Self-Assembled Chiral Film Based on Melanin Polymers.

Chirality plays a fundamental role in natural phenomena, yet its manifestation on solid surfaces remains relatively unexplored. In this study, we investigate the formation of chiroptical melanin-based self-assembled films on quartz substrates, leveraging mussel-inspired surface chemistry. Water-soluble porphyrins serve as molecular synthons, facilitating the spontaneous formation of hetero-aggregates in phosphate-buffered saline containing L- or D-DOPA. Spectroscopic analysis reveals chiral transfer from DOPA enantiomers to porphyrin hetero-aggregates, followed by the disruption of these latter and subsequent generation of chiral melanin structures in solution. Quartz substrates inserted into these solutions spontaneously accumulate homogeneous melanin-like films over days, demonstrating the feasibility of self-assembly. The resulting films exhibit characteristic UV/Vis and CD spectra, with distinct signals indicating successful chiral induction. Interestingly, the AFM characterizations reveal a distinct surface morphology, and in addition, some thermal and mechanical properties have been taken into account. Overall, this study sheds light on the formation, stability, and chiroptical properties of melanin-based films, paving the way for their application in various fields.

Chemical and Morphological Modifications Induced by Argon Plasma Treatments on Fluorinated Polybenzoxazole Films.

Fluorinated photodefinable polymers are widely employed as re-distribution layers in wafer-level packaging to produce microelectronic devices because of their suitable low dielectric constant and moisture absorption, high mechanical toughness, thermal conductivity and stability, and chemical inertness. Typically, fluorinated photodefinable polybenzoxazoles (F-PBOs) are the most used in this field. In the present work, we investigated by atomic force microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy the morphological and chemical modifications induced by Ar plasma treatments on F-PBO films. This process, used to remove surface contaminant species, as well as increase the polymeric surface roughness, to improve the adhesion to the other components during electronic packaging, is a crucial step during the manufacturing of some microelectronic devices. We found that argon plasma treatments determine the wanted drastic increase of the polymer surface roughness but, in the presence of a patterned silver layer on F-PBO, needed for the fabrication of electric contacts in microelectronic devices, also induce some unwanted formation of silver fluoride species.

3D Printing Manufacturing of Polydimethyl-Siloxane/Zinc Oxide Micro-Optofluidic Device for Two-Phase Flows Control.

Tailored ZnO surface functionalization was performed inside a polydimethyl-siloxane (PDMS) microchannel of a micro-optofluidic device (mofd) to modulate its surface hydrophobicity to develop a method for fine tuning the fluid dynamics inside a microchannel. The wetting behavior of the surface is of particular importance if two different phases are used for system operations. Therefore, the fluid dynamic behavior of two immiscible fluids, (i) air-water and (ii) air-glycerol/water in PDMS mofds and ZnO-PDMS mofds was investigated by using different experimental conditions. The results showed that air-glycerol/water fluid was always faster than air-water flow, despite the microchannel treatment: however, in the presence of ZnO microstructures, the velocity of the air-glycerol/water fluid decreased compared with that observed for the air-water fluid. This behavior was associated with the strong ability of glycerol to create an H-bond network with the exposed surface of the zinc oxide microparticles. The results presented in this paper allow an understanding of the role of ZnO functionalization, which allows control of the microfluidic two-phase flow using different liquids that undergo different chemical interactions with the surface chemical terminations of the microchannel. This chemical approach is proposed as a control strategy that is easily adaptable for any embedded micro-device.

Systematic Characterization of Plasma-Etched Trenches on 4H-SiC Wafers.

Silicon carbide power semiconductors overcome some limitations of silicon chips, and therefore, SiC is an attractive candidate for next-generation power electronics. In addition, the number of possible vertical devices that can be obtained on a given surface using the trench technique is significantly larger than that attainable using a planar setup. Moreover, a SiC trench power metal oxide semiconductor field-effect transistor (power MOSFET) structure removes the junction field-effect transistor (JFET) region (that would decrease the current flow width) and improves the channel density, thus reducing the specific electrical resistance. Consequently, in the present study, we report on the chemical bonding state of elements and structural characterization of trenches, obtained using SF6-based plasma etching, on the 4H-SiC polytype substrate. An interferometric algorithm that finds the endpoint to stop etching governed the trench depth. Scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy analyses stated the high quality and uniformity of the trenches. These materials are particularly promising for the fabrication of the SiC MOSFET to be implemented in the manufacturing of power devices.

Microstructured Surface Plasmon Resonance Sensor Based on Inkjet 3D Printing Using Photocurable Resins with Tailored Refractive Index.

In this work, a novel approach to realize a plasmonic sensor is presented. The proposed optical sensor device is designed, manufactured, and experimentally tested. Two photo-curable resins are used to 3D print a surface plasmon resonance (SPR) sensor. Both numerical and experimental analyses are presented in the paper. The numerical and experimental results confirm that the 3D printed SPR sensor presents performances, in term of figure of merit (FOM), very similar to other SPR sensors made using plastic optical fibers (POFs). For the 3D printed sensor, the measured FOM is 13.6 versus 13.4 for the SPR-POF configuration. The cost analysis shows that the 3D printed SPR sensor can be manufactured at low cost (∼15 €) that is competitive with traditional sensors. The approach presented here allows to realize an innovative SPR sensor showing low-cost, 3D-printing manufacturing free design and the feasibility to be integrated with other optical devices on the same plastic planar support, thus opening undisclosed future for the optical sensor systems.

Photodegradation of Antibiotics by Noncovalent Porphyrin-Functionalized TiO2 in Water for the Bacterial Antibiotic Resistance Risk Management.

Antibiotics represent essential drugs to contrast the insurgence of bacterial infections in humans and animals. Their extensive use in livestock farming, including aquaculture, has improved production performances and food safety. However, their overuse can implicate a risk of water pollution and related antimicrobial resistance. Consequently, innovative strategies for successfully removing antibiotic contaminants have to be advanced to protect human health. Among them, photodegradation TiO2-driven under solar irradiation appears not only as a promising method, but also a sustainable pathway. Hence, we evaluated several composite TiO2 powders with H2TCPP, CuTCPP, ZnTCPP, and SnT4 porphyrin for this scope in order to explore the effect of porphyrins sensitization on titanium dioxide. The synthesis was realized through a fully non-covalent functionalization in water at room conditions. The efficacy of obtained composite materials was also tested in photodegrading oxolinic acid and oxytetracycline in aqueous solution at micromolar concentrations. Under simulated solar irradiation, TiO2 functionalized with CuTCPP has shown encouraging results in the removal of oxytetracycline from water, by opening the way as new approaches to struggle against antibiotic's pollution and, finally, to represent a new valuable tool of public health.

Optimization of ZnO Nanorods Growth on Polyetheresulfone Electrospun Mats to Promote Antibacterial Properties.

Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic-polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staphylococcus aureus and Staphylococcus epidermidis) Grams. Since antimicrobial action is strictly related to the quantity of ZnO present on surface, a CBD process optimization is performed to achieve the best results in terms of coverage uniformity and reproducibility. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) provide morphological and compositional analysis of PES/ZnO mats while thermogravimetric analysis (TGA) is useful to assess the best process conditions to guarantee the higher amount of ZnO with respect to PES scaffold. Biocidal action is associated to Zn2+ ion leaching in solution, easily indicated by UV-Vis measurement of metallation of free porphyrin layers deposited on glass.

Long-Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin-Calixarene Assemblies.

The hierarchical assembly, in aqueous solution, of a new multi-metalloporphyrin/calixarene aggregate has been accomplished. In this supramolecular system transfer of chirality, from the outermost components to the central porphyrin reporter, takes place as a result of favorable and fully noncovalent long-range electronic communication.

Polyethersulfone Mats Functionalized with Porphyrin for Removal of Para-nitroaniline from Aqueous Solution.

The dispersion of para-nitroaniline (p-NA) in water poses a threat to the environment and human health. Therefore, the development of functional adsorbents to remove this harmful compound is crucial to the implementation of wastewater purification strategies, and electrospun mats represent a versatile and cost-effective class of materials that are useful for this application. In the present study, we tested the ability of some polyethersulfone (PES) nanofibers containing adsorbed porphyrin molecules to remove p-NA from water. The functional mats in this study were obtained by two different approaches based on fiber impregnation or doping. In particular, meso-tetraphenyl porphyrin (H2TPP) or zinc(II) meso-tetraphenyl porphyrin (ZnTPP) were immobilized on the surface of PES fiber mats by dip-coating or added to the PES electrospun solution to obtain porphyrin-doped PES mats. The presence of porphyrins on the fiber surfaces was confirmed by UV-Vis spectroscopy, fluorescence measurements, and XPS analysis. p-NA removal from water solutions was spectrophotometrically detected and evaluated.

Biocompatibility between Silicon or Silicon Carbide surface and Neural Stem Cells.

Silicon has been widely used as a material for microelectronic for more than 60 years, attracting considerable scientific interest as a promising tool for the manufacture of implantable medical devices in the context of neurodegenerative diseases. However, the use of such material involves responsibilities due to its toxicity, and researchers are pushing towards the generation of new classes of composite semiconductors, including the Silicon Carbide (3C-SiC). In the present work, we tested the biocompatibility of Silicon and 3C-SiC using an in vitro model of human neuronal stem cells derived from dental pulp (DP-NSCs) and mouse Olfactory Ensheathing Cells (OECs), a particular glial cell type showing stem cell characteristics. Specifically, we investigated the effects of 3C-SiC on neural cell morphology, viability and mitochondrial membrane potential. Data showed that both DP-NSCs and OECs, cultured on 3C-SiC, did not undergo consistent oxidative stress events and did not exhibit morphological modifications or adverse reactions in mitochondrial membrane potential. Our findings highlight the possibility to use Neural Stem Cells plated on 3C-SiC substrate as clinical tool for lesioned neural areas, paving the way for future perspectives in novel cell therapies for neuro-degenerated patients.

Covalently functionalized carbon nanoparticles with a chiral Mn-Salen: a new nanocatalyst for enantioselective epoxidation of alkenes.

A new protocol to obtain carbon nanoparticles (CNPs) covalently functionalized with a chiral Mn-Salen catalyst is described here. The new nanocatalyst (CNPs-Mn-Salen) was tested in the enantioselective epoxidation of some representative alkenes (CN-chromene, 1,2-dihydronaphthalene and cis-ß-ethyl styrene), obtaining better enantiomeric excess values than that of the catalyst single molecule, highlighting the role of the nanostructure in the enantioselectivity.

Chiral Recognition of L- and D- Amino Acid by Porphyrin Supramolecular Aggregates.

We report of the interactions between four amino acids lysine (Lys), arginine (Arg), histidine (His), and phenylalanine (Phe) with the J-aggregates of the protonated 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin H4TPPS. Several aspects of these self-assembled systems have been analyzed: (i) the chiral transfer process; (ii) the hierarchical effects leading to the aggregates formation; and, (iii) the influence of the amino acid concentrations on both transferring and storing chiral information. We have demonstrated that the efficient control on the J-aggregates chirality is obtained when all amino acids are tested and that the chirality transfer process is under hierarchical control. Finally, the chiral porphyrin aggregates obtained exhibit strong chiral inertia.

Trifunctional Epoxy Resin Composites Modified by Soluble Electrospun Veils: Effect on the Viscoelastic and Morphological Properties.

Electrospun veils from copolyethersulfones (coPES) were prepared as soluble interlaminar veils for carbon fiber/epoxy composites. Neat, resin samples were impregnated into coPES veils with unmodified resin, while dry carbon fabrics were covered with electrospun veils and then infused with the unmodified epoxy resin to prepare reinforced laminates. The thermoplastic content varied from 10 wt% to 20 wt%. TGAP epoxy monomer showed improved and fast dissolution for all the temperatures tested. The unreinforced samples were cured first at 180 °C for 2 h and then were post-cured at 220 °C for 3 h. These sample showed a high dependence on the curing cycle. Carbon reinforced samples showed significant differences compared to the neat resin samples in terms of both viscoelastic and morphological properties.

Combined Approach To Remove and Fast Detect Heavy Metals in Water Based on PES-TiO2 Electrospun Mats and Porphyrin Chemosensors.

Hybrid poly(ether sulfones) (PES)-TiO2 electrospun mats are used as selective filters to remove lead and zinc ions from water. Presence of TiO2 is functional to trigger fiber's surface charge that allows for better performances in terms of ionic adsorption with respect to bare PES mats. Temperature increase promotes a speed up of ion removal. Ability of electrospun mats to retain adsorbed ions is proven by washing procedures, which confirm the lack of released Pb2+ in solution, even after sonication. To detect presence of metal ions in aqueous solutions, water-soluble porphyrins are used as chemosensors, which are able to provide fast, in-field, and real-time analysis. In particular, cationic H2T4 metalation, occurring both in solution or at transparent glass surface, allows for a straightforward spectrophotometric (UV-vis) detection of metal ions in solution.

Laser processing of TiO2 colloids for an enhanced photocatalytic water splitting activity.

We have measured the photocatalytic water splitting activity of several titania colloids, modified by nanosecond pulsed laser irradiation. Photocatalysis has been tested using UV and visible light. We have found that laser irradiation increases the hydrogen production efficiency up to a factor of three for anatase, rutile and P25. A hydrogen production rate as high as 30mmolg-1h-1 has been obtained with good stability, tested by repeated runs. The chemical and morphological properties of the nanoparticles have been studied by electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy, showing that laser irradiation promotes the formation of disordered surface state and lattice distortion which could be responsible for the observed enhanced photocatalytic activity.

PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites.

Novel polyhedral oligomeric silsesquioxanes (POSS)-filled thermoplastic electrospun veils were used to tailor the properties of the interlaminar region of epoxy-based composites. The veils were designed to be soluble upon curing in the epoxy matrix, so that POSS could be released within the interlaminar region. Three different POSS contents, varying from 1 to 10 wt %, were tested while the percentage of coPolyethersulphone (coPES) dissolved in the epoxy resin was kept to a fixed value of 10 wt %. Good quality veils could be obtained at up to 10 wt % of POSS addition, with the nanofibers' diameters varying from 861 nm for the coPES to 428 nm upon POSS addition. The feasibility of the soluble veils to disperse POSS in the interlaminar region was proved, and the effect of POSS on phase morphology and viscoelastic properties studied. POSS was demonstrated to significantly affect the morphology and viscoelastic properties of epoxy composites, especially for the percentages 1% and 5%, which enabled the composites to avoid POSS segregates occurring. A dynamic mechanical analysis showed a significant improvement to the storage modulus, and a shift of more than 30 °C due to the POSS cages hindering the motion of the molecular chains and network junctions.

Chirality of self-assembled achiral porphyrins induced by chiral Zn(ii) Schiff-base complexes and maintained after spontaneous dissociation of the templates: a new case of chiral memory.

Herein, we exploit the induction of chirality by chiral Zn(ii) Schiff-base complexes, followed by their spontaneous dissociation in aqueous solution, providing for the first time a possibility of overcoming the template removal steps, to demonstrate memorization of chirality in porphyrin hetero-aggregates.

Effect of Pt Nanoparticles on the Photocatalytic Activity of ZnO Nanofibers.

For this study, we originally realized ZnO nanofibers (∼50 nm in mean radius) mixed with Pt nanoparticles (∼30 nm in mean radius), prepared by pulsed laser ablation in liquid, and investigated their photocatalytic performance. The material was synthesized by the simple electrospinning method coupled with subsequent thermal treatments. Methylene blue was employed as a representative dye pollutant to evaluate the photocatalytic activity of the nanofibers. It was found that the Pt-ZnO fibers exhibit a photodegradation reaction rate that is ∼40 % higher than the one obtained for reference ZnO fibers. These encouraging results demonstrate that Pt-ZnO nanofibers can be fruitfully applied for environmental applications.

Hierarchical effect behind the supramolecular chirality of silver(I)-cysteine coordination polymers.

Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths.

Spontaneous deposition of polylysine on surfaces: role of the secondary structure to optimize noncovalent coating strategies.

Understanding the factors that governs spontaneous molecular transfer from solution to solid surface is fundamental to control noncovalent surface functionalization strategies, both in term of robustness and reproducibility. The comprehension of the nature of interaction involved in the mechanism of spontaneous adsorption will allow for a fine modulation of the deposition process. Herein, we provide experimental evidences to demonstrate that poly-lysine secondary structure represents a crucial factor profoundly influencing the outcome of its spontaneous deposition on quartz surfaces. In particular, random coil to α-helix transition is required to drive an effective transfer of the poly-l-lysine at the liquid-solid interface. ß-sheet deposition requires longer times to be accomplished, while random-coil deposition is highly unfavored. Accordingly, polylysine deposition on quartz and silicon is effective when α-helix is formed in solution (pH>10). This surface noncovalent functionalization represents a simple strategy to fabricate hybrid organic-inorganic or biocompatible materials. In fact, the proposed methodology is proven robust and repeatable and compatible for combination with solution or vapor phases (i.e. MOCVD) nanomaterial deposition approaches.