Material jetting of carbon nano onions for printed electronics.

As an additive manufacturing process, material jetting techniques allow to selectively deposit droplets of materials in liquid or powder form through a small-diameter aperture, such as a nozzle of a print head. For the fabrication of printed electronics, a variety of inks and dispersions of functional materials can be deposited by drop-on-demand printing on rigid and flexible substrates. In this work, zero-dimensional multi-layer shell-structured fullerene material, also known as carbon nano-onion (CNO) or onion-like carbon, is printed on polyethylene terephthalate substrates using drop-on-demand inkjet printing. CNOs are produced using a low-cost flame synthesis technique and characterized by electron microscopy, Raman, x-ray photoelectron spectroscopy, and specific surface area and pore size measurements. The produced CNO material has an average diameter of ∼33 nm, pore diameter in the range ∼2-40 nm and a specific surface area of 160 m2.g-1. The CNO dispersions in ethanol have a reduced viscosity (∼1.2 mPa.s) and are compatible with commercial piezoelectric inkjet heads. The jetting parameters are optimized to avoid satellite drops and to obtain a reduced drop volume (52 pL), resulting in optimal resolution (220µm) and line continuity. A multi-step process is implemented without inter-layer curing and a fine control over the CNO layer thickness is achieved (∼180 nm thick layer after 10 printing passes). The printed CNO structures show an electrical resistivity of ∼600 Ω.m, a high negative temperature coefficient of resistance (-4.35 × 10-2°C-1) and a marked dependency on relative humidity (-1.29 × 10-2RH%-1). The high sensitivity to temperature and humidity, combined to the large specific area of the CNOs, make this material and the corresponding ink a viable prospect for inkjet-printed technologies, such as environmental and gas sensors.

Real-time label-free surface plasmon resonance biosensing with gold nanohole arrays fabricated by nanoimprint lithography.

In this work we present a surface plasmon resonance sensor based on enhanced optical transmission through sub-wavelength nanohole arrays. This technique is extremely sensitive to changes in the refractive index of the surrounding medium which result in a modulation of the transmitted light. The periodic gold nanohole array sensors were fabricated by high-throughput thermal nanoimprint lithography. Square periodic arrays with sub-wavelength hole diameters were obtained and characterized. Using solutions with known refractive index, the array sensitivities were obtained. Finally, protein absorption was monitored in real-time demonstrating the label-free biosensing capabilities of the fabricated devices.

Impact of surface topography on the bacterial attachment to micro- and nano-patterned polymer films.

The development of antimicrobial surfaces has become a high priority in recent times. There are two ongoing worldwide health crises: the COVID-19 pandemic provoked by the SARS-CoV-2 virus and the antibiotic-resistant diseases provoked by bacteria resistant to antibiotic-based treatments. The need for antimicrobial surfaces against bacteria and virus is a common factor to both crises. Most extended strategies to prevent bacterial associated infections rely on chemical based-approaches based on surface coatings or biocide encapsulated agents that release chemical agents. A critical limitation of these chemistry-based strategies is their limited effectiveness in time while grows the concerns about the long-term toxicity on human beings and environment pollution. An alternative strategy to prevent bacterial attachment consists in the introduction of physical modification to the surface. Pursuing this chemistry-independent strategy, we present a fabrication process of surface topographies [one-level (micro, nano) and hierarchical (micro+nano) structures] in polypropylene (PP) substrates and discuss how wettability, topography and patterns size influence on its antibacterial properties. Using nanoimprint lithography as patterning technique, we report as best results 82 and 86% reduction in the bacterial attachment of E. coli and S. aureus for hierarchically patterned samples compared to unpatterned reference surfaces. Furthermore, we benchmark the mechanical properties of the patterned PP surfaces against commercially available antimicrobial films and provide evidence for the patterned PP films to be suitable candidates for use as antibacterial functional surfaces in a hospital environment.

Antibacterial activity testing methods for hydrophobic patterned surfaces.

One strategy to decrease the incidence of hospital-acquired infections is to avoid the survival of pathogens in the environment by the development of surfaces with antimicrobial activity. To study the antibacterial behaviour of active surfaces, different approaches have been developed of which ISO 22916 is the standard. To assess the performance of different testing methodologies to analyse the antibacterial activity of hydrophobic surface patterned plastics as part of a Horizon 2020 European research project. Four different testing methods were used to study the antibacterial activity of a patterned film, including the ISO 22916 standard, the immersion method, the touch-transfer inoculation method, and the swab inoculation method, this latter developed specifically for this project. The non-realistic test conditions of the ISO 22916 standard showed this method to be non-appropriate in the study of hydrophobic patterned surfaces. The immersion method also showed no differences between patterned films and smooth controls due to the lack of attachment of testing bacteria on both surfaces. The antibacterial activity of films could be demonstrated by the touch-transfer and the swab inoculation methods, that more precisely mimicked the way of high-touch surfaces contamination, and showed to be the best methodologies to test the antibacterial activity of patterned hydrophobic surfaces. A new ISO standard would be desirable as the reference method to study the antibacterial behaviour of patterned surfaces.

Surface plasmon resonance immunoassay for the detection of the TNFα biomarker in human serum.

A simple method for the detection of TNF-alpha protein biomarker in human serum with great sensitivity has been developed using a surface plasmon resonance biosensor. Signal amplification based on a sandwich immunoassay including gold nanoparticles was used. Detection in serum proved to be challenging due to high undesirable non-specific binding to the sensor surface stemming from the matrix nature of the sample. After optimization of the assay parameters and, in the case of serum, of a sample dilution buffer to minimize the non-specific binding, very low limits of detection were achieved: 11.6 pg/mL (211 fM) and 54.4 pg/mL (989 fM) for spiked buffer and human serum respectively. The amplification steps with high affinity biotinylated antibodies and streptavidin-fuctionalized nanoparticles greatly enhanced the signal with the advantage of additional specificity. Due to its simplicity and sensitivity, the immunoassay has proved feasible to be used for detection of low concentration biomarkers in real samples.