ZnO tetrapod morphology influence on UV sensing properties.

The aim of this work was to investigate how ZnO tetrapod (ZnO-T) morphology, structure, and surface charge properties (i.e. Debye length) influence their UV sensing properties, shedding light on the underlying photoresponse mechanisms. ZnO-Ts were synthesized and centrifuged to obtain three different fractions with tuned morphology, which were characterized by scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy microscopies, x-ray diffraction analysis, Brunauer-Emmett-Teller measurements, FTIR and UV-vis spectroscopies. ZnO-T UV sensors were fabricated and tested comparing among ZnO-T fractions and commercial ZnO nanoparticles. ZnO-T photoresponse was mostly influenced by ZnO-T leg diameter, with the optimal value close to the double Debye length. We also demonstrated how fractionating ZnO-Ts for morphology optimization can increased the responsivity by 2 orders of magnitude. Moreover, ZnO-T showed 3 orders of magnitude higher responsivity compared to commercial ZnO nanopowder. These results are beneficial for the engineering of efficient UV sensors and contribute to a deeper understanding the overall mechanism governing UV photoresponse.

From gaseous HCN to nucleobases at the cosmic silicate dust surface: an experimental insight into the onset of prebiotic chemistry in space.

HCN in the gas form is considered as a primary nitrogen source for the synthesis of prebiotic molecules in extraterrestrial environments. Nevertheless, the research mainly focused on the reactivity of HCN and its derivatives in aqueous systems, often using external high-energy supply in the form of cosmic rays or high energy photons. Very few studies have been devoted to the chemistry of HCN in the gas phase or at the gas/solid interphase, although they represent the more common scenarios in the outer space. In this paper we report about the reactivity of highly pure HCN in the 150-300 K range at the surface of amorphous and crystalline Mg2SiO4 (forsterite olivine), i.e. of solids among the constituents of the core of cosmic dust particles, comets, and meteorites. Amorphous silica and MgO were also studied as model representatives of Mg2SiO4 structural building blocks. IR spectroscopic results and the HR-MS analysis of the reaction products revealed Mg2+O2- acid/base pairs at the surface of Mg2SiO4 and MgO to be key in promoting the formation of HCN oligomers along with imidazole and purine compounds, already under very mild temperature and HCN pressure conditions, i.e. in the absence of external energetic triggers. Products include adenine nucleobase, a result which supports the hypothesis that prebiotic molecular building blocks can be easily formed through surface catalytic processes in the absence of high-energy supply.

Polyserine repeats promote coiled coil-mediated fibril formation and length-dependent protein aggregation.

Short polyserine (polyS) repeats are frequently found in proteins and longer ones are produced in neurological disorders such as Huntington disease (HD) owing to translational frameshifting or non-ATG-dependent translation, together with polyglutamine (polyQ) and polyalanine (polyA) repeats, forming intracellular aggregates. However, the physiological and pathological structures of polyS repeats are not clearly understood. Early studies highlighted their structural versatility, similar to other homopolymers whose conformation is influenced by the surrounding protein context. As polyS stretches are frequently near polyQ and polyA repeats, which can be part of coiled coil (CC) structures, and the frameshift-derived polyS repeats in HD directly flank CC heptads important for aggregation, we investigate here the structural and aggregation properties of polyS in the context of CC structures. We have taken advantage of peptide models, previously used to study polyQ and polyA in CCs, in which we inserted polyS repeats of variable length and studied them in comparison with polyQ and polyA peptides. We found that polyS repeats promote CC-mediated polymerization and fibrillization as revealed by circular dichroism, chemical crosslinking, and atomic force microscopy. Furthermore, they promote CC-based, length-dependent intracellular aggregation, which is negligible with 7 and widespread with 49 serines. These findings show that polyS repeats can participate in the formation of CCs, as previously found for polyQ and polyA, conferring to peptides distinctive structural properties with aggregation kinetics that are intermediate between those of polyA and polyQ CCs, and contribute to an overall structural definition of the pathophysiogical roles of homopolymeric repeats in CC structures.

Resonance Raman and IR spectroscopy of aligned carbon nanotube arrays with extremely narrow diameters prepared with molecular catalysts on steel substrates.

Carbon nanotubes (CNTs) are considered promising for a large range of emerging technologies ranging from advanced electronics to utilization as nanoreactors. Here we report a controlled facile synthesis of aligned carbon nanotubes with very small dimensions directly grown on steel grid substrates via two-step catalytic chemical vapor deposition (CCVD) of a molecular catalyst (ferrocene) with ethylene as the carbon source. The system is characterized by resonance Raman spectroscopy and the results show single walled carbon nanotube (SWCNT) arrays composed of 0.80 nm to 1.24 nm semiconducting CNTs, as analyzed using Kataura analysis, which is approaching the lowest diameters attainable for SWCNTs. The G+ and G- mode splitting, G- line shapes and ring breathing modes (RBMs) are analyzed to characterize the CNTs. The approach results in close packed and vertically aligned SWCNT bundles formed into hair shapes, with some contribution from multiwall CNTs (MWCNTs). IR spectroscopy is utilized to characterize the edge/defect states that have the ability to form esters and ether bonds in the as-prepared CNTs. The stepwise deposition of the catalyst followed by the carbon source gives control over the formation of small diameter single walled carbon nanotubes (SWCNTs). The utilization of molecular catalysts for narrow diameter growth directly on steel grid substrates forms a promising approach for producing cost-effective CNT substrates for a plethora of sensing and catalytic applications.

MoS2 Nanoparticles Decorating Titanate-Nanotube Surfaces: Combined Microscopy, Spectroscopy, and Catalytic Studies.

MoS2/TNTs composites have been obtained by impregnation of titanate nanotubes (TNTs) with a centrifuged solution of nanosized MoS2 particles in isopropyl alcohol (IPA). The characterization has been performed by combining UV-vis-NIR, Raman, AFM, and HRTEM analyses, before and after impregnation. HRTEM images show that the contact between single-layer MoS2 nanoparticles and the support is efficient, so justifying the decoration concept. The volatility of IPA solvent allows the preparation of composites at low temperature and free of carbonaceous impurities. MoS2 nanoparticles have strong excitonic transitions, which are only slightly shifted with respect to the bulk because of quantum size effects. Concentrations of MoS2, less than 0.1 wt %, are enough to induce strong absorption in the visible. Photodegradation of methylene blue (MB) has been performed on TNTs and MoS2/TNTs to verify the effect of the presence of MoS2. The first layer of adsorbed MB is consumed first, followed by clustered MB in the second and more external layers. The presence of low concentrated MoS2 nanoparticles does not substantially alter the photocatalytic properties of TNTs. This result is due to poor overlapping between the high frequency of MoS2 C, D excitonic transitions and the TNTs band gap transition.

Combined DFT-D3 Computational and Experimental Studies on g-C3N4: New Insight into Structure, Optical, and Vibrational Properties.

Graphitic carbon nitride (g-C3N4) has emerged as one of the most promising solar-light-activated polymeric metal-free semiconductor photocatalysts due to its thermal physicochemical stability but also its characteristics of environmentally friendly and sustainable material. Despite the challenging properties of g-C3N4, its photocatalytic performance is still limited by the low surface area, together with the fast charge recombination phenomena. Hence, many efforts have been focused on overcoming these drawbacks by controlling and improving the synthesis methods. With regard to this, many structures including strands of linearly condensed melamine monomers, which are interconnected by hydrogen bonds, or highly condensed systems, have been proposed. Nevertheless, complete and consistent knowledge of the pristine material has not yet been achieved. Thus, to shed light on the nature of polymerised carbon nitride structures, which are obtained from the well-known direct heating of melamine under mild conditions, we combined the results obtained from XRD analysis, SEM and AFM microscopies, and UV-visible and FTIR spectroscopies with the data from the Density Functional Theory method (DFT). An indirect band gap and the vibrational peaks have been calculated without uncertainty, thus highlighting a mixture of highly condensed g-C3N4 domains embedded in a less condensed "melon-like" framework.

Thickness of multiwalled carbon nanotubes affects their lung toxicity.

Two samples of highly pure multiwalled carbon nanotubes (MWCNTs) similar in hydrophobicity and surface reactivity were prepared with similar length, <5 µm, but markedly different diameter (9.4 vs 70 nm). The samples were compared for their cytotoxic activity, uptake, and ability to induce oxidative stress (ROS production and intracellular GSH depletion) in vitro in murine alveolar macrophages (MH-S). The in vivo toxicity was evaluated by measuring biochemical (LDH activity and total proteins) and cellular responses in bronchoalveolar lavage (BAL) after intratracheal instillation in rats. Both samples were internalized in MH-S cells. However, thin MWCNTs appeared significantly more toxic than the thicker ones, both in vitro and in vivo, when compared on a mass-dose basis. The data reported herein suggest that the nanotube diameter is an important parameter to be considered in the toxicological assessment of CNTs.

Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications.

The field of two-dimensional (2D) layered nanomaterials, their hybrid structures, and composite materials has been suddenly increasing since 2004, when graphene-almost certainly the most known 2D material-was successfully obtained from graphite via mechanical exfoliation [...].

Thermal, Morphological, Electrical Properties and Touch-Sensor Application of Conductive Carbon Black-Filled Polyamide Composites.

Polyamide 66 (PA66) is a well-known engineering thermoplastic polymer, primarily employed in polymer composites with fillers and additives of different nature and dimensionality (1D, 2D and 3D) used as alternatives to metals in various technological applications. In this work, carbon black (CB), a conductive nanofiller, was used to reinforce the PA66 polymer in the 9-27 wt. % CB loading range. The reason for choosing CB was intrinsically associated with its nature: a nanostructured carbon filler, whose agglomeration characteristics affect the electrical properties of the polymer composites. Crystallinity, phase composition, thermal behaviour, morphology, microstructure, and electrical conductivity, which are all properties engendered by nanofiller dispersion in the polymer, were investigated using thermal analyses (thermogravimetry and differential scanning calorimetry), microscopies (scanning electron and atomic force microscopies), and electrical conductivity measurements. Interestingly, direct current (DC) electrical measurements and conductive-AFM mapping through the samples enable visualization of the percolation paths and the ability of CB nanoparticles to form aggregates that work as conductive electrical pathways beyond the electrical percolation threshold. This finding provides the opportunities to investigate the degree of filler dispersion occurring during the transformation processes, while the results of the electrical properties also contribute to enabling the use of such conductive composites in sensor and device applications. In this regard, the results presented in this paper provide evidence that conductive carbon-filled polymer composites can work as touch sensors when they are connected with conventional low-power electronics and controlled by inexpensive and commercially available microcontrollers.

Multifunctional Conductive Paths Obtained by Laser Processing of Non-Conductive Carbon Nanotube/Polypropylene Composites.

Functional materials are promising candidates for application in structural health monitoring/self-healing composites, wearable systems (smart textiles), robotics, and next-generation electronics. Any improvement in these topics would be of great relevance to industry, environment, and global needs for energy sustainability. Taking into consideration all these aspects, low-cost fabrication of electrical functionalities on the outer surface of carbon-nanotube/polypropylene composites is presented in this paper. Electrical-responsive regions and conductive tracks, made of an accumulation layer of carbon nanotubes without the use of metals, have been obtained by the laser irradiation process, leading to confined polymer melting/vaporization with consequent local increase of the nanotube concentration over the electrical percolation threshold. Interestingly, by combining different investigation methods, including thermogravimetric analyses (TGA), X-ray diffraction (XRD) measurements, scanning electron and atomic force microscopies (SEM, AFM), and Raman spectroscopy, the electrical properties of multi-walled carbon nanotube/polypropylene (MWCNT/PP) composites have been elucidated to unfold their potentials under static and dynamic conditions. More interestingly, prototypes made of simple components and electronic circuits (resistor, touch-sensitive devices), where conventional components have been substituted by the carbon nanotube networks, are shown. The results contribute to enabling the direct integration of carbon conductive paths in conventional electronics and next-generation platforms for low-power electronics, sensors, and devices.

Effect of Injection Molding Conditions on Crystalline Structure and Electrical Resistivity of PP/MWCNT Nanocomposites.

Polypropylene (PP) / multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt-mixing and used to manufacture samples by injection molding. The effect of processing conditions on the crystallinity and electrical resistivity was studied. Accordingly, samples were produced varying the mold temperature and injection rate, and the DC electrical resistivity was measured. The morphology of MWCNT clusters was studied by optical and electron microscopy, while X-ray diffraction was used to study the role of the crystalline structure of PP. As a result, an anisotropic electrical behavior induced by the process was observed, which is further influenced by the injection molding processing condition. It was demonstrated that a reduction of electrical resistivity can be obtained by increasing mold temperature and injection rate, which was associated to the formation of the γ-phase and the related inter-cluster morphology of the MWCNT conductive network.

Few-Layer MoS2 Nanodomains Decorating TiO2 Nanoparticles: A Case Study for the Photodegradation of Carbamazepine.

S-doped TiO2 and hybrid MoS2/TiO2 systems have been synthesized, via the sulfidation with H2S of the bare TiO2 and of MoOx supported on TiO2 systems, with the aim of enhancing the photocatalytic properties of TiO2 for the degradation of carbamazepine, an anticonvulsant drug, whose residues and metabolites are usually inefficiently removed in wastewater treatment plants. The focus of this study is to find a relationship between the morphology/structure/surface properties and photoactivity. The full characterization of samples reveals the strong effects of the H2S action on the properties of TiO2, with the formation of defects at the surface, as shown by transmission electron microscopy (TEM) and infrared spectroscopy (IR), while also the optical properties are strongly affected by the sulfidation treatment, with changes in the electronic states of TiO2. Meanwhile, the formation of small and thin few-layer MoS2 domains, decorating the TiO2 surface, is evidenced by both high-resolution transmission electron microscopy (HRTEM) and UV-Vis/Raman spectroscopies, while Fourier-transform infrared (FTIR) spectra give insights into the nature of Ti and Mo surface sites. The most interesting findings of our research are the enhanced photoactivity of the MoS2/TiO2 hybrid photocatalyst toward the carbamazepine mineralization. Surprisingly, the formation of hazardous compounds (i.e., acridine derivatives), usually obtained from carbamazepine, is precluded when treated with MoS2/TiO2 systems.

From biowaste to magnet-responsive materials for water remediation from polycyclic aromatic hydrocarbons.

Composted urban biowaste-derived substances (BBS-GC) are used as carbon sources for the preparation of carbon-coated magnet-sensitive nanoparticles obtained via co-precipitation method and the subsequent thermal treatment at 550 °C under nitrogen atmosphere. A multitechnique approach has been applied to investigate the morphology, magnetic properties, phase composition, thermal stability of the obtained magnet-sensitive materials. In particular, pyrolysis-induced modifications affecting the BBS-GC/carbon shell were highlighted. The adsorption capacity of such bio-derivative magnetic materials for the removal of hydrophobic contaminants such as polycyclic aromatic hydrocarbons was evaluated in order to verify their potential application in wastewater remediation process. The promising results suggest their use as a new generation of magnet-responsive easily-recoverable adsorbents for water purification treatments.

Carbon Domains on MoS2/TiO2 System via Catalytic Acetylene Oligomerization: Synthesis, Structure, and Surface Properties.

Carbon domains have been obtained at the surface of a MoS2/TiO2 (Evonik, P25) system via oligomerization and cyclotrimerization reactions involved in the interaction of the photoactive material with acetylene. Firstly, MoS2 nanosheets have been synthesized at the surface of TiO2, via sulfidation of a molybdenum oxide precursor with H2S (bottom-up method). Secondly, the morphology and the structure, the optical and the vibrational properties of the obtained materials, for each step of the synthesis procedure, have been investigated by microscopy and spectroscopy methods. In particular, transmission electron microscopy images provide a simple tool to highlight the effectiveness of the sulfidation process, thus showing 1L, 2L, and stacked MoS2 nanosheets anchored to the surface of TiO2 nanoparticles. Lastly, in-situ FTIR spectroscopy investigation gives insights into the nature of the oligomerized species, showing that the formation of both polyenic and aromatic systems can be taken into account, being their formation promoted by both Ti and Mo catalytic sites. This finding gives an opportunity for the assembly of extended polyenic, polyaromatic, or mixed domains firmly attached at the surface of photoactive materials. The presented approach, somehow different from the carbon adding or doping processes of TiO2, is of potential interest for the advanced green chemistry and energy conversion/transport applications.

Cu+(H2) and Na+(H2) adducts in exchanged ZSM-5 zeolites.

Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces.

Altered excitability of cultured chromaffin cells following exposure to multi-walled carbon nanotubes.

We studied the effects of multi-walled carbon nanotubes (MWCNTs) on the electrophysiological properties of cultured mouse chromaffin cells, a model of spontaneously firing cells. The exposure of chromaffin cells to MWCNTs at increasing concentrations (30-263 µg/ml) for 24 h reduced, in a dose-dependent way, both the cell membrane input resistance and the number of spontaneously active cells (from 80-52%). Active cells that survived from the toxic effects of MWCNTs exhibited more positive resting potentials, higher firing frequencies and unaltered voltage-gated Ca(2+), Na(+) and K+ current amplitudes. MWCNTs slowed down the inactivation kinetics of Ca(2+)-dependent BK channels. These electrophysiological effects were accompanied by MWCNTs internalization, as confirmed by transmission electron microscopy, indicating that most of the toxic effects derive from a dose-dependent MWCNTs-cell interaction that damages the spontaneous cell activity.

(I(2))(n) encapsulation inside TiO(2): a way to tune photoactivity in the visible region.

We report on the synthesis of nanovoid-structured TiO(2) material via a sol-gel route using titanium isopropoxide as precursor. The nanovoids are formed during the thermal treatment in air at 773 K. The surfaces of internal cavities are populated by the partial oxidation products of the organic part of the Ti precursor (CO(2), hydrogen carbonates, and residual isopropoxide groups). The thermal treatment in air at 773 K allows the maintainence, in the internal voids, of the encapsulated species. Addition of iodine in the synthesis procedure results in a new nanovoid-structured titanium oxide able to absorb light in the whole visible part of the electromagnetic spectrum. The origin of this absorption is attributed to the presence of (I(2))(n) adducts encapsulated in the nanocavities. These species coexist with partial combustion products of isopropoxide groups. Due to the protection of the TiO(2) walls, the (I(2))(n) adducts are not destroyed by thermal treatments in air. We have investigated whether the electron promoted in the excited state of the dye molecule (upon absorption of visible light from the (I(2))(n) adducts) can be injected into either the TiO(2) conduction band or some titanium-localized acceptor, followed by migration of the injected electron to the surface where it reduces adsorbed organic molecules. Preliminarily experiments conducted with sunlight show that the surface-specific efficiency of this process, tested by following the degradation of methylene blue, is about 10 times higher than that of the P25 commercial TiO(2) photocatalyst.