Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

Humic substance/metal-oxide multifunctional nanoparticles as advanced antibacterial-antimycotic agents and photocatalysts for the degradation of PLA microplastics under UVA/solar radiation.

As a result of the accumulation of plastic in the environment, microplastics have become part of the food chain, boosting the resistance of fungi and bacteria which can frequently encounter human beings. Employing photocatalytic degradation is a possible route towards the removal of chemical and biological pollutants, such as plastics and microplastic wastes as well as microorganisms. Using biowaste materials to design hybrid nanoparticles with enhanced photocatalytic and antimicrobial features would uphold the principles of the circular bioeconomy. Here, two unexpensive semiconductors-namely titanium dioxide (TiO2) and zinc oxide (ZnO) - were synthetized through solvothermal synthesis and combined with humic substances deriving from agrifood biomass. The preparation led to hybrid nanoparticles exhibiting enhanced ROS-generating properties for simultaneous applications as antimicrobial agents against different bacterial and fungal strains and as photoactive catalysts to degrade polylactic acid (PLA) microplastics under UVA and solar irradiation. In comparison to bare nanoparticles, hybrid nanoparticles demonstrated higher antibacterial and antimycotic capabilities toward various pathogenic microorganisms as well as advanced photocatalytic activity in the degradation of PLA with a carbonyl index reduction in the range of 15-23%, thus confirming a noteworthy ability in microplastics photodegradation under UVA and solar irradiation.

Label-Free Protein Analysis by Pyro-Electrohydrodynamic Jet Printing of Gold Nanoparticles.

The pyro-electrohydrodynamic jet (p-jet) printing technology has been used for the fabrication of confined assemblies of gold nanoparticles with a round shape and a diameter ranging between 100 and 200 µm. The surface-enhanced Raman spectroscopy (SERS) performance of the p-jet substrate was evaluated by using Rhodamine 6G (R6G) as a reference. The results demonstrate that this kind of SERS substrate exhibits strong plasmonic effects and a significant reproducibility of the signal with a coefficient of variation below 15%. We tested the signal behavior also in case of the bovine serum albumin (BSA) as a model analyte, to demonstrate the affinity with biomolecules. Strong SERS activity was measured also for BSA across the whole spot area. The spectral patterns collected in different locations of the sensing area were highly reproducible. This observation was substantiated by multivariate analysis of the imaging datasets and opens the route towards a potential application of this kind of SERS substrate in biosensing.

Quantitative determination of rapid biomass formation on pyro-electrified polymer sheets.

The ability of a bacterial strain to form a biofilm is strictly related to its pathogenicity. Bacterial adherence and early biofilm formation are influenced by chemical, physical and biological factors that determine their pathogenic properties. We recently presented in literature the ability of pyro-electrified polymer sheets to promote rapid biofilm formation, based on what we called biofilm electrostatic test (BET) carriers. Here we performed a step forward by presenting a comprehensive characterization of the BET methodology through a quantitative evaluation of the biomass on the BET-carrier in the very early stages of incubation. Two bacterial suspensions of Escherichia coli were added to the surface of the BET-carrier, with one order of magnitude difference in initial optical density. The biofilms were stained at different incubation times, while the crystal violet assay and the live/dead reaction kit were used for evaluating the biomass and the viability, respectively. The BET-carrier systematically promoted a faster biofilm formation even in case of very diluted bacterial concentration. The results suggest that the BET-carrier could be used for evaluating rapidly the ability of bacteria to form biofilms and thus their inclination to pathogenicity, thanks to the challenging acceleration in biofilm formation.

Detecting Collagen Molecules at Picogram Level through Electric Field-Induced Accumulation.

The demand for sensors capable of measuring low-abundant collagen in human fluids has highly increased in recent years. Indeed, collagen is expected to be a biomarker for chronic diseases and could monitor their progression. Here we show detection of highly diluted samples of collagen at picogram level thanks to an innovative pyro-electrohydrodynamic jet (p-jet) system. Through the intense electric fields generated by the pyroelectric effect in a ferroelectric crystal, the collagen solution was concentrated on a small area of a slide that was appropriately functionalized to bind proteins. The collagen molecules were labeled by an appropriate fluorophore to show how the number of tiny droplets influences the limit of detection of the technique. The results show that the p-jet is extremely promising for overcoming the current detection limits of collagen-based products in human fluids, performing 10 times better than the enzyme-linked immunosorbent assay (ELISA) and thus paving the way for the early diagnosis of related chronic diseases.

Pyro-Electrification of Freestanding Polymer Sheets: A New Tool for Cation-Free Manipulation of Cell Adhesion in vitro.

Localized electric fields have become, in recent years, a source of inspiration to researchers and laboratories thanks to a huge amount of applications derived from it, including positioning of microparticles as building blocks for electrical, optical, and magnetic devices. The possibility of producing polymeric materials with surface charge thus opens new perspectives for applications where process simplicity and cost-effectiveness of flexible electronics are of fundamental importance. In particular, the influence of surface charges is widely studied and is a critical issue especially when new materials and functional technologies are introduced. Here, we report a voltage-free pyro-electrification (PE) process able to induce a permanent dipole orientation into polymer sheets under both mono- and bipolar distribution. The technique makes use of the pyroelectric effect for generating electric potentials on the order of kilovolts by an easy-to-accomplish thermal treatment of ferroelectric lithium niobate (LN) crystals. The PE allows us to avoid the expensive and time-consuming fabrication of high-power electrical circuits, as occurs in traditional generator-based techniques. Since the technique is fully compatible with spin-coating-based procedures, the pyro-electrified polymer sheets are easily peeled off the surface of the LN crystal after PE completion, thus providing highly stable and freestanding charged sheets. We show the reliability of the technique for different polymers and for different applications ranging from live cell patterning to biofilm formation tests for bacteria linked to food-processing environments.

Maskless Arrayed Nanofiber Mats by Bipolar Pyroelectrospinning.

The numerous advantages of micro- and nanostructures produced by electrospinning (ES) have stimulated enormous interest in this technology with potential application in several fields. However, ES still has some limitations in controlling the geometrical arrangement of the fiber mats so that expensive and time-consuming technologies are usually employed for producing ordered geometries. Here we present a technique that we call "bipolar pyroelectrospinning" (b-PES) for generating ordered arrays of fiber mats in a direct manner by using the bipolar pyroelectric field produced by a periodically poled lithium niobate crystal (PPLN). The b-PES is free from expensive electrodes, nozzles, and masks because it makes use simply of the structured pyroelectric field produced by the PPLN crystal used as collector. The results show clearly the reliability of the technique in producing a wide variety of arrayed fiber mats that could find application in bioengineering or many other fields. Preliminary results of live cells patterning under controlled geometrical constraints is also reported and discussed in order to show potential exploitation as a scaffold in tissue engineering.

Simple and Rapid Bioink Jet Printing for Multiscale Cell Adhesion Islands.

A simple and rapid process for multiscale printing of bioinks with dot widths ranging from hundreds of microns down to 0.5 µm is presented. The process makes use of spontaneous surface charges generated pyroelectrically that are able to draw little daughter droplets directly from the free meniscus of a mother drop through jetting ("p-jet"), thus avoiding time-consuming and expensive fabrication of microstructured nozzles. Multiscale can be easily achieved by modulating the parameters of the p-jet process. Here, it is shown that the p-jet allows us to print well-defined adhesion islands where NIH-3T3 fibroblasts are constrained to live into cluster configurations ranging from 20 down to single cell level. The proposed fabrication approach can be useful for high-throughput studies on cell adhesion, cytoskeleton organization, and stem cell differentiation.

Bipolar Patterning of Polymer Membranes by Pyroelectrification.

Polymer freestanding membranes with permanent bipolar patterns are fabricated by "pyroelectrification". The thermal stimulation of periodically poled lithium niobate (PPLN) crystals simultaneously generates the pyroelectric effect, the glass transition of the polymer, and therefore the periodic electric poling of the polymer. The reliability of these membranes is demonstrated for applications under both dry and wet conditions, including cell patterning.