthropogenic greenhouse gas emission sources; although it is now reducing in carbon intensity due to switching from coal to gas, this is only part of a bridging solution that will require the utilization of carbon capture technologies. Gas turbines, such as those at the UK Carbon Capture Storage Research Centre's Pilot-scale Advanced CO2 Capture Technology (UKCCSRC PACT) National Core Facility, have high exhaust gas mass flow rates with relatively low CO2 concentrations; therefore solvent-based post-combustion capture is energy intensive. Exhaust gas recirculation (EGR) can increase CO2 levels, reducing the capture energy penalty. The aim of this paper is to simulate EGR through enrichment of the combustion air with CO2 to assess changes to turbine performance and potential impacts on complete generation and capture systems. The oxidising air was enhanced with CO2, up to 6.29%vol dry, impacting mechanical performance, reducing both engine speed by over 400 revolutions per minute and compression temperatures. Furthermore, it affected complete combustion, seen in changes to CO and unburned hydrocarbon emissions. This impacted on turbine efficiency, which increased specific fuel consumption (by 2.9%). CO2 enhancement could therefore result in significant efficiency gains for the capture plant