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The synthesis of novel catalysts for the oxygen reduction reaction, by means of a fast one-pot microwave-assisted procedure, is reported herein and deeply explained. In particular, the important role of doping atoms, like sulfur and nitrogen, in Fe 2 O 3 -reduced graphene oxide nanocomposites is described to address the modification of catalytic performance. The presence of dopants is confirmed by X-ray Photoelectron Spectroscopy analysis, while the integration of iron oxide nanoparticles, by means of decoration of the graphene structure, is corroborated by electron microscopy, which also confirms that there is no damage to the graphene sheets induced by the synthesis procedure. The electrochemical characterizations put in evidence the synergistic catalysis effects of dopant atoms with Fe 2 O 3 and, in particular, the importance of sulfur introduction into the graphene lattice. Catalytic performance of as-prepared materials toward oxygen reduction shows values close to the Pt/C reference material, commonly used for fuel cell and metal-air battery applications., Competing Interests: The authors declare no conflicts of interest.

In the past few years, due to the Covid-19 pandemic, the interest towards textiles with antimicrobial functionalities faced a significant boost. This study proposes a rapid and convenient method, in terms of reactants and equipment, for fabricating antimicrobial coatings on textiles. Through the electroless silver plating reaction, silver coatings were successfully applied on cotton and polyester, rapidly and at room temperature. Functionalized samples were characterized by morphological (optical and scanning electron microscopies) and chemical tests (X-ray photoelectron spectroscopy, XPS) to investigate the nature of the silver coating. Although distinct nanoparticles did not form, XPS analysis detected the presence of silver, which resulted in an increased surface roughness and hydrophobicity of both cotton and polyester textiles. Ag-coated samples exhibited approximately 80% biocompatibility with murine L929 fibroblasts or human HaCaT cells, and strong antibacterial properties against Escherichia coli in direct contact tests. In antiviral experiments with SARS-CoV-2 virus, treated cotton showed a 100% viral reduction in 30 min, while polyester achieved 100% reduction in 1 h. With a human norovirus surrogate, the Feline Calicivirus, both treated textiles have a faster antiviral response, with more than 60% viral reduction after 5 min, while achieving a 100% reduction in 1 h. In conclusion, this study presents a fast, efficient, and low-cost solution for producing antimicrobial textiles with broad applications in medical and healthcare scenarios., Competing Interests: Declaration of conflicting interestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Metasurfaces have garnered increasing research interest in recent years due to their remarkable advantages, such as efficient miniaturization and novel functionalities compared to traditional optical elements such as lenses and filters. These advantages have facilitated their rapid commercial deployment. Recent advancements in nanofabrication have enabled the reduction of optical metasurface dimensions to the nanometer scale, expanding their capabilities to cover visible wavelengths. However, the pursuit of large-scale manufacturing of metasurfaces with customizable functions presents challenges in controlling the dimensions and composition of the constituent dielectric materials. To address these challenges, the combination of block copolymer (BCP) self-assembly and sequential infiltration synthesis (SIS), offers an alternative for fabrication of high-resolution dielectric nanostructures with tailored composition and optical functionalities. However, the absence of metrological techniques capable of providing precise and reliable characterization of the refractive index of dielectric nanostructures persists. This study introduces a hybrid metrology strategy that integrates complementary synchrotron-based traceable X-ray techniques to achieve comprehensive material characterization for the determination of the refractive index on the nanoscale. To establish correlations between material functionality and their underlying chemical, compositional and dimensional properties, TiO 2 nanostructures model systems were fabricated by SIS of BCPs. The results from synchrotron-based analyses were integrated into physical models, serving as a validation scheme for laboratory-scale measurements to determine effective refractive indices of the nanoscale dielectric materials.

Face masks can filter droplets containing viruses and bacteria minimizing the transmission and spread of respiratory pathogens but are also an indirect source of microbes transmission. A novel antibacterial and antiviral Ag-coated polypropylene surgical mask obtained through the in situ and one-step deposition of metallic silver nanoparticles, synthesized by silver mirror reaction combined with sonication or agitation methods, is proposed in this study. SEM analysis shows Ag nanoparticles fused together in a continuous and dense layer for the coating obtained by sonication, whereas individual Ag nanoparticles around 150 nm were obtained combining the silver mirror reaction with agitation. EDX, XRD and XPS confirm the presence of metallic Ag in both coatings and also oxidized Ag in samples by agitation. A higher amount of Ag nanoparticles is deposited on samples by sonication, as calculated by TGA. Further, both coatings are biocompatible and show antibacterial properties: coating by sonication caused 24 % and 40 % of bacterial reduction while coating by agitation 48 % and 96 % against S. aureus and E. coli, respectively. At 1 min of contact with SARS-CoV-2, the coating by agitation has an antiviral capacity of 75 % against 24 % of the one by sonication. At 1 h, both coatings achieve 100 % of viral inhibition. Nonetheless, larger samples could be produced only through the silver mirror reaction combined with agitation, preserving the integrity of the mask. In conclusion, the silver-coated mask produced by silver mirror reaction combined with agitation is scalable, has excellent physico-chemical characteristics as well as significant biological properties, with higher antimicrobial activities, providing additional protection and preventing the indirect transmission of pathogens., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Highly efficient, separable, and stable magnetic iron-based-photocatalysts produced from ultra-stable Y (USY) zeolite were applied, for the first time, to the photo-Fenton removal of phenol under solar light. USY Zeolite with a Si/Al molar ratio of 385 was impregnated under vacuum with an aqueous solution of Fe 2+ ions and thermally treated (500-750 °C) in a reducing atmosphere. Three catalysts, Fe-USY500°C-2h, Fe-USY600°C-2h and Fe-USY750°C-2h, containing different amounts of reduced iron species entrapped in the zeolitic matrix, were obtained. The catalysts were thoroughly characterized by absorption spectrometry, X-ray powder diffraction with synchrotron source, followed by Rietveld analysis, X-ray photoelectron spectroscopy, N 2 adsorption/desorption at -196 °C, high-resolution transmission electron microscopy and magnetic measurements at room temperature. The catalytic activity was evaluated in a recirculating batch photoreactor irradiated by solar light with online analysis of evolved CO 2 . Photo-Fenton results showed that the catalyst obtained by thermal treatment at 500 °C for 2 h under a reducing atmosphere (FeUSY-500°C-2h) was able to completely mineralize phenol in 120 min of irradiation time at pH = 4 owing to the presence of a higher content of entrapped nano-sized magnetite particles. The latter promotes the generation of hydroxyl radicals in a more efficient way than the Fe-USY catalysts prepared at 600 and 750 °C because of the higher Fe 3 O 4 content in ultra-stable Y zeolite treated at 500 °C. The FeUSY-500°C-2h catalyst was recovered from the treated water through magnetic separation and reused five times without any significant worsening of phenol mineralization performances. The characterization of the FeUSY-500°C-2h after the photo-Fenton process demonstrated that it was perfectly stable during the reaction. The optimized catalyst was also effective in the mineralization of phenol in tap water. Finally, a possible photo-Fenton mechanism for phenol mineralization was assessed based on experimental tests carried out in the presence of scavenger molecules, demonstrating that hydroxyl radicals play a major role., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: The containment measures linked to the COVID-19 pandemic negatively affected the phyco-physical well-being of the population, especially older adults with neurocognitive disorders (NCDs). This study aims to evaluate whether the frailty of NCD patients was associated with different changes in multiple health domains, in particular in relation to loneliness and social isolation, pre- and post-lockdown., Materials and Methods: Patients were recruited from 10 Italian Centers for Cognitive Disorders and Dementia. Data were collected in the pre-pandemic period (T0), during the pandemic lockdown (T1), and 6-9 months post-lockdown (T2). The UCLA Loneliness Scale-3, Activities of Daily Living (ADL), Instrumental ADL (IADL), Mini-Mental State Examination, and Neuropsychiatric Inventory (NPI) were administered. Caregivers' burden was also tested. Patients were categorized as non-frail, pre-frail, and frail according to the Fatigue, Resistance, Ambulation, Illness, and Loss of Weight scale., Results: The sample included 165 subjects (61.9% women, mean age 79.5 ± 4.9 years). In the whole sample, the ADL, IADL, and NPI scores significantly declined between T0 and T2. There were no significative variations in functional and cognitive domains between the frail groups. During lockdown we recorded higher Depression Anxiety Stress Scales and Perceived Stress Scale scores in frail people. In multivariable logistic regression, frailty was associated with an increase in social isolation, and a loss of IADL., Conclusions: We observed a global deterioration in functional and neuro-psychiatric domains irrespective of the degree of frailty. Frailty was associated with the worsening of social isolation during lockdown. Frail patients and their caregivers seemed to experience more anxiety and stress disorders during SARS-CoV-2 pandemic., (© 2023 The Authors. Psychogeriatrics published by John Wiley & Sons Australia, Ltd on behalf of Japanese Psychogeriatric Society.)

The development of efficient CO 2 capture and utilization technologies driven by renewable energy sources is mandatory to reduce the impact of climate change. Herein, seven imidazolium-based ionic liquids (ILs) with different anions and cations were tested as catholytes for the CO 2 electrocatalytic reduction to CO over Ag electrode. Relevant activity and stability, but different selectivities for CO 2 reduction or the side H 2 evolution were observed. Density functional theory results show that depending on the IL anions the CO 2 is captured or converted. Acetate anions (being strong Lewis bases) enhance CO 2 capture and H 2 evolution, while fluorinated anions (being weaker Lewis bases) favour the CO 2 electroreduction. Differently from the hydrolytically unstable 1-butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-Methylimidazolium Triflate was the most promising IL, showing the highest Faradaic efficiency to CO (>95%), and up to 8 h of stable operation at high current rates (-20 mA & -60 mA), which opens the way for a prospective process scale-up., (© 2023. The Author(s).)

The sequential infiltration synthesis (SIS) of inorganic materials in nanostructured block copolymer templates has rapidly progressed in the last few years to develop functional nanomaterials with controllable properties. To assist this rapid evolution, expanding the capabilities of nondestructive methods for quantitative characterization of the materials properties is required. In this paper, we characterize the SIS process on three model polymers with different infiltration profiles through ex situ quantification by reference-free grazing incidence X-ray fluorescence. More qualitative depth distribution results were validated by means of X-ray photoelectron spectroscopy and scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The direct hydrogenation of CO 2 into dimethyl-ether (DME) has been studied in the presence of ferrierite-based CuZnZr hybrid catalysts. The samples were synthetized with three different techniques and two oxides/zeolite mass ratios. All the samples (calcined and spent) were properly characterized with different physico-chemical techniques for determining the textural and morphological nature of the catalytic surface. The experimental campaign was carried out in a fixed bed reactor at 2.5 MPa and stoichiometric H 2 /CO 2 molar ratio, by varying both the reaction temperature (200-300 °C) and the spatial velocity (6.7-20.0 NL∙g cat -1 ∙h -1 ). Activity tests evidenced a superior activity of catalysts at a higher oxides/zeolite weight ratio, with a maximum DME yield as high as 4.5% (58.9 mg DME ∙g cat -1 ∙h -1 ) exhibited by the sample prepared by gel-oxalate coprecipitation. At lower oxide/zeolite mass ratios, the catalysts prepared by impregnation and coprecipitation exhibited comparable DME productivity, whereas the physically mixed sample showed a high activity in CO 2 hydrogenation but a low selectivity toward methanol and DME, ascribed to a minor synergy between the metal-oxide sites and the acid sites of the zeolite. Durability tests highlighted a progressive loss in activity with time on stream, mainly associated to the detrimental modifications under the adopted experimental conditions.

This study presents the immobilization with aldehyde groups (glyoxyl carbon felt) of alcohol dehydrogenase (ADH) and formate dehydrogenase (FDH) on carbon-felt-based electrodes. The compatibility of the immobilization method with the electrochemical application was studied with the ADH bioelectrode. The electrochemical regeneration process of nicotinamide adenine dinucleotide in its oxidized form (NAD + ), on a carbon felt surface, has been deeply studied with tests performed at different electrical potentials. By applying a potential of 0.4 V versus Ag/AgCl electrode, a good compromise between NAD + regeneration and energy consumption was observed. The effectiveness of the regeneration of NAD + was confirmed by electrochemical oxidation of ethanol catalyzed by ADH in the presence of NADH, which is the no active form of the cofactor for this reaction. Good reusability was observed by using ADH immobilized on glyoxyl functionalized carbon felt with a residual activity higher than 60 % after 3 batches., (© 2022 The Authors. Published by Wiley-VCH GmbH.)

Self-assembled monolayers (SAM) of 7-mercapto-4-methylcoumarin (MMC) on a flat gold surface were studied by molecular dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoelectron spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidence for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the bennet acceptance ratio method, based again on MD simulations. The monolayer density was also measured with GIXRF, which provided the absolute quantification of the number of sulfur atoms in a dense self-assembled monolayer (SAM) on flat gold surfaces. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer. The comparison of theoretical and experimental SAM densities, and the XPS analysis strongly support the picture of a monolayer formed by chemisorbed, dissociated thiyls.

Detection of Zn(II) in oil-polluted seawater via square-wave anodic stripping voltammetry (SW-ASV) utilizing thin gold electrodes sputtered onto nanoporous poly(acrylic acid)-grafted-poly(vinylidene difluoride) (PAA-g-PVDF) membrane is herein reported. Prior to SW-ASV, PAA grafted nanopores demonstrated to efficiently trap Zn(II) ions at open circuit. This passive adsorption followed a Langmuir law. An affinity constant of 1.41 L [Formula: see text]mol[Formula: see text] and a maximum Zn(II) adsorbed mass q[Formula: see text] of 1.21 [Formula: see text]mol g[Formula: see text] were found. Applied SW-ASV protocol implied an accumulation step (- 1.2 V for 120 s) followed by a stripping step (- 1.2 to 1 V; 25 Hz; step: 4 mV; amplitude: 25 mV; acetate buffer (pH 5.5)). It revealed a Zn redox potential at - 0.8 V (Ag/AgCl pseudo-reference). Multiple measurements in synthetic waters close to the composition of production waters exhibited a decreasing precision with the number of readings R (1.65[Formula: see text] (R = 2) and 6.56[Formula: see text] (R = 3)). These membrane-electrodes should be used as disposable. The intra-batch mean precision was 14[Formula: see text] (n = 3) while inter-batches precision was 20[Formula: see text] (n = 15). Linear and linear-log calibrations allow exploitation of Zn(II) concentrations ranging from 10 to 500 [Formula: see text]g L[Formula: see text] and 100 to 1000 [Formula: see text]g L[Formula: see text] respectively. The LOD was 4.2 [Formula: see text]g L[Formula: see text] (3S/N). Thanks to obtained calibration, a detected Zn(II) content of 1 ppm in a raw production water from North Sea oil platform was determined., (© 2022. The Author(s).)

Carbon monoxide (CO) and formic acid (HCOOH) are suggested to be the most convenient products from electrochemical reduction of CO 2 according to techno-economic analysis. To date, tremendous advances have been achieved in the development of catalysts and processes, which make this research topic even more interesting to both academic and industrial sectors. In this work, we report nanostructured Cu-Al materials that are able to convert CO 2 to CO and HCOOH with good efficiency. The catalysts are synthesized via a green microwave-assisted solvothermal route, and are composed of Cu 2 O crystals modified by Al. In KHCO 3 electrolyte, these catalysts can selectively convert CO 2 to HCOOH and syngas with H 2 /CO ratios between 1 and 2 approaching one unit faradaic efficiency in a wide potential range. Good current densities of 67 and 130 mA cm -2 are obtained at -1.0 V and -1.3 V vs. reversible hydrogen electrode (RHE), respectively. When switching the electrolyte to KOH, a significant selectivity up to 20% is observed for C 2 H 4 formation, and the current densities achieve 146 and 222 mA cm -2  at -1.0 V and -1.3 V vs. RHE, respectively. Hence, the choice of electrolyte is critically important as that of catalyst in order to obtain targeted products at industrially relevant current densities., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Zeng, Castellino, Fontana, Sacco, Monti, Chiodoni and Pirri.)

The development of efficient catalysts is one of the main challenges in CO 2 conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu +1 were studied to convert CO 2 via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO 2 reduction to reduce the kinetic barrier and enhance C-C coupling to obtain C 2+ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·g cat -1 ·h -1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C 1 products like formate and methanol. During CO 2 hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·g cat -1 ·h -1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu 1+ /Cu 0 interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu 0 and crystalline ZnO prevailed under CO 2 hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu 0 catalyst surface in the TC process than in the Cu 1+ present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu 1+ + Cu 0 species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C 2+ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO 2 conversion products.

In this study, we report on the facile synthesis of a novel electrocatalysts for the oxygen reduction reaction (ORR), based on reduced graphene oxide (RGO), functionalized with metallic and non-metallic elements. In particular, thanks to a fast one-pot microwave-assisted procedure, we induced, in the RGO graphene lattice, a combined doping with nitrogen and sulphur, and the simultaneous decoration with antimony oxide nanocrystals. The multi-doped-decorated material shows enhanced catalytic performance towards ORR, with respect to common nitrogen- or sulphur-doped carbon-based materials. The presence of co-doping is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy analysis. The detailed electrochemical characterization shows the simultaneous effects of dopant atoms on the catalytic behavior. In particular, the importance of nitrogen and sulphur atoms in driving the oxygen absorption, together with the role of antimony in enhancing the electrochemical performance toward the ORR, are discussed.

Inspired by the knowledge of the thermocatalytic CO 2 reduction process, novel nanocrystalline CuZnAl-oxide based catalysts with pyramidal mesoporous structures are here proposed for the CO 2 electrochemical reduction under ambient conditions. The XPS analyses revealed that the co-presence of ZnO and Al 2 O 3 into the Cu-based catalyst stabilize the CuO crystalline structure and introduce basic sites on the ternary as-synthesized catalyst. In contrast, the as-prepared CuZn- and Cu-based materials contain a higher amount of superficial Cu 0 and Cu 1+ species. The CuZnAl-catalyst exhibited enhanced catalytic performance for the CO and H 2 production, reaching a Faradaic efficiency (FE) towards syngas of almost 95% at -0.89 V vs. RHE and a remarkable current density of up to 90 mA cm -2 for the CO 2 reduction at -2.4 V vs. RHE. The physico-chemical characterizations confirmed that the pyramidal mesoporous structure of this material, which is constituted by a high pore volume and small CuO crystals, plays a fundamental role in its low diffusional mass-transfer resistance. The CO-productivity on the CuZnAl-catalyst increased at more negative applied potentials, leading to the production of syngas with a tunable H 2 /CO ratio (from 2 to 7), depending on the applied potential. These results pave the way to substitute state-of-the-art noble metals (e.g., Ag, Au) with this abundant and cost-effective catalyst to produce syngas. Moreover, the post-reaction analyses demonstrated the stabilization of Cu 2 O species, avoiding its complete reduction to Cu 0 under the CO 2 electroreduction conditions.

The electrocatalytic reduction of CO 2 into useful fuels, exploiting rationally designed, inexpensive, active, and selective catalysts, produced through easy, quick, and scalable routes, represents a promising approach to face today's climate challenges and energy crisis. This work presents a facile strategy for the preparation of doped SnO 2 as an efficient electrocatalyst for the CO 2 reduction reaction to formic acid and carbon monoxide. Zn or Ti doping was introduced into a mesoporous SnO 2 matrix via wet impregnation and atomic layer deposition. It was found that doping of SnO 2 generates an increased amount of oxygen vacancies, which are believed to contribute to the CO 2 conversion efficiency, and among others, Zn wet impregnation resulted the most efficient process, as confirmed by X-ray photoelectron spectroscopy analysis. Electrochemical characterization and active surface area evaluation show an increase of availability of surface active sites. In particular, the introduction of Zn elemental doping results in enhanced performance for formic acid formation, in comparison to un-doped SnO 2 and other doped SnO 2 catalysts. At -0.99 V versus reversible hydrogen electrode, the total faradaic efficiency for CO 2 conversion reaches 80%, while the partial current density is 10.3 mA cm -2 . These represent a 10% and a threefold increases for faradaic efficiency and current density, respectively, with respect to the reference un-doped sample. The enhancement of these characteristics relates to the improved charge transfer and conductivity with respect to bare SnO 2 .

A catalyst plays a key role in the electrochemical reduction of CO 2 to valuable chemicals and fuels. Hence, the development of efficient and inexpensive catalysts has attracted great interest from both the academic and industrial communities. In this work, low-cost catalysts coupling Cu and Zn are designed and prepared with a green microwave-assisted route. The Cu to Zn ratio in the catalysts can be easily tuned by adjusting the precursor solutions. The obtained Cu-Zn catalysts are mainly composed of polycrystalline Cu particles and monocrystalline ZnO nanoparticles. The electrodes with optimized Cu-Zn catalysts show enhanced CO production rates of approximately 200 μmol h -1  cm -2 with respect to those with a monometallic Cu or ZnO catalyst under the same applied potential. At the bimetallic electrodes, ZnO-derived active sites are selective for CO formation and highly conductive Cu favors electron transport in the catalyst layer as well as charge transfer at the electrode/electrolyte interface., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The light responsivity of ortho-nitrobenzyl esters (o-NBE) is exploited to inscribe µ-scale 2.5D patterns in thiol-ene networks by direct laser writing. For this purpose, a multifunctional thiol and a photosensitive alkene with an o-NBE chromophore are cured upon visible light exposure without inducing a premature photocleavage of the o-NBE links. Once the network is formed, a laser beam source with a wavelength of 375 nm is used for selectively inducing the photocleavage reaction of the o-NBE groups. Positive tone patterns are directly inscribed onto the sample surface without the requirement of a subsequent development step (removing soluble species in an appropriate organic solvent). Along with the realization of dry-developable micropatterns, the chemical surface composition of the exposed areas can be conveniently adjusted since different domains with a tailored content of carboxylic groups are obtained simply by modulating the laser energy dose. In a following step, those are activated and exploited as anchor points for attaching an Alexa-546 conjugated Protein A. Thus, the laser writable thiol-ene networks do not only provide a convenient method for the fabrication of positive tone patterns but also open future prospectives for a wide range of biosensing applications., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Microgreens are gaining increasing interest as a potential functional food due to their relevant contents of micronutrients and bioactive compounds, including carotenoids. Nevertheless, the analysis of carotenoids is inherently difficult, due to their thermal and chemical susceptibility, as well as to their varying polarity. From this point of view, extraction is the most critical step, compared to chromatographic separation and detection. Thus, the reliability of data on carotenoids should be guaranteed by a constant focus on analytical issues, with appropriate adaptations to each sample matrix. In this research, a specific extraction procedure for the analysis of carotenoids in microgreens was developed. Solvent composition, extraction time, solvent/sample ratio, and repeated extractions were evaluated. The obtained protocol showed recovery of 97.2%, limits of quantitation of 5.2 μg·g -1 for lutein and 15.9 μg·g -1 for β-carotene, as well as intra-day mean repeatability of 5.7% and inter-day mean repeatability of 4.7%.

Nanostructured materials possess unique physical-chemical characteristics and have attracted much attention, among others, in the field of energy conversion and storage devices, for the possibility to exploit both their bulk and surface properties, enabling enhanced electron and ion transport, fast diffusion of electrolytes, and consequently high efficiency in the electrochemical processes. In particular, titanium dioxide received great attention, both in the form of amorphous or crystalline material for these applications, due to the large variety of nanostructures in which it can be obtained. In this paper, a comparison of the performance of titanium dioxide prepared through the oxidation of Ti foils in hydrogen peroxide is reported. In particular, two thermal treatments have been compared. One, at 150 °C in Ar, which serves to remove the residual hydrogen peroxide, and the second, at 450 °C in air. The material, after the treatment at 150 °C, results to be not stoichiometric and amorphous, while the treatment at 450 °C provide TiO 2 in the anatase form. It turns out that not-stoichiometric TiO 2 results to be a highly stable material, being a promising candidate for applications as high power Li-ion batteries, while the anatase TiO 2 shows lower cyclability, but it is still promising for energy-storage devices., Competing Interests: The authors declare no conflict of interest.

This paper illustrates a methodology to get a reliable estimation of the local wave properties, based on the reconstruction of the motion of a moving sailboat by means of GNSS receivers installed on board and an original kinematic positioning approach. The wave parameters reconstruction may be used for many useful practical purposes, e.g. to improve of autopilots, for real-time control systems of ships, to analyze and improve the performance of race sailboats, and to estimate the local properties of the waves. A Class 40 oceanic vessel (ECO40) left from the port of "Riva di Traiano" located close to Rome (Italy) on 19 October 2014 to perform a non-stop sailing alone around the world in energy and food self-sufficiency. The proposed system was installed on ECO40 and the proposed method was applied to estimate the wave properties during a storm in the Western Mediterranean Sea. The results compared against two sets of hindcast data and wave buoy records demonstrated the reliability of the method.

Herein we report a novel, easy, fast and reliable microwave-assisted synthesis procedure for the preparation of colloidal zinc oxide nanocrystals (ZnO NCs) optimized for biological applications. ZnO NCs are also prepared by a conventional solvo-thermal approach and the properties of the two families of NCs are compared and discussed. All of the NCs are fully characterized in terms of morphological analysis, crystalline structure, chemical composition and optical properties, both as pristine nanomaterials or after amino-propyl group functionalization. Compared to the conventional approach, the novel microwave-derived ZnO NCs demonstrate outstanding colloidal stability in ethanol and water with long shelf-life. Furthermore, together with their more uniform size, shape and chemical surface properties, this long-term colloidal stability also contributes to the highly reproducible data in terms of biocompatibility. Actually, a significantly different biological behavior of the microwave-synthesized ZnO NCs is reported with respect to NCs prepared by the conventional synthesis procedure. In particular, consistent cytotoxicity and highly reproducible cell uptake toward KB cancer cells are measured with the use of microwave-synthesized ZnO NCs, in contrast to the non-reproducible and scattered data obtained with the conventionally-synthesized ones. Thus, we demonstrate how the synthetic route and, as a consequence, the control over all the nanomaterial properties are prominent points to be considered when dealing with the biological world for the achievement of reproducible and reliable results, and how the use of commercially-available and under-characterized nanomaterials should be discouraged in this view., Competing Interests: There are no conflicts to declare.

Besides the variety of colours and flavours, microgreens show interesting nutritional properties, mainly regarding their contents of mineral nutrients and bioactive compounds. To date, the literature has prevalently focused on the individual nutritional features of microgreens usually belonging to Brassicaceae. The present study reports an articulated nutritional profile of six genotypes of microgreens, belonging to three species and two families: chicory (Cichorium intybus L., Puglia's local variety 'Molfetta', CM, and cultivar 'Italico a costa rossa', CR) and lettuce (Lactuca sativa L. Group crispa, cultivar 'Bionda da taglio', LB, and 'Trocadero', LT), from Asteraceae; and broccoli (Brassica oleracea L. Group italica Plenk, Puglia's local variety 'Mugnuli', BM, and cultivar 'Natalino', BN) from Brassicaceae. All the microgreens, except LB, can be considered good sources of Ca, whilst LT and CM also showed considerable amounts of K. As regards bioactive compounds, Brassica microgreens were the richest in phenolic antioxidants. The microgreens also presented higher amounts of α-tocopherol and carotenoids compared to mature vegetables. In particular, broccoli microgreens and LB showed the highest amounts of vitamin E, while Asteraceae microgreens presented the highest levels of carotenoids. Due to their delicate tissues, fresh cut microgreens showed a shelf life not exceeding ten days at 5 °C. The results obtained highlight the possibility to exploit genetic biodiversity in order to obtain tailored microgreens with the desired nutritional profiles, with particular regard to mineral nutrients and bioactive compounds. Appropriate pre- and post-harvest strategies should be developed, so as to allow microgreens to retain as long as possible their nutritional value.

In the present work, the activity of Ce and Er-doped ZrO 2 nanopowders for sun-driven photocatalytic water oxidation has been investigated. ZrO 2 powders with tunable amounts of tetragonal, monoclinic and cubic polymorphs have been synthesized by introducing Ce and Er (from 0.5 to 10 mol % on an oxide basis) through hydrothermal method. The aim of this work is to investigate the role of rare earth (RE) ions rich of electrons (Er 3+ ) and with entirely empty levels (Ce 4+ ) in the ZrO 2 matrix for the sun-driven photocatalytic water oxidation reaction. The samples have been characterized by means of UV-Vis spectroscopy, X-Ray diffraction (XRD), N 2 adsorption, X-ray photoelectron spectrophotometry (XPS) and transmission electronic microscopy (TEM) with energy dispersive spectroscopy (EDS). With respect to the bare ZrO 2 mainly containing monoclinic (m-) phase, an increasing amount of rare-earth (RE) dopant was found to improve the specific BET surface area and to stabilize the tetragonal (t-) or cubic (c-) polymorphs of ZrO 2 at room temperature. XRD data confirmed that dopants were mainly inserted in the t-ZrO 2 phase. The photocatalytic O 2 evolution from water under AM 1.5 G simulated sunlight illumination of the prepared samples have been correlated with their optical, structural and chemical properties. The effect of the dopant concentration on the chemical-physical and photocatalytic properties of the Er- and Ce-doped ZrO 2 materials was elucidated. The samples with 5% of RE oxide were the most active, i.e., three times more than pure zirconia. Their superior photocatalytic activity was found to be mainly correlated to two factors: (i) an optimal surface concentration of RE ions of about 3.7%, which increased charge carriers separation in the photocatalysts surface due more superficial defects of the t-ZrO 2 and a higher surface area, thus enhancing the reaction kinetics, (ii) a controlled amount of monoclinic vs. tetragonal (or cubic) polymorphs of zirconia with an optimum ratio of about 70/30 of t-ZrO 2 /m-ZrO 2 . Instead, the increased ability of the RE-doped ZrO 2 to harvest visible light was found to have a secondary role on the photocatalytic activity of the Ce-doped ZrO 2 material.

Chronic kidney disease represents a global problem together with other so-called 'lifestyle-related diseases'. Unlike the healthy population, for the patients with impaired kidney function, it is of course prudent to recommend a restriction of high-potassium foods. Thus, it is suggested to limit the consumption of vegetables, because they generally contain high concentrations of potassium. At the same time, a lower consumption of vegetables reduces the intake of healthy compounds such as vitamins, fibers, and antioxidants, which also reduces the vegetables' potential benefit in chronic kidney disease patients. Microgreens are an emerging class of specialty crop that represent a nutritious and refined food. In this study, for the first time, some chicory (local variety 'Molfetta' and cultivar 'Italico a costa rossa') and lettuce (cultivar 'Bionda da taglio') genotypes were grown using a hydroponic system with different potassium (K) levels (0, 29.1, 58.4, and 117 mg L -1 ) in order to produce microgreens with a low potassium content. The crop performances, cations content, proximate composition, and antioxidant activity were analyzed. Independent of the genotype, the K content in the microgreens was successfully reduced using a nutrient solution (NS), without K or with 29.1 mg K L -1 , which supplied between 103 and 129 mg of K 100 g -1 FW (about 7.7⁻8.6% of the K daily intake that was recommended for the patients that were affected by chronic kidney disease). Whereas, 100 g of microgreens that were grown by using an NS with 58.4 or 117 mg K L -1 supply between 225 and 250 mg of K (about 15.8⁻16.5% of the K daily intake recommended for patients affected by chronic kidney disease). No differences were observed in terms of the shoot height, dry matter, proximate composition, and visual quality. A slightly lower yield was observed using an NS with a K concentration.

Manganese oxides (Mn x O y ) are considered as a promising catalyst alternative to platinum in fuel cell applications. In fact, a proper catalyst is needed in order to facilitate the oxygen reduction reaction (ORR) at the cathode, and platinum is considered the best material due to its low overpotential for this reaction. Contrary to platinum, Mn x O y is inexpensive, environmentally friendly and can be shaped into several nanostructures; furthermore, most of them show significant electro-catalytic performance. Several strategies have been carried out in order to increase their efficiency, by preparing light and high-surface area materials. In this framework, nanofibres are among the most promising nanostructures that can be used for this purpose. In this work, a study of the thermal, morphological and catalytic behavior of Mn x O y nanofibres obtained through the electrospinning technique is proposed. Emphasis is given to the thermal evolution of the precursors, proposing a possible crystallization mechanism of the different manganese oxides obtained. It turns out that manganese oxide nanofibres exhibit good catalytic performance for the ORR, comparable to those obtained by using Pt-based catalysts.

Vanadium doped ZnO (VZO) thin films were grown by RF magnetron sputtering, starting from a ZnO:V ceramic target. The crystal structure, chemical composition, electric and piezoelectric properties of the films were investigated either on the as-grown thin films or after a post-deposition rapid thermal annealing (RTA) treatment performed at 600 °C for different lengths of time (1 and 5 min) in an oxygen atmosphere. Substitutional doping of Zn 2+ with V 3+ and V 5+ ions strongly deteriorated the hexagonal wurtzite ZnO structure of the as-grown thin films due to lattice distortion. The resulting slight amorphization led to a poor piezoelectric response and higher resistivity. After the RTA treatment, strong c-axis oriented VZO thin films were obtained, together with a partial conversion of the starting V 3+ ions into V 5+ . The improvement of the crystal structure and the stronger polarity of both V 3+ - O and V 5+ - O chemical bonds, together with the corresponding easier rotation under the application of an external electric field, positively affected the piezoelectric response and increased conductivity. This was confirmed by closed-loop butterfly piezoelectric curves, by a maximum d 33 piezoelectric coefficient of 85 pm·V -1 , and also by ferroelectric switching domains with a well-defined polarization hysteresis curve, featuring a residual polarization of 12.5 μC∙cm -2 ., Competing Interests: The authors declare no competing financial interests.

A hybrid aerogel, composed of MoS 2 sheets of 1T (distorted octahedral) and 2H (trigonal prismatic) phases, finely mixed with few layers of reduced graphene oxide (rGO) and obtained by means of a facile environment-friendly hydrothermal cosynthesis, is proposed as electrode material for supercapacitors. By electrochemical characterizations in three- and two-electrode configurations and symmetric planar devices, unique results have been obtained, with specific capacitance values up to 416 F g -1 and a highly stable capacitance behavior over 50000 charge-discharge cycles. The in-depth morphological and structural characterizations through field emission scanning electron microscopy, Raman, X-ray photoelectron spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller, and transmission electron microscopy analysis provides the proofs of the unique assembly of such 3D structured matrix. The unpacked MoS 2 structure exhibits an excellent distribution of 1T and 2H phase sheets that are highly exposed to interaction with the electrolyte, and so available for surface/near-surface redox reactions, notwithstanding the quite low overall content of MoS 2 embedded in the reduced graphene oxide (rGO) matrix. A comparison with other "more conventional" hybrid rGO-MoX 2 electrochemically active materials, synthesized in the same conditions, is provided to support the outstanding behavior of the cosynthesized rGO-MoS 2 .

A simple and straightforward synthesis was developed to prepare the siloxy-substituted bis(acylphosphane)oxide 4-(trimethoxysilyl)butyl-3-[bis(2,4,6-trimethylbenzoyl)phosphinoyl]-2-methyl-propionate TMESI(2)-BAPO. This new photoinitiator was successfully fixed to glass surfaces. Subsequent irradiation with UV light in the presence of either a partially fluorinated acrylate or a specifically synthesized polysiloxane containing polymerizable acrylate functions allowed the generation of polymer chains which grew from the surface in an efficient radical polymerization process ("grafting-from" procedure). Durable hydrophobic surfaces were prepared which have contact angles between 93° and 95°. The silanization process with the photoinitiator and the grafting process were followed and analyzed with various techniques including high-resolution X-ray photoelectron spectroscopy.

A well-organized immobilization of bio-receptors is a crucial goal in biosensing, especially to achieve high reproducibility, sensitivity and specificity. These requirements are usually attained with a controlled chemical/biochemical functionalization that creates a stable layer on a sensor surface. In this work, a chemical modification protocol for silicon-based surfaces to be applied in biosensing devices is presented. An anhydrous silanization step through 3-aminopropylsilane (APTES), followed by a further derivatization with succinic anhydride (SA), is optimized to generate an ordered flat layer of carboxylic groups. The properties of APTES/SA modified surface were compared with a functionalization in which glutaraldehyde (GA) is used as crosslinker instead of SA, in order to have a comparison with an established and largely applied procedure. Moreover, a functionalization based on the controlled deposition of a plasma polymerized acrylic acid (PPAA) thin film was used as a reference for carboxylic reactivity. Advantages and drawbacks of the considered methods are highlighted, through physico-chemical characterizations (OCA, XPS, and AFM) and by means of a functional Protein G/Antibody immunoassay. These analyses reveal that the most homogeneous, reproducible and active surface is achieved by using the optimized APTES/SA coupling., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Plastic smart windows are becoming one of the key elements in view of the fabrication of inexpensive, lightweight electrochromic (EC) devices to be integrated in the new generation of high-energy-efficiency buildings and automotive applications. However, fabricating electrochromic devices on polymer substrates requires a reduction of process temperature, so in this work we focus on the development of a completely room-temperature deposition process aimed at the preparation of ITO-coated polycarbonate (PC) structures acting as transparent and conductive plastic supports. Without providing any substrate heating or surface activation pretreatments of the polymer, different deposition conditions are used for growing indium tin oxide (ITO) thin films by the radiofrequency magnetron sputtering technique. According to the characterization results, the set of optimal deposition parameters is selected to deposit ITO electrodes having high optical transmittance in the visible range (∼90%) together with low sheet resistance (∼8 ohm/sq). The as-prepared ITO/PC structures are then successfully tested as conductive supports for the fabrication of plastic smart windows. To this purpose, tungsten trioxide thin films are deposited by the reactive sputtering technique on the ITO/PC structures, and the resulting single electrode EC devices are characterized by chronoamperometric experiments and cyclic voltammetry. The fast switching response between colored and bleached states, together with the stability and reversibility of their electrochromic behavior after several cycling tests, are considered to be representative of the high quality of the EC film but especially of the ITO electrode. Indeed, even if no adhesion promoters, additional surface activation pretreatments, or substrate heating were used to promote the mechanical adhesion among the electrode and the PC surface, the observed EC response confirmed that the developed materials can be successfully employed for the fabrication of lightweight and inexpensive plastic EC devices.

We report on an easy, fast, eco-friendly, and reliable method for the synthesis of reduced graphene oxide/SnO2 nanocomposite as cathode material for application in microbial fuel cells (MFCs). The material was prepared starting from graphene oxide that has been reduced to graphene during the hydrothermal synthesis of the nanocomposite, carried out in a microwave system. Structural and morphological characterizations evidenced the formation of nanocomposite sheets, with SnO2 crystals of few nanometers integrated in the graphene matrix. Physico-chemical analysis revealed the formation of SnO2 nanoparticles, as well as the functionalization of the graphene by the presence of nitrogen atoms. Electrochemical characterizations put in evidence the ability of such composite to exploit a cocatalysis mechanism for the oxygen reduction reaction, provided by the presence of both SnO2 and nitrogen. In addition, the novel composite catalyst was successfully employed as cathode in seawater-based MFCs, giving electrical performances comparable to those of reference devices employing Pt as catalyst.

Bismuth oxide thin films were obtained by the spray pyrolysis method using bismuth acetate as the precursor salt. The films were characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), UV-vis diffuse reflectance, X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). The XRD patterns indicated that the pure β phase is obtained at 450 °C and was also confirmed by FTIR. This phase presents a nanoplate morphology which is adequate for the photocatalytic reactions. Moreover, the band gap value was 2.6 eV indicating a good capacity of visible light absorption. The photocatalytic degradation of the Methyl Orange (MO) dye was pH dependent, an acid solution being easier to degrade. However, the Bi2O3 films were easily converted into BiOCl when they were in contact with a solution containing HCl. In order to preserve the β-Bi2O3 phase, the Acid Blue 113 dye with its natural pH of 8 was used to evaluate the stability of the photocatalytic activity after five degradation cycles. The photoactivity was practically stable indicating a good performance of the material. This encouraged us to test the films in a continuous flow solar reactor prototype for the degradation of the dye solution using sunlight radiation exclusively. The good performance of the β-Bi2O3 films indicates that they can be used for sustainable water treatment applications.

Since hundreds of studies on photoanodes and cathodes show that the electrode/electrolyte interfaces represent a key aspect at the base of dye-sensitized solar cell (DSSC) performances, it is reported here that these interfaces can be managed by a smart design of the spatial composition of quasi-solid electrolytes. By means of a cheap, rapid, and green process of photoinduced polymerization, composition-tailored polymer electrolyte membranes (PEMs) with siloxane-enriched surfaces are prepared, and their properties are thoroughly described. When assembled in DSSCs, the interfacial action promoted by the composition-tailored PEMs enhances the photocurrent and fill factor values, thus increasing the global photovoltaic conversion efficiency with respect to the non-modified PEMs. Moreover, the presence of the siloxane-chain-enriched surface increases the hydrophobicity and reduces the water vapor permeation into the device, thus enhancing the cell's durability., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel aldehyde-bearing trithiocarbonate has been synthesized and reacted with carbon nanostructures with different dimensionalities (nanotubes, fullerenes, graphite). The decoration of these carbon nanostructures with trithiocarbonate moieties should provide a powerful tool for the design of advanced carbon nanofillers.

Carboxylic functionalization (-COOH groups) of carbon nanotubes is known to improve their dispersion properties and increase the electrical conductivity of carbon-nanotube-polymer nanocomposites. We have studied experimentally the effects of this type of functionalization on the thermal conductivity of the nanocomposites. It was found that while even small quantities of carbon nanotubes (~1 wt %) can increase the electrical conductivity, a larger loading fraction (~3 wt %) is required to enhance the thermal conductivity of nanocomposites. Functionalized multi-wall carbon nanotubes performed the best as filler material leading to a simultaneous improvement of the electrical and thermal properties of the composites. Functionalization of the single-wall carbon nanotubes reduced the thermal conductivity enhancement. The observed trends were explained by the fact that while surface functionalization increases the coupling between carbon nanotube and polymer matrix, it also leads to formation of defects, which impede the acoustic phonon transport in the single-wall carbon nanotubes. The obtained results are important for applications of carbon nanotubes and graphene flakes as fillers for improving thermal, electrical and mechanical properties of composites.

The vast majority of stent thrombosis occurs in the acute and sub-acute phases and is more common in patients with acute coronary syndromes, due to the thrombotic milieu where stent struts are positioned. Stent thrombosis is likely due to incomplete tissue coverage of metallic stents as the contact between metallic stents and blood elements may lead to platelet adhesion and trigger vessel thrombosis. If a stent is covered after 7 days, the risk that it will be found uncovered at later stages is very low (<1%). In this article, we demonstrate that diamond-like carbon (DLC) coatings, deposited by physical vapour deposition, promote rapid endothelisation of coronary stent devices, with very low platelets activation, reducing thrombotic clots. We relate these behaviours to the surface and bulk material properties of the DLC films, subjected to a comprehensive chemico-physical characterisation using several techniques (X-ray photoelectron spectroscopy, atomic force microscopy, field-emission scanning electron microscope, transmission electron microscopy combined with electron energy loss spectroscopy, Raman and dispersive X-ray spectroscopy). In vivo studies, conducted on 24 pigs, have shown complete endothelisation after 7 days, with no fibrin mesh and with only rare monocytes scattered on the endothelial layer while 30 and 180 days tests have shown reduced inflammatory activation and a complete stabilisation of the vessel healing, with a minimal neointimal proliferation. The integral and permanent DLC film coating improves haemo- and bio-compatibility and leads to an excellent early vessel healing of the stent whilst the extremely thin strut thickness reduces the amount of late neointima and consequently the risk of late restenosis. These data should translate into a reduced acute and sub-acute stent thrombosis.

In this work, we aim to study the hydrogen adsorption in several kinds of carbon nanotubes grown under different process conditions and to correlate the findings with the morphological microstructure and physical properties of these materials. The growth conditions and the behaviour with respect to hydrogen interaction of various carbon nanotubes are discussed, to establish microstructure-process-property relationships. In particular, we have analyzed several types of carbon nanotubes, namely one single-walled and five multi-walled having different tube diameter (due to different deposition techniques and conditions), different defectiveness and submitted to different surface treatments. To better understand the differences among the various samples, they have been investigated using field emission scanning electron microscopy and high resolution transmission electron microscopy for the morphological and structural characteristics, thermo-gravimetric analysis for the sample purity and Brunauer-Emmett-Teller analysis for the surface area. The experimental measurements on the ability of the different types of carbon nanotubes to adsorb and/or releasing hydrogen have been performed at 77 K with a volumetric Sievert analytical tool. Our findings clearly demonstrate a direct correlation between the exposed surface area and adsorbed hydrogen capacity, which confirms their linear relationship observed previously. For instance, single-walled nanotubes with surface area density of approximately 800 m2/g have showed hydrogen storage of approximately 1.7 wt% at a pressure of 35 atm. Adsorption process seems to be perfectly reversible. The adsorption values have been compared with a simple model, in order to evaluate the potentialities for carbon-based nanomaterials in future hydrogen storage applications.

Massive carpets of well packed, vertically aligned and very long multiwall carbon nanotubes were synthesized by an efficient thermal Chemical Vapour Deposition process. Electrical properties of the material were evaluated, both in terms of "global" characteristics (bulk resistivity) and in terms of "local" properties (Scanning Tunnel Spectroscopy measurements) for as-grown and annealed at different temperatures samples. The behaviour of bulk resistivity as a function of temperature was evaluated in the range 3-300 K, with a four-probe technique. The resistivity shows a linear dependence with the square root of temperature in the investigated range. From the electrical analyses, it was found that the quality of the MWNTs was improved by the annealing process, since the resistivity decreases. Heat transport properties were evaluated by the laser flash technique in order to study thermal diffusivity. Moreover high temperature behavior of the specific heat capacity of single and multi-wall carbon nanotubes, was measured up to 800 K with a Differential Scanning Calorimeter.

The present application is based on the use of carbon nanotubes (CNTs) for biomolecular analysis using electrochemiluminescence (ECL) detection technique [1]-[9]. For this purpose we have grown self standing cylinder-shaped blocks of multi-wall CNTs (MWCNTs) by means of a catalytic chemical vapour deposition system, fed by camphor and ferrocene gases. The blocks were subsequently back-contacted and encapsulated into epoxy resin as electrical insulator and sealant, for their use as voltammetric electrodes. A ruthenium-complex solution has been used as ECL label. It has been observed a periodical light emission that lasts for hundreds of cycles, likely due to the CNTs structure. Thanks to a data-processing algorithm which exploits this behavior, the experiments show that it is possible to obtain a great increase in detection limit as compared to the common working metal electrodes (for example Au or Pt).

In this work, we aim to study the hydrogen adsorption in several kinds of carbon nanotubes grown under different process conditions and to correlate the findings with the morphological microstructure and physical properties of these materials. The growth conditions and the behaviour with respect to hydrogen interaction of various carbon nanotubes are discussed, to establish microstructure-process-property relationships. In particular, we have analyzed several types of carbon nanotubes, namely one single-walled and five multi-walled having different tube diameter (due to different deposition techniques and conditions), different defectiveness and submitted to different surface treatments. To better understand the differences among the various samples, they have been investigated using field emission scanning electron microscopy and high resolution transmission electron microscopy for the morphological and structural characteristics, thermo-gravimetric analysis for the sample purity and Brunauer-Emmett-Teller analysis for the surface area. The experimental measurements on the ability of the different types of carbon nanotubes to adsorb and/or releasing hydrogen have been performed at 77 K with a volumetric Sievert analytical tool. Our findings clearly demonstrate a direct correlation between the exposed surface area and adsorbed hydrogen capacity, which confirms their linear relationship observed previously. For instance, single-walled nanotubes with surface area density of approximately 800 m2/g have showed hydrogen storage of approximately 1.7 wt% at a pressure of 35 atm. Adsorption process seems to be perfectly reversible. The adsorption values have been compared with a simple model, in order to evaluate the potentialities for carbon-based nanomaterials in future hydrogen storage applications.