One-step rapid formation of wrinkled fractal antibiofouling coatings from environmentally friendly, waste-derived terpenes.

Wrinkled coatings are a potential drug-free method for mitigating bacterial attachment and biofilm formation on materials such as medical and food grade steel. However, their fabrication typically requires multiple steps and often the use of a stimulus to induce wrinkle formation. Here, we report a facile plasma-based method for rapid fabrication of thin (<250 nm) polymer coatings from a single environmentally friendly precursor, where wrinkle formation and fractal pattern development are controlled solely by varying the deposition time from 3 s to 60 s. We propose a mechanism behind the observed in situ development of wrinkles in plasma, as well as demonstrate how introducing specific topographical features on the surface of the substrata can result int the formation of even more complex, ordered wrinkle patterns arising from the non-uniformity of plasma when in contact with structured surfaces. Thus-fabricated wrinkled surfaces show good adhesion to substrate and an antifouling activity that is not observed in the equivalent smooth coatings and hence is attributed to the specific pattern of wrinkles.

How to Survive at Point Nemo? Fischer-Tropsch, Artificial Photosynthesis, and Plasma Catalysis for Sustainable Energy at Isolated Habitats.

Inhospitable, inaccessible, and extremely remote alike the famed pole of inaccessibility, aka Point Nemo, the isolated locations in deserts, at sea, or in outer space are difficult for humans to settle, let alone to thrive in. Yet, they present a unique set of opportunities for science, economy, and geopolitics that are difficult to ignore. One of the critical challenges for settlers is the stable supply of energy both to sustain a reasonable quality of life, as well as to take advantage of the local opportunities presented by the remote environment, e.g., abundance of a particular resource. The possible solutions to this challenge are heavily constrained by the difficulty and prohibitive cost of transportation to and from such a habitat (e.g., a lunar or Martian base). In this essay, the advantages and possible challenges of integrating Fischer-Tropsch, artificial photosynthesis, and plasma catalysis into a robust, scalable, and efficient self-contained system for energy harvesting, storage, and utilization are explored.

Enhanced Antimicrobial Activity through Synergistic Effects of Cold Atmospheric Plasma and Plant Secondary Metabolites: Opportunities and Challenges.

The emergence of antibiotic resistant microorganisms possesses a great threat to human health and the environment. Considering the exponential increase in the spread of antibiotic resistant microorganisms, it would be prudent to consider the use of alternative antimicrobial agents or therapies. Only a sustainable, sustained, determined, and coordinated international effort will provide the solutions needed for the future. Plant secondary metabolites show bactericidal and bacteriostatic activity similar to that of conventional antibiotics. However, to effectively eliminate infection, secondary metabolites may need to be activated by heat treatment or combined with other therapies. Cold atmospheric plasma therapy is yet another novel approach that has proven antimicrobial effects. In this review, we explore the physiochemical mechanisms that may give rise to the improved antimicrobial activity of secondary metabolites when combined with cold atmospheric plasma therapy.

Carbon Nanocomposites in Aerospace Technology: A Way to Protect Low-Orbit Satellites.

Recent advancements in space technology and reduced launching cost led companies, defence and government organisations to turn their attention to low Earth orbit (LEO) and very low Earth orbit (VLEO) satellites, for they offer significant advantages over other types of spacecraft and present an attractive solution for observation, communication and other tasks. However, keeping satellites in LEO and VLEO presents a unique set of challenges, in addition to those typically associated with exposure to space environment such as damage from space debris, thermal fluctuations, radiation and thermal management in vacuum. The structural and functional elements of LEO and especially VLEO satellites are significantly affected by residual atmosphere and, in particular, atomic oxygen (AO). At VLEO, the remaining atmosphere is dense enough to create significant drag and quicky de-orbit satellites; thus, thrusters are needed to keep them on a stable orbit. Atomic oxygen-induced material erosion is another key challenge to overcome during the design phase of LEO and VLEO spacecraft. This review covered the corrosion interactions between the satellites and the low orbit environment, and how it can be minimised through the use of carbon-based nanomaterials and their composites. The review also discussed key mechanisms and challenges underpinning material design and fabrication, and it outlined the current research in this area.

Recent innovations in the technology and applications of low-dimensional CuO nanostructures for sensing, energy and catalysis.

Low-dimensional copper oxide nanostructures are very promising building blocks for various functional materials targeting high-demanded applications, including energy harvesting and transformation systems, sensing and catalysis. Featuring a very high surface-to-volume ratio and high chemical reactivity, these materials have attracted wide interest from researchers. Currently, extensive research on the fabrication and applications of copper oxide nanostructures ensures the fast progression of this technology. In this article we briefly outline some of the most recent, mostly within the past two years, innovations in well-established fabrication technologies, including oxygen plasma-based methods, self-assembly and electric-field assisted growth, electrospinning and thermal oxidation approaches. Recent progress in several key types of leading-edge applications of CuO nanostructures, mostly for energy, sensing and catalysis, is also reviewed. Besides, we briefly outline and stress novel insights into the effect of various process parameters on the growth of low-dimensional copper oxide nanostructures, such as the heating rate, oxygen flow, and roughness of the substrates. These insights play a key role in establishing links between the structure, properties and performance of the nanomaterials, as well as finding the cost-and-benefit balance for techniques that are capable of fabricating low-dimensional CuO with the desired properties and facilitating their integration into more intricate material architectures and devices without the loss of original properties and function.

Microbial electrosynthesis: carbonaceous electrode materials for CO2 conversion.

Microbial electrosynthesis (MES) is a sustainable approach to address greenhouse gas (GHG) emissions using anthropogenic carbon dioxide (CO2) as a building block to create clean fuels and highly valuable chemicals. The efficiency of MES-based CO2 conversion is closely related to the performance of electrode material and, in particular, the cathode for which carbonaceous materials are frequently used. Compared to expensive metal electrodes, carbonaceous materials are biocompatible with a high specific surface area, wide range of possible morphologies, and excellent chemical stability, and their use can maximize the growth of bacteria and enhance electron transfer rates. Examples include MES cathodes based on carbon nanotubes, graphene, graphene oxide, graphite, graphite felt, graphitic carbon nitride (g-C3N4), activated carbon, carbon felt, carbon dots, carbon fibers, carbon brushes, carbon cloth, reticulated vitreous carbon foam, MXenes, and biochar. Herein, we review the state-of-the-art MES, including thermodynamic and kinetic processes that underpin MES-based CO2 conversion, as well as the impact of reactor type and configuration, selection of biocompatible electrolytes, product selectivity, and the use of novel methods for stimulating biomass accumulation. Specific emphasis is placed on carbonaceous electrode materials, their 3D bioprinting and surface features, and the use of waste-derived carbon or biochar as an outstanding material for further improving the environmental conditions of CO2 conversion using carbon-hungry microbes and as a step toward the circular economy. MES would be an outstanding technique to develop rocket fuels and bioderived products using CO2 in the atmosphere for the Mars mission.

Plasma for aquaponics.

Global environmental, social, and economic challenges call for innovative solutions to food production. Current food production systems require advances beyond traditional paradigms, acknowledging the complexity arising from sustainability and a present lack of awareness about technologies that may help limit, for example, loss of nutrients from soil. Aquaponics, a closed-loop system that combines aquaculture with hydroponics, is a step towards the more efficient management of scarce water, land, and nutrient resources. However, its large-scale use is currently limited by several significant challenges of maintaining desirable water chemistry and pH, managing infections in fish and plants, and increasing productivity efficiently, economically, and sustainably. This paper investigates the opportunities presented by plasma technologies in meeting these challenges, potentially opening new pathways for sustainability in food production.

Spinel CoFe2O4 Nanoflakes: A Path to Enhance Energy Generation and Environmental Remediation Potential of Waste-Derived rGO.

Carbon nanomaterials derived from agricultural waste streams present an exciting material platform that hits multiple sustainability targets by reducing waste entering landfill, and enabling clean energy and environmental remediation technologies. In this work, the energy and photocatalytic properties of reduced graphene oxide fabricated from coconut coir using a simple reduction method using ferrocene are substantially improved by introducing metallic oxides flakes. A series of cobalt ferrite rGO/CoFe2O4 nanocomposites were assembled using a simple soft bubble self-templating assembly, and their potential for clean energy applications confirmed. The transmission electron microscopy images revealed the uniform dispersion of the metal oxide on the rGO sheets. The functional group of the as synthesized metal oxide and the rGO nanocomposites, and its individual constituents, were identified through the FTIR and XPS studies, respectively. The composite materials showed higher specific capacitance then the pure materials, with rGO spinal metal oxide nanocomposites showing maximum specific capacitance of 396 F/g at 1 A/g. Furthermore, the hybrid super capacitor exhibits the excellent cyclic stability 2000 cycles with 95.6% retention. The photocatalytic properties of the synthesized rGO nanocomposites were analyzed with the help of malachite green dye. For pure metal oxide, the degradation rate was only around 65% within 120 min, while for rGO metal oxide nanocomposites, more than 80% of MG were degraded.

Antioxidant, Anti-Bacterial, and Congo Red Dye Degradation Activity of AgxO-Decorated Mustard Oil-Derived rGO Nanocomposites.

Scaling up the production of functional reduced graphene oxide (rGO) and its composites requires the use of low-cost, simple, and sustainable synthesis methods, and renewable feedstocks. In this study, silver oxide-decorated rGO (AgxO-rGO) composites were prepared by open-air combustion of mustard oil, essential oil-containing cooking oil commercially produced from the seeds of Brassica juncea. Silver oxide (AgxO) nanoparticles (NPs) were synthesized using Coleus aromaticus leaf extract as a reducing agent. Formation of mustard seed rGO and AgxO NPs was confirmed by UV-visible characteristic peaks at 258 nm and 444 nm, respectively. rGO had a flake-like morphology and a crystalline structure, with Raman spectra showing clear D and G bands with an ID/IG ratio of 0.992, confirming the fewer defects in the as-prepared mustard oil-derived rGO (M-rGO). The rGO-AgxO composite showed a degradation efficiency of 81.9% with a rate constant k-1 of 0.9506 min-1 for the sodium salt of benzidinediazo-bis-1-naphthylamine-4-sulfonic acid (known as the azo dye Congo Red) in an aqueous solution under visible light irradiation. The composite also showed some antimicrobial activity against Klebsilla pneomoniae, Escherichiacoli, and Staphylococcusaureus bacterial cells, with inhibition zones of ~15, 18, and 14 mm, respectively, for a concentration of 300 µg/mL. At 600 µg/mL concentration, the composite also showed moderate scavenging activity for 2,2-diphenyl-1-picrylhydrazyl of ~30.6%, with significantly lower activities measured for AgxO (at ~18.1%) and rGO (~8%) when compared to control.

Potential of plant secondary metabolite-based polymers to enhance wound healing.

There is a global epidemic of non-healing wounds. Chronic inflammation, overexpression of pro-inflammatory cytokines, oxidative stress and bacterial infection are implicated in delayed wound healing. Natural extracts are a rich source of bioactive molecules called plant secondary metabolites (PSMs) that include terpenes and phenols. These molecules may facilitate wound healing through their antioxidant, anti-inflammatory, and antibacterial activity. After briefly outlining the process of wound healing and how it is compromised in chronic wounds, this review focuses on investigating how PSMs-based polymers may improve wound healing. Best methods for incorporating PSMs into wound dressings are reviewed and critically compared. The exiting body of literature strongly suggests that PSMs-based polymers incorporated into wound dressings could have clinical value in aiding wound healing. STATEMENT OF SIGNIFICANCE: Chronic wounds develop by the persistence of inflammation, oxidative stress and infection. Chronic wounds affect the worldwide population, by reducing quality of life of patients with significant cost to healthcare systems. To help chronic wounds to heal and overcome this burden, materials with anti-inflammatory, antioxidant and antibacterial properties are required. Plant secondary metabolites (PSMs) are volatile materials that have all these properties. PSMs-based polymers can be fabricated by polymerization techniques. The present review provides an overview of the state-of-the-art of the wound healing mechanisms of PSMs. Current developments in the field of PSMs-based polymers are reviewed and their potential use as wound dressings is also covered.

Controlled Deposition of Nanostructured Hierarchical TiO2 Thin Films by Low Pressure Supersonic Plasma Jets.

Plasma-assisted supersonic jet deposition (PA-SJD) is a precise technique for the fabrication of thin films with a desired nanostructured morphology. In this work, we used quadrupole mass spectrometry of the neutral species in the jet and the extensive characterization of TiO2 films to improve our understanding of the relationship between jet chemistry and film properties. To do this, an organo-metallic precursor (titanium tetra-isopropoxide or TTIP) was first dissociated using a reactive argon-oxygen plasma in a vacuum chamber and then delivered into a second, lower pressure chamber through a nozzle. The pressure difference between the two chambers generated a supersonic jet carrying nanoparticles of TiO2 in the second chamber, and these were deposited onto the surface of a substrate located few centimeters away from the nozzle. The nucleation/aggregation of the jet nanoparticles could be accurately tuned by a suitable choice of control parameters in order to produce the required structures. We demonstrate that high-quality films of up to several µm in thickness and covering a surface area of few cm2 can be effectively produced using this PA-SJD technique.

Decontamination-Induced Modification of Bioactivity in Essential Oil-Based Plasma Polymer Coatings.

Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance under standard operating conditions; however, when used in e.g., a dental implant, these coatings may inadvertently become subject to in situ cleaning treatments, such as those using an atmospheric pressure plasma jet, a promising tool for the effective in situ removal of biofilms from tissues and implant surfaces. Here, we investigated the effect of such an exposure on the antimicrobial performance of the Melaleuca alternifolia polymer coating. It was found that direct exposure of the polymer coating surface to the jet for periods less than 60 s was sufficient to induce changes in its surface chemistry and topography, affecting its ability to retard subsequent microbial attachment. The exact effect of the jet exposure depended on the chemistry of the polymer coating, the length of plasma treatment, cell type, and incubation conditions. The change in the antimicrobial activity for polymer coatings fabricated at powers of 20-30 W was not statistically significant due to their limited baseline bioactivity. Interestingly, the bioactivity of polymer coatings fabricated at 10 and 15 W against Staphylococcus aureus cells was temporarily improved after the treatment, which could be attributed to the generation of loosely attached bioactive fragments on the treated surface, resulting in an increase in the dose of the bioactive agents being eluted by the surface. Attachment and proliferation of Pseudomonas aeruginosa cells and mixed cultures were less affected by changes in the bioactivity profile of the surface. The sensitivity of the cells to the change imparted by the jet treatment was also found to be dependent on their origin culture, with mature biofilm-derived P. aeruginosa bacterial cells showing a greater ability to colonize the surface when compared to its planktonic broth-grown counterpart. The presence of plasma-generated reactive oxygen and nitrogen species in the culture media was also found to enhance the bioactivity of polymer coatings fabricated at power levels of 10 and 15 W, due to a synergistic effect arising from simultaneous exposure of cells to reactive oxygen and nitrogen species (RONS) and eluted bioactive fragments. These results suggest that it is important to consider the possible implications of inadvertent changes in the properties and performance of plasma polymer coatings as a result of exposure to in situ decontamination, to both prevent suboptimal performance and to exploit possible synergies that may arise for some polymer coating-surface treatment combinations.

Functional nanomaterials, synergisms, and biomimicry for environmentally benign marine antifouling technology.

Marine biofouling remains one of the key challenges for maritime industries, both for seafaring and stationary structures. Currently used biocide-based approaches suffer from significant drawbacks, coming at a significant cost to the environment into which the biocides are released, whereas novel environmentally friendly approaches are often difficult to translate from lab bench to commercial scale. In this article, current biocide-based strategies and their adverse environmental effects are briefly outlined, showing significant gaps that could be addressed through advanced materials engineering. Current research towards the use of natural antifouling products and strategies based on physio-chemical properties is then reviewed, focusing on the recent progress and promising novel developments in the field of environmentally benign marine antifouling technologies based on advanced nanocomposites, synergistic effects and biomimetic approaches are discussed and their benefits and potential drawbacks are compared to existing techniques.

Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition.

If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality.

Plasma and Polymers: Recent Progress and Trends.

Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages over other processing methods. The fluxes of energy and matter toward the surface enable rapid and efficient processing, whereas the charged nature of plasma-generated particles provides a means for their control. The range of materials that can be treated by plasmas is incredibly broad, spanning pure polymers, polymer-metal, polymer-wood, polymer-nanocarbon composites, and others. In this review, we briefly outline some of the recent examples of the state-of-the-art in the plasma-based polymer treatment and functionalization techniques.

Translocation of silica nanospheres through giant unilamellar vesicles (GUVs) induced by a high frequency electromagnetic field.

Membrane model systems capable of mimicking live cell membranes were used for the first time in studying the effects arising from electromagnetic fields (EMFs) of 18 GHz where membrane permeability was observed following exposure. A present lack of understanding of the mechanisms that drive such a rapid change in membrane permeabilization as well as any structural or dynamic changes imparted on biomolecules affected by high-frequency electromagnetic irradiation limits the use of 18 GHz EMFs in biomedical applications. A phospholipid, 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) labelled with a fluorescent marker 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(lissamine rhodamine B sulfonyl) (rhodamine-DOPE) was used in constructing the giant unilamellar vesicles (GUVs). After three cycles of exposure, enhanced membrane permeability was observed by the internalisation of hydrophilic silica nanospheres of 23.5 nm and their clusters. All-atom molecular dynamics simulations of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) membranes exposed to high frequency electric fields of different field strengths showed that within the simulation timeframe only extremely high strength fields were able to cause an increase in the interfacial water dynamics characterized by water dipole realignments. However, a lower strength, high frequency EMF induced changes of the water hydrogen bond network, which may contribute to the mechanisms that facilitate membrane permeabilization in a longer timeframe.

Cold Atmospheric Plasma: A Promising Controller of Cancer Cell States.

Rich in reactive oxygen and nitrogen species, cold atmospheric plasma has been shown to effectively control events critical to cancer progression; selectively inducing apoptosis, reducing tumor volume and vasculature, and halting metastasis by taking advantage of, e.g., synergies between hydrogen peroxide and nitrites. This paper discusses the efficacy, safety and administration of cold atmospheric plasma treatment as a potential tool against cancers, with a focus on the mechanisms by which cold atmospheric plasma may affect critical transitional switches that govern tumorigenesis: the life/death control, tumor angiogenesis and epithelial-mesenchymal transition, and drug sensitivity spectrum. We introduce the possibility of modeling cell transitions between the normal and cancerous states using cold atmospheric plasma as a novel research avenue to enhance our understanding of plasma-aided control of oncogenesis.

Power-to-chemicals: Low-temperature plasma for lignin depolymerisation in ethanol.

Lignin valorisation into renewable fuels and platform chemicals is desirable but still encounters major challenges due to lignin's recalcitrant structure, and the lack of cost-, energy-, and material efficient conversion processes. Herein, we report a low-temperature plasma-based route to lignin depolymerisation at mild conditions. The discharge over ethanol surface locally creating a high-energy and reactive environment rich in free electrons, energetic H radicals, and other reactive species, is well suited for lignin depolymerisation. Furthermore, assisted with a Fenton reaction (by adding Fe2O3 and H2O2) to sustain a more oxidative environment, the lignin conversion yield increases from 42.6% to 66.0%. Thus-obtained renewable chemicals are rich in aromatics and dicarboxylic acid derivatives. The proposed strategy on intensifying reactive chemistry by high-power plasmas enables an effective power-to-chemicals conversion of lignin and may provide useful guidelines for modern biorefineries.