Zinc Electrode Cycling in Deep Eutectic Solvent Electrolytes: An Electrochemical Study.

Among post-lithium ion battery technologies, rechargeable chemistries with Zn anodes bear notable technological promise owing to their high theoretical energy density, lower manufacturing cost, availability of raw materials and inherent safety. However, Zn anodes, when employed in aqueous electrolytes, suffer from hydrogen evolution, passivation, and shape changes. Alternative electrolytes can help tackle these issues, preserving the green and safe characteristics of aqueous-based ones. Deep eutectic solvents (DESs) are promising green and low-cost non-aqueous solvents for battery electrolytes. Specifically, the cycling of Zn anodes in DESs is expected to be reversible, chiefly owing to their dendrite-suppression capability. Nevertheless, apart from a few studies on Zn plating, insight into the cathodic-anodic electrochemistry of Zn in DESs is still very limited. In view of developing DES-based battery electrolytes, it is crucial to consider that a potential drawback might be their low ionic conductivity. Water molecules can be added to the eutectic mixtures by up to 40% to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature. In this study, we address the electrochemistry of Zn in two different hydrated DESs (ChU and ChEG with ~30% H2O). Fundamental electrokinetic and electrocrystallization studies based on cyclic voltammetry and chronoamperometry at different cathodic substrates are completed with a galvanostatic cycling test of Zn|Zn symmetric CR2032 coin cells, SEM imaging of electrodes and in situ SERS spectroscopy. This investigation concludes with the proposal of a specific DES/H2O/ZnSO4-based electrolyte that exhibits optimal functional performance, rationalized on the basis of fundamental electrochemical data, morphology evaluation and modeling of the cycling response.

Pedot:PSS/Graphene Oxide (GO) Ternary Nanocomposites for Electrochemical Applications.

Among conductive polymers, poly(3,4 ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) has been widely used as an electrode material for supercapacitors, solar cells, sensors, etc. Although PEDOT:PSS-based thin films have acceptable properties such as good capacitive and electrical behaviour and biocompatibility, there are still several challenges to be overcome in their use as an electrode material for supercapacitors. For this reason, the aim of this work is to fabricate and characterise ternary nanocomposites based on PEDOT:PSS and graphene oxide (GO), blended with green additives (glucose (G) or ascorbic acid (AA)), which have the benefits of being environmentally friendly, economical, and easy to use. The GO reduction process was first accurately investigated and demonstrated by UV-Vis and XRD measurements. Three-component inks have been developed, and their morphological, rheological, and surface tension properties were evaluated, showing their printability by means of Aerosol Jet® Printing (AJ®P), an innovative direct writing technique belonging to the Additive Manufacturing (AM) for printed electronics applications. Thin films of the ternary nanocomposites were produced by drop casting and spin coating techniques, and their capacitive behaviour and chemical structures were evaluated through Cyclic Voltammetry (CV) tests and FT-IR analyses. CV tests show an increment in the specific capacitance of AAGO-PEDOT up to 31.4 F/g and excellent overtime stability compared with pristine PEDOT:PSS, suggesting that this ink can be used to fabricate supercapacitors in printed (bio)-electronics. The inks were finally printed by AJ®P as thin films (10 layers, 8 × 8 mm) and chemically analysed by FT-IR, demonstrating that all components of the formulation were successfully aerosolised and deposited on the substrate.

GO/PEDOT:PSS nanocomposites: effect of different dispersing agents on rheological, thermal, wettability and electrochemical properties.

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

Electrodeposition of nanostructured bioactive hydroxyapatite-heparin composite coatings on titanium for dental implant applications.

In this paper we describe the one-pot fabrication of hydroxyapatite (HA)-heparin composites by electrodeposition onto Ti substrates and their characterisation in terms of structure, morphology, heparin content and bioactivity. HA coatings are well known and widely applied osteointegration enhancers, but post-implant healing rate in dental applications is still suboptimal: e.g. coagulation control plays a key role and the incorporation of an anticoagulant is considered a highly desirable option. In this study, we have developed an improved, simple and robust growth procedure for single-phase, pure HA-heparin films of thickness 1/3 µm. HA-heparin, forming nanowires, has the ideal morphology for bone mineralisation. Staining assays revealed homogeneous incorporation of sizable amounts of heparin in the composite films. The bioactivities of the HA and HA-heparin coatings on Ti were compared by HeLa cell proliferation/viability tests and found to be enhanced by the presence of the anticoagulant.

Electrodeposition of Co/CoO nanoparticles onto graphene for ORR electrocatalysis: a study based on micro-X-ray absorption spectroscopy and X-ray fluorescence mapping.

Electrodeposition of graphene-supported Co for ORR electrocatalysts from an acetonitrile solution has been studied by a multi-technique approach, combining a suite of spectroscopic methods with electrochemical measurements, allowing a molecular-level understanding of potentiostatic and pulsed-potential plating processes from the organic solvent onto a freestanding graphene film. The formation of the graphene film by the light-scribe approach has been monitored by Raman spectroscopy; the electrodeposition process has been clarified by cyclic voltammetry and the compositional and chemical-state distribution of Co have been investigated ex situ by soft X-ray absorption spectroscopy and fluorescence mapping, showing that both spatial distribution and valence state are homogeneous and independent of the local current density. The deposit consists in micrometric aggregates of Co/CoO nanoparticles with diameter ca. 30 nm (pulsed) and 200 nm (potentiostatic deposition). Potentiostatic deposition allows to obtain better ORR electrocatalytic perfomance in terms of nnumber of transferred electrons, onset/ half-wave potential and current density.

On the effect of pepsin incubation on type I collagen from horse tendon: Fine tuning of its physico-chemical and rheological properties.

Type I collagen is commonly recognized as the gold standard biomaterial for the manufacturing of medical devices for health-care related applications. In recent years, with the final aim of developing scaffolds with optimal bioactivity, even more studies focused on the influence of processing parameters on collagen properties, since processing can strongly affect the architecture of collagen at various length scales and, consequently, scaffolds macroscopic performances. The ability to finely tune scaffold properties in order to closely mimic the tissues' hierarchical features, preserving collagen's natural conformation, is actually of great interest. In this work, the effect of the pepsin-based extraction step on the material final properties was investigated. Thus, the physico-chemical properties of fibrillar type I collagens upon being extracted under various conditions were analyzed in depth. Correlations of collagen structure at the supramolecular scale with its microstructural properties were done, confirming the possibility of tuning rheological, viscoelastic and degradation properties of fibrillar type I collagen.

High-Temperature Corrosion of Flame-Sprayed Power Boiler Components with Nickel Alloy Powders.

The development trends in the energy sector clearly indicate an increase in the share of biomass and alternative fuels fed for combustion in power boilers, which results in the imposition of many unfavourable factors and a demanding working environment. During the operation of the energy system, this means a sharp increase in corrosion of the gas-tight pipe walls and coils by the destructive action of chlorine and sulphur. Implementing advanced surface protection in addition to the selection of materials of better quality and resistance to difficult working conditions would significantly reduce their wear by high temperature corrosion. Thermally sprayed coatings offer a great opportunity to protect machine components and energy systems against corrosion, erosion, impact load and abrasive wear. This article presents the test results of high-temperature corrosion resistance of coatings made with Ni-Cr-B-Si and Ni-B-Si alloy powders on a boiler steel substrate. Samples with sprayed coatings were exposed to an atmosphere with a composition of N2 + 9% O2 + 0.08% SO2 + 0.15% HCl at 800 °C for 250, 500, 750 and 1000 h. Tests results of coatings made of Ni-Cr-B-Si alloys subjected to the influence of a corrosive environment showed the formation of a layer of scale on the surface, composed mainly of Cr2O3 oxide, which was a passive layer, reducing the rate of corrosion. Coatings sprayed with Ni-B-Si alloys showed significantly lower corrosion resistance. It was found that the developed technology of subsonic flame spraying with powders of the Ni-Cr-B-Si type allows the production of coatings compliant with the requirements of the energy industry, which allows their use as anti-corrosion protection on boiler elements intended for waste disposal and biomass combustion.

Hydrophobic, Mechanical, and Physical Properties of Polyurethane Nanocomposite: Synergistic Impact of Mg(OH)2 and SiO2.

Polyurethane (PU) is one of the most well-known polymer coatings because of its favorable characteristics, which include its low density, nontoxicity, nonflammability, longevity, adhesion, simple manufacture, flexibility, and hardness. However, PU does come with several major drawbacks, among which are poor mechanical properties as well as low thermal and chemical stability, particularly in the high-temperature mode, where becomes gets flammable and loses adhesion ability. The limitations have inspired researchers to develop a PU composite to improve the weaknesses by adding different reinforcements. Magnesium hydroxide, having the ability to be produced with exceptional properties such as flammability, has consistently attracted the interest of researchers. Additionally, silica nanoparticles with high strength and hardness are one of the excellent reinforcements of polymers these days. The hydrophobic, physical, and mechanical properties of pure polyurethane and the composite type (nano, micro, and hybrid) fabricated with the drop casting method were examined in this study. 3-Aminopropyl triethoxysilane was applied as a functionalized agent. To confirm that hydrophilic particles turned into hydrophobic, FTIR analysis was carried out. The impact of size, percentage, and kind of fillers on different properties of PU/Mg(OH)2-SiO2 was then investigated using different analyses including spectroscopy and mechanical and hydrophobicity tests. The resultant observations demonstrated that different surface topographies can be obtained from the presence of particles of different sizes and percentages on the hybrid composite's surface. Surface roughness allowed for exceptionally high water contact angles, which confirmed the hybrid polymer coatings' superhydrophobic properties. According to the particle size and content, the distribution of fillers in the matrix also improved the mechanical properties.

In situ electrochemical SFG/DFG study of CN- and nitrile adsorption at Au from 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ionic liquid([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]diazenyl} benzonitrile (CTDB) and K[Au(CN)2].

In this paper we report an in situ electrochemical Sum-/Difference Frequency Generation (SFG/DFG) spectroscopy investigation of the adsorption of nitrile and CN⁻ from the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]-diazenyl}benzonitrile (CTDB) at Au electrodes in the absence and in the presence of the Au-electrodeposition process from K[Au(CN)2]. The adsorption of nitrile and its coadsorption with CN⁻ resulting either from the cathodic decomposition of the dye or from ligand release from the Au(I) cyanocomplex yield potential-dependent single or double SFG bands in the range 2,125-2,140 cm⁻¹, exhibiting Stark tuning values of ca. 3 and 1 cm⁻¹ V⁻¹ in the absence and presence of electrodeposition, respectively. The low Stark tuning found during electrodeposition correlates with the cathodic inhibiting effect of CTDB, giving rise to its levelling properties. The essential insensitivity of the other DFG parameters to the electrodeposition process is due to the growth of smooth Au.

Civilization in transition. The contemporary imperative for an active unus mundus.

Jung's conception of 'unus mundus' takes on new relevance. More than ever, the question arises of what we need today to come back into harmony with the creative and healing forces of the universe. Through synchronistic events, we experience connectedness and how the world as a whole affects us. With the help of the Tarot and the Chinese wisdom book I Ching, the spiritual dimension of unus mundus can be experienced. With the Hexagram '56 Lü - the Wanderer', as well as in the great Arcano 'the Sun' in the Tarot, and in the symbol of the snake, it is shown that one should be adaptable and willing to learn constantly. All archetypal images speak about the need to be aware, that periods of transition are dangerous and exciting. The important exercise here is to prepare oneself for the cosmic order of constant changes.

La conception de Jung sur « l'unus mundus ¼ acquiert une pertinence nouvelle. La question se pose plus que jamais de ce dont nous avons besoin aujourd'hui pour retrouver une harmonie avec les forces de guérison créatrices de l'univers. Par les événements synchronistiques nous faisons l'expérience de l'interdépendance et de comment nous sommes affectés par le monde en tant qu'unité globale. A l'aide du Tarot et du livre de sagesse Chinoise - le Yi King - nous pouvons faire l'expérience de la dimension spirituelle de l'unus mundus. Avec l'hexagramme 56 « Liu - le voyageur ¼ comme avec l'arcane majeur « Le Soleil ¼ dans le Tarot, ainsi que dans le symbole du serpent, il est montré que l'on devrait être adaptable et disposé à apprendre continuellement. Toutes les images archétypales parlent du besoin d'avoir conscience que les périodes de transition sont dangereuses et excitantes. Ici l'exercice important est de se préparer soi pour l'ordre cosmique de changements continuels.

La concepción de 'unus mundus' de Jung cobra nueva relevancia. Más que nunca, emerge la pregunta acerca de que necesitamos hoy para volver a estar en armonía con las fuerzas sanadoras y creativas del universo. A través de eventos sincronísticos, experimentamos un sentido de conexión y de cómo el mundo como totalidad nos afecta. Con la ayuda del Tarot y del libro de la sabiduría China, I Ching, la dimensión espiritual del unus mundus puede ser experimentada. El hexagrama'56 Lü - El Andariego', así como el Arcano Mayor 'El Sol' en el Tarot, y el símbolo de la serpiente, muestran que deberíamos ser adaptables y dispuestos a aprender constantemente. Todas las imágenes arquetípicas hablan de la necesidad de estar conscientes, de que los períodos de transición son peligrosos y emocionantes. El importante ejercicio, aquí, es prepararse uno mismo para el orden cósmico de cambios constantes.

A concepção de Jung de 'unus mundus' assume nova relevância. Mais do que nunca, surge a questão do que precisamos hoje para voltar à harmonia com as forças criativas e curativas do universo. Através de eventos sincrônicos, experimentamos a conexão e como o mundo como um todo nos afeta. Com a ajuda do Tarô e do livro de sabedoria chinesa I Ching, a dimensão espiritual de unus mundus pode ser experimentada. Com o Hexagrama '56 Lü - o Andarilho', bem como no grande Arcano "o Sol" no Tarô e no símbolo da cobra, mostra-se que se deve ser adaptável e disposto a aprender constantemente. Todas as imagens arquetípicas falam sobre a necessidade de estar ciente de que os períodos de transição são perigosos e emocionantes. O exercício importante aqui é se preparar para a ordem cósmica de constantes mudanças.

Autofluorescence of Model Polyethylene Terephthalate Nanoplastics for Cell Interaction Studies.

This work contributes to fill one of the gaps regarding nanoplastic interactions with biological systems by producing polyethylene terephthalate (PET) model nanoplastics, similar to those found in the marine environment, by means of a fast top-down approach based on mechanical fragmentation. Their size distribution and morphology were characterized by laser diffraction and atomic force microscopy (AFM). Their autofluorescence was studied by spectrofluorimetry and fluorescence imaging, being a key property for the evaluation of their interaction with biota. The emission spectra of label-free nanoplastics were comparable with those of PET nanoplastics labeled with Nile red. Finally, the suitability of label-free nanoplastics for biological studies was assessed by in vitro exposure with Mytilus galloprovincialis hemolymphatic cells in a time interval up to 6 h. The nanoplastic internalization into these cells, known to be provided with phagocytic activity, was assessed by fluorescence microscopy. The obtained results underlined that the autofluorescence of the model PET nanoplastics produced in the laboratory was adequate for biological studies having the potential to overcome the disadvantages commonly associated with several fluorescent dyes, such as the tendency to also stain other organic materials different from plastics, to form aggregates due to intermolecular interactions at high concentrations with a consequent decrease in fluorescence intensity, and to dye desorption from nanoparticles. The results of the autofluorescence study provide an innovative approach for plastic risk assessment.

Corrosion of Ni in 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethylsulfonyl) amide room-temperature ionic liquid: an in situ X-ray imaging and spectromicroscopy study.

This paper reports a pioneering application of soft X-ray scanning transmission microscopy (STXM), combined with micro-spot X-ray absorption spectroscopy (XAS) and X-ray fluorescence spectroscopy (XRF), for the investigation of the corrosion of metal electrodes in contact with room-temperature ionic liquids (RTIL). Using an open electrochemical cell in vacuo we explore some fundamental aspects of the aggressiveness of the 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP][TFSA]) RTIL towards Ni under in situ electrochemical polarisation. The possibility of imaging electrochemically-induced morphological features in conjunction with micro-XAS and XRF spectroscopies has provided unprecedented details regarding the space distribution and chemical state of corrosion products.

Electrochemical behaviour and surface characterisation of Zr exposed to an SBF solution containing glycine, in view of dental implant applications.

Zr and Ti alloys are extensively used in the biomedical field owing to their optimal mechanical properties and excellent corrosion resistance. Fully ceramic implants based on zirconia are appealing with respect to the traditional Ti-based metallic ones for several reasons, such as: (i) improved aesthetic impact, (ii) better biocompatibility and (iii) better osteointegration. Nevertheless, fully ceramic implants exhibit serious mechanical and clinical drawbacks, chiefly brittleness and impossibility of post-implant position adjustments. In this paper we propose the novel approach of using a metal-based system, consisting of metallic Zr, for the bulk of the implant and an electrochemically grown zirconia coating, ensuring contact of the ceramic with the biological environment and isolation from the underlying metal. This solution combines the outstanding mechanical properties of the metal in the bulk with the optimal biochemical properties exclusively where they are needed: at the surface. The present paper-focussed on the electrochemical behaviour of the proposed system at the implant-wound and implant-growing bone interface-reports a time-dependent electrochemical corrosion study of zirconia-coated zirconium, performed in the following ways: (i) exposure and measurements in SBF (simulating the inorganic part of human plasma, relevant to wound chemistry), (ii) exposure and measurements in SBF with added glycine (the simplest, ubiquitous amino acid found in proteins), (iii) exposure in SBF with added glycine and measurements in SBF. Electrochemical impedance spectra were measured and interpreted with the equivalent-circuit approach, yielding estimates of the time-variation of the oxide film thickness and resistance were estimated. FT-IR, Surface Raman and VIS reflectance spectroscopies were used to characterise the surface before and after the exposure to SBF solutions. Spectroelectrochemical measurements revealed an higher corrosion resistance of the oxide films formed on Zr in the presence of glycine in the SBF matrix and a smoother electrode surface.

Quantification of hepatitis C virus (HCV) RNA in a multicenter study: implications for management of HCV genotype 1-infected patients.

Assessment of the viral load in hepatitis C virus (HCV) genotype 1-infected patients is critical before, during, and after antiviral therapy. In patients achieving a rapid virological response at week 4 of treatment, the viral load at the baseline is considered a predictive criterion of a sustained virological response 24 weeks after the discontinuation of treatment. A >or=2-log(10) drop in the viral load at week 12 of treatment (early virological response) triggers the continuation of therapy. We organized a multicenter study (MS) for diagnostic laboratories involved in the quantification of HCV RNA. Commercial assays, including two based on real-time reverse transcription-PCR (TaqMan system), and in-house methods, were used by the 61 participants. The overall reproducibility of the commercial quantitative nucleic acid amplification techniques (qNAT) was acceptable. As the intermethod variability among commercial qNAT for HCV RNA was still present, the manufacturers of these test kits should join efforts to harmonize the means of quantification of HCV RNA. This study also shows that caution should be exercised when the baseline viral load is evaluated and when the 2-log(10) reduction after 12 weeks of therapy is interpreted. Finally, this MS confirms the higher sensitivity of the commercial qNAT based on the TaqMan system, making them the elective assays for the monitoring of therapy.