Two novel hexacoordinated Co(II)-based single-ion magnets were prepared and characterised. Both neutral complexes feature metal-centred coordination with one terminal and one bidentate nitrate anions along with tridentate derivatives of a 2,6-bis(1H-benzimidazole-2-yl)pyridine ligand containing either n-octyl (complex 1) or n-dodecyl (complex 2) chains. The presence of long aliphatic chains ensures their solubility in low polarity and volatile solvents frequently used for lithography patterning. This enabled the preparation of microstructural layers and patterns on technologically relevant substrates by easy-to-handle and low-cost wet lithographic techniques. On the other hand, attempts at surface deposition via sublimation were not successful due to thermal instability. The electronic structure of complexes typically features an orbitally non-degenerate ground state well-separated from the lowest excited state, which allows one to analyse magnetic anisotropy by the spin Hamiltonian approach. Zero-field splitting parameters obtained from CASSCF-NEVPT2 calculations and from the analysis of magnetic data suggest that both compounds display positive axial D parameters within a range of 17-25 cm(-1). Combined results from high-field electron paramagnetic resonance (X-band and HF-EPR) and Fourier-transform infrared magnetic spectroscopy (FIRMS) simulated with the spin Hamiltonian provided the axial and rhombic zerofield splitting terms D = +23.7 cm(-1) for complex 1 and D = +24.2 cm(-1) for complex 2, together with pronounced rhombicity in the range of E/D approximate to 0.15-0.19 for both compounds. Dynamic magnetic investigations have revealed the field-induced slow relaxation of magnetisation, with maximal relaxation times (tau) of 7.6 ms for 1 and 0.8 ms for 2. This relaxation is governed via a combination of several relaxation mechanisms, among which the quantum tunnelling was efficiently suppressed by the applied static magnetic field. The effective barriers of spin reversal U-eff = 77(4) K for 1 and U-eff = 70(2) K for 2 are consistent with the expected values calculated using the ZFS parameters.

Hydrogen production via water electrolysis defines the novel energy vector for achieving a sustainable society. However, the true progress of the given technology is hindered by the sluggish and complex hydrogen evolution reaction (HER) occurring at the cathodic side of the system where overpriced and scarce Pt-based electrocatalysts are usually employed. Therefore, efficient platinum group metals (PGMs)-free electrocatalysts to carry out HER with accelerated kinetics are urgently demanded. In this scenario, molybdenum disulfide (MoS2) owing to efficacious structural attributes and optimum hydrogen-binding free energy (?GH*) is emerging as a reliable alternative to PGMs. However, the performance of MoS2-based electrocatalysts is still far away from the benchmark performance. The HER activity of MoS2 can be improved by engineering the structural parameters i.e., doping, defects inducement, modulating the electronic structure, stabilizing the 1 T phase, creating nanocomposites, and altering the morphologies using appropriate fabrication pathways. Here, we have comprehensively reviewed the majority of the scientific endeavors published in recent years to uplift the HER activity of MoS2-based electrocatalysts using different methods. Advancements in the major fabrication strategies including hydrothermal synthesis methods, chemical vapor deposition, exfoliation techniques, plasma treatments, chemical methodologies, etc. to tune the structural parameters and hence their ultimate influence on the electrocatalytic activity in acidic and/or alkaline media have been thoroughly discussed. This study can provide encyclopedic insights about the fabrication routes that have been pursued to improve the HER performance of MoS2-based electrocatalysts.

In membrane-based water purification technology, control of the membrane pore structure is fundamental to defining its performance. The present study investigates the effect of the preparation conditions on the final pore size distribution and on the dye removal efficiency of cellulose acetate membranes. The membranes were fabricated by means of phase inversion (using different speeds of film casting and different thicknesses of the casted solution) and introducing modifications in the preparation conditions, such as the use of a coagulation bath instead of pure water and the addition of a surfactant as a solution additive. Both isotropic and anisotropic membranes could be fabricated, and the membranes' pore size, porosity, and water permeability were found to be greatly influenced by the fabrication conditions. The removal capacity towards different types of water contaminants was investigated, considering, as model dyes, Azure A and Methyl Orange. Azure A was removed with higher efficiency due to its better chemical affinity for cellulose acetate, and for both dyes the uptake could be fitted using a pseudo-second order model, evidencing that the rate-limiting step is chemisorption involving valency forces through the sharing or exchange of electrons between the dye and the membrane.

We herein address the problem of polymorph selection by introducing a general and straightforward concept based on their ordering. We demonstrated the concept by the ordered patterning of four compounds capable of forming different polymorphs when deposited on technologically relevant surfaces. Our approach exploits the fact that, when the growth of a crystalline material is confined within sufficiently small cavities, only one of the possible polymorphs is generated. We verify our method by utilizing several model compounds to fabricate micrometric "logic patterns" in which each of the printed pixels is easily identifiable as comprising only one polymorph and can be individually accessed for further operations.

Here, we exploited the UV light and thermal triggered E <-> Z photoisomerization of an azobenzene compound to fabricate multimodal readable and rewritable data matrix based devices. We first demonstrated that the UV light sensing capabilities can be simultaneously monitored by the change in optical, spectroscopic, and electrical properties. Then we exploited this capability by integrating tetra(azobenzene)methane crystals in a micrometric TAG whose information can be modified and repristinated by local UV treatment and thermal annealing. The system was characterized by polarized optical microscopy, Raman spectroscopy, conductive atomic force microscopy and Kelvin Probe Force Microscopy.

Here, we applied rubbing on thiophene-basedorganic semiconductor thin films to induce a reversible mechanical amorphisation. Amorphisation is associated with fluorescence switching, which is regulated by the polymorphic nature of the film. Thermal annealing of rubbed films produces an opposite effect with respect to rubbing, inducing film crystallization. Notably, thermal crystallisation starts at a low temperature but generates the polymorph stable at a high temperature in the bulk. The mechanism of mechanical transformation is explained considering the mechanical properties of the material and demonstrated through combined X-ray diffraction, atomic force microscopy and photoluminescence at confocal microscopy.

Nanoparticles (NPs) have been studied for biomedical applications, ranging from prevention, diagnosis and treatment of diseases. However, the lack of the basic understanding of how NPs interact with the biological environment has severely limited their delivery efficiency to the target tissue and clinical translation. Here, we show the effective regulation of the surface properties of NPs, by controlling the surface ligand density, and their effect on serum protein adsorption, cellular uptake and cytotoxicity. The surface properties of NPs are tuned through the controlled replacement of native ligands, which favor protein adsorption, with ligands capable of increasing protein adsorption resistance. The extent and composition of the protein layer adsorbed on NPs are strongly correlated to the degree of ligands replaced on their surface and, while BSA is the most abundant protein detected, ApoE is the one whose amount is most affected by surface properties. On increasing the protein resistance, cellular uptake and cytotoxicity in mouse embryonic fibroblasts of NPs are drastically reduced, but the surface coating has no effect on the process by which NPs mainly induce cell death. Overall, this study reveals that the tuning of the surface properties of NPs allows us to regulate their biological outcomes by controlling their ability to adsorb serum proteins. This journal is

Materials possessing long-term antibacterial behavior and high cytotoxicity are of extreme interest in several applications, from biomedical devices to food packaging. Furthermore, for the safeguard of the human health and the environment, it is also stringent keeping in mind the need to gather good functional performances with the development of ecofriendly materials and processes. In this study, we propose a green fabrication method for the synthesis of silver nanoparticles supported on oxidized nanocellulose (ONCs), acting as both template and reducing agent. The complete structural and morphological characterization shows that well-dispersed and crystalline Ag nanoparticles of about 10-20 nm were obtained in the cellulose matrix. The antibacterial properties of Ag-nanocomposites (Ag-ONCs) were evaluated through specific Agar diffusion tests against E. coli bacteria, and the results clearly demonstrate that Ag-ONCs possess high long-lasting antibacterial behavior, retained up to 85% growth bacteria inhibition, even after 30 days of incubation. Finally, cell viability assays reveal that Ag-ONCs show a significant cytotoxicity in mouse embryonic fibroblasts.

Subtracting technologies: Unconventional Nanolithography

Herein, we propose an easy and practical method for the fabrication of highly ordered supramolecular structures. The proposed approach combines fractional precipitation and wet lithography, to obtain a spatially-defined pattern of submicrometric structures with a high molecular order of poly(3-hexylthiophene). The process is demonstrated by XRD, confocal and time-resolved spectroscopy and by the performance of an effective field effect transistor.

Here we applied a novel concept of "sublimation-aided nanostructuring" to control the polymorphism of a model material. The process exploits fractional precipitation as a tool for crystallisation in confinement using a templating agent that sublimes away from the system at the end of the process.

The long-known class of compounds called naphthalene diimides (NDI), bearing alkyl substituents on the imide nitrogen atoms, have been widely used as active materials in thin film devices with interesting optical, sensing and electrical applications. Less is known about their rich crystal chemical behaviour, which comprises numerous polymorphic transitions, and the appearance of elusive liquid crystalline phases. It is this behaviour which determines the response of the devices based on them. Here we fully characterized, by combining differential scanning calorimetry, powder and thin film diffraction and optical microscopy techniques, two newly synthesized NDI materials bearing n-octyl and n-decyl side-chains, as well as lighter analogues, of known room temperature crystal structures. In search for a rationale of their physico-chemical properties, phase stability and thermally induced solid-state transition reversibility, the differential behaviour of these NDI materials is interpreted here based on the competitive role of intermolecular pi-pi interactions and the alkyl chain flexibility. The appearance of comparable local minima of the molecular conformational energy hypersurface for shorter alkyls, and, for longer ones, of rotator phases, is here invoked.

In this work, the electrodeposition of smooth bismuth thin films was investigated. Bismuth is known for its peculiar magnetic, thermal and electrical properties but the deposition of a uniform and flat film, which are features required for its application in electronic devices, is not trivial. We investigated the morphology of Bi film electrodeposited at increasing overpotential on a monocrystalline silver electrode. We found that the presence of an underpotential deposition (UPD) layer, previously deposited on the surface, drives the overpotential deposition to a smoother growth. The samples were investigated by means of different techniques: atomic force microscopy (AFM) and scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDS) to study the morphology, X-ray photoemission spectroscopy (XPS) to assess the composition and X-ray diffraction spectroscopy (XRD) to check the crystallinity. We also found an unexpected form birefringence behaviour, which has been preliminary investigated with cross polarized light microscopy (CPL).

Nanomaterials are being widely used in medical applications and consumer products such as cosmetics, fabrics, and food packaging, although their impact on health and the environment is yet to be understood. Strategies enabling reliable and reproducible safety assessment of nanomaterials are needed because predicting their toxic effects is challenging as there is no simple correlation between their properties and the interaction with living systems. Here, the real-time monitoring of toxic effects induced by nanoparticles on cells using organic electrochemical transistors (OECTs) is reported. Noteworthy, OECTs are able to assess the coating-dependent toxicity of nanoparticles on both barrier and non-barrier tissue cells and, moreover, to monitor the cell health status as a function of exposure time, allowing useful insight on the interaction processes between nanomaterials and cells. These results demonstrate that OECTs are effective devices for real-time cell monitoring and in vitro assessment of nanomaterial toxicity.

Polysulfone-based materials were fabricated as casted films, porous membranes, and nanofibers by solution casting, phase inversion process, and electrospinning technique, respectively. Photoactive rhodamine B hydrazide molecules were loaded into the fabrics either in preloading or postloading processes. The morphological structure of the fabrics was investigated by scanning electron microscopy and the wettability was determined by contact angle measurements. Detailed spectroscopic characterizations of the closed and open forms of rhodamine B was performed both in solution and in the solid-state composite materials. Theoretical investigations supported the depiction of the absorption and emission features of the two forms. The response of the prepared composite materials to Cu(II) ions has been tested by absorption and emission spectroscopy and confocal fluorescence imaging. The most effective materials for Cu(II) detection were found to be polysulfone films prepared by phase inversion and postloaded with 10% rhodamine B hydrazide. These results open the way to the development of composite sensory membranes. (c) 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48408.

Current technologies to monitor formation and disruption in in vitro cell cultures are based either on optical techniques or on electrical impedance/resistance measurement, which often rely on cumbersome and time-consuming measurements and data analyses. In this paper, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)-based organic electrochemical transistors (OECTs) are proposed with channel areas specifically designed and dimensioned as fast and real-time monitoring devices for a large variety of cell lines, with a broad range of tissue resistance. In particular, it is investigated how and why two device configurations provide a different response to leaky-barrier (NIH-3T3) and strong-barrier (CaCo-2) cell lines growth and detachment, achieving a continuous monitoring also for leaky-barrier cell layer growth and detachment. Data are collected using the transistor dynamic behavior to a DC potential pulse on the gate, providing an excellent time resolution and thus enhancing the amount of information that can be collected for fast biological processes (<5 s).

Here, we present a suitable advancement of parallel local oxidation nanolithography, demonstrating its feasibility in alternate current mode (AC-PLON). For demonstration, we fabricated model structures consisting of an array of parallel nanostripes of electrochemical SiOx with a controlled roughness. Besides, we proved the repeatability of AC-PLON and its integrability with conventional parallel local oxidation nanolithography.

The increasing scarcity of freshwater sources and the global demand for water is expected to grow in the oncoming decades which urge the need to develop alternative water supplies, including reuse and recycling of wastewater. Membrane-based separation for water treatment is playing an increasingly important role to provide adequate water resources of the desirable quality. H2020-MSCA-IF-project "Enhanced-MUMs" targets the development of advanced multifunctional and low-cost polymeric membranes for water treatment and desalination. The current work represents optimization of the preparation conditions of cellulose acetate membranes by phase inversion technique using automatic film applicator and water as a coagulation medium. The prepared bare membranes have a well-defined anisotropic microscopic structure with a pure water flux range from 150 L/m2.h to 990 L/m2.h using different membrane thicknesses and under different applied pressures. Modified membranes have been prepared using salt coagulation bath as well as in-situ salt addition to the polymer solution during the membrane fabrication. It was found that the preparation conditions greatly affect the microscopic and surface characteristics.The prepared membranes under different conditions were investigated for the separation organic dyes from their aquose solutions either by absorption or by rejection. Cationic and anionic dye models were investigated to understand the mechanism of the separation process. Other aims of the project are to improve the microscopic structure with regard to the pore size and structure and improve the mechanical properties of the modified membranes. In addition, the project aims also to study and control the fouling characteristics of the membranes by imparting photo-induced properties for enhanced antimicrobial and antifouling effects.

Access to clean water continues to be the most urgent and pressing global issue. The increasing scarcity of freshwater sources and the global demand for water is expected to grow in the oncoming decades which urge the need to develop alternative water supplies, including seawater desalination, reuse and recycling of wastewater. Membrane-based separations for water treatment and desalination are playing an increasingly important role to provide adequate water resources of desirable quality for a wide spectrum of designated applications. H2020-MSCA-IF-project "Enhanced-MUMs" targets the development of advanced multifunctional and low-cost polymeric membranes for water treatment and desalination. The project is a multidisciplinary one and its main innovation resides in the combination of (1) enhanced structural properties: high porosity and reinforcement, for improved water treatment and desalination characteristics and (2) light-induced antifouling and antimicrobial activity based on the loading of photosensitizers in the polymeric membrane. The current work represents optimization of the preparation conditions of cellulose acetate membranes by phase inversion technique using automatic film applicator and water as a coagulation medium. The prepared bare membranes have a well-defined anisotropic microscopic structure with a pure water flux range from 150 L/m2.h to 990 L/m2.h using different membrane thickness and under different applied pressure. Modified membranes have been prepared using salt coagulation bath as well as in-situ salt addition to the polymer solution during the membrane fabrication. It was found that the preparation conditions greatly affect the microscopic and surface characteristics. The project also aims to: improve the microscopic structure with regard to the pore size and structure and improve the mechanical properties of the modified membranes. In addition, the project aims also to study and control the fouling characteristics of the membranes by imparting photo-induced properties for enhanced antimicrobial and antifouling effects.

Polymorphism is a widespread phenomenon occurring in many solid materials having important effects in many scientific disciplines. Since molecular packing can determine the functional properties of materials but is often difficult to control, polymorphism has usually been considered a drawback for technological applications. Thanks to advances in its control over the past few years, polymorphism is now often considered more as an opportunity because it allows a much wider range of functionality in, for example, a solid molecular material, where a corresponding packing type can be selected or even promoted. This tutorial review introduces the reader to the most representative progress in applications of polymorphism as an additional functionality of materials especially in its current promise for technological applications. In addition, it examines the most powerful strategies to control and fully exploit the intrinsic properties of polymorphism and transitions between its various metastable states, through fine-tuning of molecular packing in a reproducible manner. The aim is to create awareness about polymorphism as a novel enabling technology rather than as a problem.