Plasma-Driven Tuning of Dielectric Permittivity in Graphene.

Materials with tunable negative electromagnetic performance, i.e., where dielectric permittivity becomes negative, have long been pursued in materials research due to their peculiar electromagnetic (EM) characteristics. Here, this promising feature is reported in materials on the case of plasma-synthesized nitrogen-doped graphene sheets with tunable permittivity over a wide (1-40 GHz) frequency range. Selectively incorporated nitrogen atoms in a graphene scaffold tailor the electronic structure in a way that provides an ultra-low energy (0.5-2 eV) 2D surface plasmon excitation, leading to subunitary and negative dielectric constant values in the Ka-band, from 30 up to 40 GHz. By allowing the tailoring of structures at atomic scale, this novel plasma-based approach creates a new paradigm for designing 2D nanomaterials like nanocarbons with controllable and tunable permittivity, opening a path to the next generation of 2D metamaterials.

Bacterial DNA Recognition by SERS Active Plasma-Coupled Nanogold.

It is shown that surface-enhanced Raman spectroscopy (SERS) can identify bacteria based on their genomic DNA composition, acting as a "sample-distinguishing marker". Successful spectral differentiation of bacterial species was accomplished with nanogold aggregates synthesized through single-step plasma reduction of the ionic gold-containing vapored precursor. A high enhancement factor (EF = 107) in truncated coupled plasmonic particulates allowed SERS-probing at nanogram sample quantities. Simulations confirmed the occurrence of the strongest electric field confinement within nanometric gaps between gold dimers/chains from where the molecular fingerprints of bacterial DNA fragments gained photon scattering enhancement. The most prominent Raman modes linked to fundamental base-pair molecular vibrations were deconvoluted and used to proceed with nitrogenous base content estimation. The genomic composition (percentage of guanine-cytosine and adenine-thymine) was successfully validated by third-generation sequencing using nanopore technology, further proving that the SERS technique can be employed to swiftly specify bioentities by the discriminative principal-component statistical approach.

Synergistic Remediation of Organic Dye by Titanium Dioxide/Reduced Graphene Oxide Nanocomposite.

In this work, nanocomposites based on titanium dioxide and reduced graphene oxide (TiO2@rGO) with different weight percentages of rGO (4, 8, and 16 wt%) were prepared by the hydrothermal/solvothermal synthesis method and thermally treated at 300 °C. The prepared nanocomposites were explored for the removal of methylene blue dye (MB) in the presence of simulated solar illumination as well as natural sunlight. The structural, morphological, chemical, and optical properties of the as-synthesized TiO2@rGO nanocomposites were characterized. The obtained results of the graphene-based nanocomposite materials indicated the existence of interactions between TiO2 and rGO, i.e., the Ti-O-C bond, which confirmed the successful integration of both components to form the TiO2@rGO nanocomposites. The addition of rGO increased the specific surface area, decreased the band gap energy, and increased the photocatalytic degradation efficiency of MB from water compared to TiO2 nanoparticles. The results of photocatalytic activity indicated that the amount of rGO in the prepared TiO2@rGO nanocomposites played a significant role in the application of different photocatalytic parameters, including the initial dye concentration, catalyst concentration, water environment, and illumination source. Our studies show that the reinforcement of the nanocomposite with 8 wt% of rGO allowed us to obtain the maximum photocatalytic decomposition performance of MB (10 mg·L-1) with a removal percentage of 99.20 after 2 h. Additionally, the obtained results show that the prepared TiO2@rGO_8 wt% nanocomposite can be used in three consecutive cycles while maintaining photocatalytic activity over 90%.

Label-Free Mycotoxin Raman Identification by High-Performing Plasmonic Vertical Carbon Nanostructures.

Mycotoxins are widespread chemical entities in the agriculture and food industries that can induce cancer growth and immune deficiency, posing a serious health threat for humankind. These hazardous compounds are produced naturally by various molds (fungi) that contaminate different food products and can be detected in cereals, nuts, spices, and other food products. However, their detection, especially at minimally harmful concentrations, remains a serious analytical challenge. This research shows that high-performing plasmonic substrates (analytical enhancement factor = 5 × 107 ) based on plasma-grown vertical hollow carbon nanotubes can be applied for immediate detection of the most toxic mycotoxins. Due to excellent sensitivity allowing operation at ppb concentrations, it is possible to collect vibrational fingerprints of aflatoxin B1 , zearalenone, alternariol, and fumonisin B1 , highlighting the key spectral differences between them using principal component analysis. Regarding time-consuming conventional methods, including thin-layer chromatography, gas chromatography, high-performance liquid chromatography, and enzyme-linked immunosorbent assay, the designed surface-enhanced Raman spectroscopy substrates provide a clear roadmap to reducing the detection time-scale of mycotoxins down to seconds.

Halochromic Silk Fabric as a Reversible pH-Sensor Based on a Novel 2-Aminoimidazole Azo Dye.

Textiles are important components for the development of lightweight and flexible displays useful in smart materials. In particular, halochromic textiles are fibrous materials with a color-changing ability triggered by pH variations mainly based on pH-sensitive dye molecules. Recently, a novel class of 2-aminoimidazole azo dyes was developed with distinct substituent patterns. In this work, silk fabric was functionalized through exhaustion for the first time with one of these dyes (AzoIz.Pip). The halochromic properties of the dye were assessed in an aqueous solution and after silk functionalization. The solutions and the fabrics were thoroughly analyzed by ultraviolet-visible (UV-vis) spectra, color strength (K/S), color difference (∆E), CIE L*a*b* coordinates, and the ultraviolet protection factor (UPF). The dyeing process was optimized, and the halochromic performance (and reversibility) was assessed in universal Britton-Robinson buffers (ranging from pH 3 to 12) and artificial body fluids (acid and alkaline perspiration, and wound exudate). AzoIz.Pip showed vibrant colors and attractive halochromic properties with a hypsochromic shift from blue (557 nm) to magenta (536 nm) in aqueous buffered solutions. Similarly, the functionalized silk showed a shift in wavelength of the maximum K/S value from 590 nm to 560 nm when pH increases. The silk fabric showed a high affinity to AzoIz.Pip, and promoted additional color stabilization of the dye, avoiding color loss as observed when the dye is in solution at alkaline pH after 24 h. The color reversibility was effective up to the fourth cycle and the fastness tests denoted suitable results, except washing fastness. The cytotoxicity of the silk fabric extracts was assessed, depicting reduced viability of HaCaT cells to <70% only when the dye concentration in the fabric is higher or equal to 64 µg·mL-1. Nevertheless, lower concentrations were also very effective for the halochromic performance in silk. These materials can thus be a helpful tool for developing sensors in several sectors such as biomedicine, packaging, filtration, agriculture, protective apparel, sports, camouflage, architecture, and design.

Ultrasonic photoacoustic emitter of graphene-nanocomposites film on a flexible substrate.

Photoacoustic devices generating high-amplitude and high-frequency ultrasounds are attractive candidates for medical therapies and on-chip bio-applications. Here, we report the photoacoustic response of graphene nanoflakes - Polydimethylsiloxane composite. A protocol was developed to obtain well-dispersed graphene into the polymer, without the need for surface functionalization, at different weight percentages successively spin-coated onto a Polydimethylsiloxane substrate. We found that the photoacoustic amplitude scales up with optical absorption reaching 11 MPa at ∼ 228 mJ/cm2 laser fluence. We observed a deviation of the pressure amplitude from the linearity increasing the laser fluence, which indicates a decrease of the Grüneisen parameter. Spatial confinement of high amplitude (> 40 MPa, laser fluence > 55 mJ/cm2) and high frequency (Bw-6db ∼ 21.5 MHz) ultrasound was achieved by embedding the freestanding film in an optical lens. The acoustic gain promotes the formation of cavitation microbubbles for moderate fluence in water and in tissue-mimicking material. Our results pave the way for novel photoacoustic medical devices and integrated components.

Stabilization of Silver Nanoparticles on Polyester Fabric Using Organo-Matrices for Controlled Antimicrobial Performance.

Antimicrobial textiles are helpful tools to fight against multidrug-resistant pathogens and nosocomial infections. The deposition of silver nanoparticles (AgNPs) onto textiles has been studied to achieve antimicrobial properties. Yet, due to health and environmental safety concerns associated with such formulations, processing optimizations have been introduced: biocompatible materials, environmentally friendly agents, and delivery platforms that ensure a controlled release. In particular, the functionalization of polyester (PES) fabric with antimicrobial agents is a formulation in high demand in medical textiles. However, the lack of functional groups on PES fabric hinders the development of cost-effective, durable systems that allow a controlled release of antimicrobial agents. In this work, PES fabric was functionalized with AgNPs using one or two biocompatible layers of chitosan or hexamethyldisiloxane (HMDSO). The addition of organo-matrices stabilized the AgNPs onto the fabrics, protected AgNPs from further oxidation, and controlled their release. In addition, the layered samples were efficient against Staphylococcus aureus and Escherichia coli. The sample with two layers of chitosan showed the highest efficacy against S. aureus (log reduction of 2.15 ± 1.08 after 3 h of contact). Against E. coli, the sample with two layers of chitosan showed the best properties. Chitosan allowed to control the antimicrobial activity of AgNPs, avoid the complete loss of AgNPs after washings and act in synergy with AgNPs. After 3 h of incubation, this sample presented a log reduction of 4.81, and 7.27 of log reduction after 5 h of incubation. The antimicrobial results after washing showed a log reduction of 3.47 and 4.88 after 3 h and 5 h of contact, respectively. Furthermore, the sample with a final layer of HMDSO also presented a controlled antimicrobial effect. The antimicrobial effect was slower than the sample with just an initial layer of HMDSO, with a log reduction of 4.40 after 3 h of incubation (instead of 7.22) and 7.27 after 5 h. The biocompatibility of the composites was confirmed through the evaluation of their cytotoxicity towards HaCaT cells (cells viability > 96% in all samples). Therefore, the produced nanocomposites could have interesting applications in medical textiles once they present controlled antimicrobial properties, high biocompatibility and avoid the complete release of AgNPs to the environment.