Improved Photocatalytic Activity of Polysiloxane TiO2 Composites by Thermally Induced Nanoparticle Bulk Clustering and Dye Adsorption

Fine control of nanoparticle clustering within polymeric matrices can be tuned to enhance the physicochemical properties of the resulting composites, which are governed by the interplay of nanoparticle surface segregation and bulk clustering. To this aim, out-of-equilibrium strategies can be leveraged to program the multiscale organization of such systems. Here, we present experimental results indicating that bulk assembly of highly photoactive clusters of titanium dioxide nanoparticles within an in situ synthesized polysiloxane matrix can be thermally tuned. Remarkably, the controlled nanoparticle clustering results in improved degradation photocatalytic performances of the material under …

On the Interaction between 1D Materials and Living Cells

One-dimensional (1D) materials allow for cutting-edge applications in biology, such as single-cell bioelectronics investigations, stimulation of the cellular membrane or the cytosol, cellular capture, tissue regeneration, antibacterial action, traction force investigation, and cellular lysis among others. The extraordinary development of this research field in the last ten years has been promoted by the possibility to engineer new classes of biointerfaces that integrate 1D materials as tools to trigger reconfigurable stimuli/probes at the sub-cellular resolution, mimicking the in vivo protein fibres organization of the extracellular matrix. After a brief overview of the theoretical models r…

Artificial Biosystems by Printing Biology

The continuous progress of printing technologies over the past 20 years has fueled the development of a plethora of applications in materials sciences, flexible electronics, and biotechnologies. More recently, printing methodologies have started up to explore the world of Artificial Biology, offering new paradigms in the direct assembly of Artificial Biosystems (small condensates, compartments, networks, tissues, and organs) by mimicking the result of the evolution of living systems and also by redesigning natural biological systems, taking inspiration from them. This recent progress is reported in terms of a new field here defined as Printing Biology, resulting from the intersection betwee…

Mastering the Tools: Natural versus Artificial Vesicles in Nanomedicine

Naturally occurring extracellular vesicles and artificially made vesicles represent important tools in nanomedicine for the efficient delivery of biomolecules and drugs. Since its first appearance in the literature 50 years ago, the research on vesicles is progressing at a fast pace, with the main goal of developing carriers able to protect cargoes from degradation, as well as to deliver them in a time- and space-controlled fashion. While natural occurring vesicles have the advantage of being fully compatible with their host, artificial vesicles can be easily synthetized and functionalized according to the target to reach. Research is striving to merge the advantages of natural and artifici…

Aqueous Processed Biopolymer Interfaces for Single-Cell Microarrays

Single-cell microarrays are emerging tools to unravel intrinsic diversity within complex cell populations, opening up new approaches for the in-depth understanding of highly relevant diseases. However, most of the current methods for their fabrication are based on cumbersome patterning approaches, employing organic solvents and/or expensive materials. Here, we demonstrate an unprecedented green-chemistry strategy to produce single-cell capture biochips onto glass surfaces by all-aqueous inkjet printing. At first, a chitosan film is easily inkjet printed and immobilized onto hydroxyl-rich glass surfaces by electrostatic immobilization. In turn, poly(ethylene glycol) diglycidyl ether is graft…

Insight into mechanisms of creatinine optical sensing using fluorescein-gold complex

Abstract Creatinine level in biological fluids is a clinically relevant parameter to monitor vital functions and it is well assessed that measuring creatinine levels in the human body can be of great utility to evaluate renal, muscular, or thyroid dysfunctions. The accurate detection of creatinine levels may have a critical role in providing information on health status and represents a tool for the early diagnosis of severe pathologies. Among different methods for creatinine detection that have been introduced and that are evolving with increasing speed, fluorescence-based and colorimetric sensors represent one of the best alternatives, thanks to their affordability, sensitivity and easy r…

A combined physical-chemical and microbiological approach to unveil the fabrication, provenance, and state of conservation of the Kinkarakawa-gami art.

AbstractKinkarakawa-gami wallpapers are unique works of art produced in Japan between 1870 and 1905 and exported in European countries, although only few examples are nowadays present in Europe. So far, neither the wallpapers nor the composing materials have been characterised, limiting the effective conservation–restoration of these artefacts accounting also for the potential deteriogen effects of microorganisms populating them. In the present study, four Kinkarakawa-gami wallpapers were analysed combining physical–chemical and microbiological approaches to obtain information regarding the artefacts’ manufacture, composition, dating, and their microbial community. The validity of these met…

Printing ZnO Inks: From Principles to Devices

Solution-based printing approaches permit digital designs to be converted into physical objects by depositing materials in a layer-by-layer additive fashion from microscale to nanoscale resolution. The extraordinary adaptability of this technology to different inks and substrates has received substantial interest in the recent literature. In such a context, this review specifically focuses on the realization of inks for the deposition of ZnO, a well-known wide bandgap semiconductor inorganic material showing an impressive number of applications in electronic, optoelectronic, and piezoelectric devices. Herein, we present an updated review of the latest advancements on the ink formulations an…

Imbibition of Femtoliter-Scale DNA-Rich Aqueous Droplets into Porous Nylon Substrates by Molecular Printing

This work presents the first reported imbibition mechanism of femtoliter (fL)-scale droplets produced by microchannel cantilever spotting (μCS) of DNA molecular inks into porous substrates (hydrophilic nylon). Differently from macroscopic or picoliter droplets, the downscaling to the fL-size leads to an imbibition process controlled by the subtle interplay of evaporation, spreading, viscosity, and capillarity, with gravitational forces being quasi-negligible. In particular, the minimization of droplet evaporation, surface tension, and viscosity allows for a reproducible droplet imbibition process. The dwell time on the nylon surface permits further tuning of the droplet lateral size, in acc…

Superhydrophobic TiO2/Fluorinated Polysiloxane Hybrid Coatings with Controlled Morphology for Solar Photocatalysis

Abstract Technological applications of polysiloxane coatings have been influenced by their intrinsic low surface energy, which increases their water repellence. Accurate control of composition and interfacial properties through the introduction of perfluorinated moieties further lowers the polysiloxane surface energy, while mixing with metal oxide nanoparticles enhances roughness, resulting in a great potential in the development of superhydrophobic materials for photocatalysis. Herein, a series of hydrophobic and superhydrophobic hybrid coatings were prepared by dehydrocoupling and hydrosilylation reactions of polymethylhydrosiloxane with 1H,1H,2H,2H‐perfluorooctyltriethoxysilane and 1,3-d…

Nanolimes-based ternary formulations for paper reduction, deacidification and consolidation

Enhanced plasmonic processes in amino-rich plasma polymer films for applications at the biointerface

A new plasmonic biosensor was developed in a planar chip-based format by coupling the plasmonic properties of gold nanoparticles (Au NPs) with the mechanical and bioadhesive features of unconventional organic thin films deposited from plasma, namely primary amine-based plasma polymer films (PPFs). A self-assembled layer of spherical Au NPs, 12 nm in diameter, was electrostatically immobilized onto optically transparent silanised glass. In the next step, the Au NP layer was coated with an 18 nm polymeric thick PPF layerviathe simultaneous polymerization/deposition of a cyclopropylamine (CPA) precursor performed by radio frequency discharge, both in pulsed and in continuous wave modes. The CP…

Blue light activated photodegradation of biomacromolecules by N-doped titanium dioxide in a chitosan hydrogel matrix

The use of photocatalysis activated by titanium dioxide nanostructured materials is a promising solution for many biomedical applications ranging from drug-free antibacterial to anticancer therapies, as well as for innovative hydrogel-supported phototherapies. This makes the effects of photocatalysis on the structure of biomolecules of a great relevance in order to define the applicability of photocatalytic materials in the biomedical fields. In this work, the effects of nitrogen-doped titanium dioxide (N-TiO2) dispersed in a biocompatible chitosan/PEG hydrogel on myoglobin and bovine serum albumin as target model proteins were investigated. The efficiency of this composite biocompatible ma…

Self-Cleaning Bending Sensors Based on Semitransparent ZnO Nanostructured Films

The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs syst…

Identification of microplastics using 4‐dimethylamino‐4′‐nitrostilbene solvatochromic fluorescence

In this work, we introduce the use of 4-dimethylamino-4'-nitrostilbene (DANS) fluorescent dye for applications in the detection and analysis of microplastics, an impendent source of pollution made of synthetic organic polymers with a size varying from less than 5 mm to nanometer scale. The use of this dye revealed itself as a versatile, fast and sensitive tool for readily discriminate microplastics in water environment. The experimental evidences herein presented demonstrate that DANS efficiently absorbs into a variety of polymers constituting microplastics, and its solvatochromic properties lead to a positive shift of the fluorescence emission spectrum according to the polarity of the poly…

DNA-based biosensor on flexible nylon substrate by dip-pen lithography for topoisomerase detection

Dip-pen lithography (DPL) technique has been employed to develop a new flexible biosensor realized on nylon with the aim to detect the activity of human topoisomerase. The sensor is constituted by an ordered array of a DNA substrate on flexible nylon supports that can be exploited as a drug screening platform for anticancer molecules. Here, we demonstrate a rapid protocol that permits to immobilize minute quantities of DNA oligonucleotides by DPL on nylon surfaces. Theoretical and experimental aspects have been investigated to successfully print DNA oligonucleotides by DPL on such a porous and irregular substrate.

Oil-in-Water fL Droplets by Interfacial Spontaneous Fragmentation and Their Electrical Characterization

Inkjet printing is here employed for the first time as a method to produce femtoliter-scale oil droplets dispersed in water. In particular, picoliter-scale fluorinated oil (FC40) droplets are printed in the presence of perfluoro-1-octanol surfactant at a velocity higher than 5 m/s. Femtoliter-scale oil droplets in water are spontaneously formed through a fragmentation process at the water/air interface using minute amounts of nonionic surfactant (down to 0.003% v/v of Tween 80). This fragmentation occurs by a Plateau-Rayleigh mechanism at a moderately high Weber number (10(1)). A microfluidic chip with integrated microelectrodes allows droplets characterization in terms of number and diamet…

Photocatalytic activity of N-doped TiO2-based materials embedded with gold NPs for applications in antibacterial photodynamic therapy (aPDT)

Antibacterial photodynamic therapy (aPDT) is a potential treatment for antibiotic-resistant bacterial infections. It is based on the photosensitization of bacterial cells with exogenous agents that, when exposed to light, produce reactive oxygen species (ROS), such as OH-, O2-, H2O2. ROS can induce complex oxidative-reductive chains of reactions, resulting in damage of cellular components in target tissues1. Photocatalysts, like inorganic semiconductor oxides, represent an interesting class of materials to design new strategies for aPTD. As exposed to light of proper wavelengths, photocatalysts induce the formation of electron-hole pairs capable of producing a cascade of reactions suitable …