The fractal geometry of polymeric materials surfaces: surface area and fractal length scales.

Using three common polymeric materials (polypropylene (PP), polytetrafluoroethylene (PTFE) and polycaprolactone (PCL)), a standard oxygen-plasma treatment and atomic force microscopy (AFM), we performed a scaling analysis of the modified surfaces yielding effective Hurst exponents (H ≃ 0.77 ± 0.02 (PP), ≃0.75 ± 0.02 (PTFE), and ≃0.83 ± 0.02 (PCL)), for the one-dimensional profiles, corresponding to the transversal sections of the surface, by averaging over all possible profiles. The surface fractal dimensions are given by ds = 3 - H, corresponding to ds ≃ 2.23, 2.25, and 2.17, respectively. We present a simple method to obtain the surface area from the AFM images stored in a matrix of 512 × 512 pixels. We show that the considerable increase found in the surface areas of the treated samples w.r.t. to the non-treated ones (43% for PP, 85% for PTFE, and 25% for PCL, with errors of about 2.5% on samples of 2 µm × 2 µm) is consistent with the observed increase in the length scales of the fractal regime to determine H, typically by a factor of about 2, extending from a few to hundreds of nanometres. We stipulate that the intrinsic roughness already present in the original non-treated material surfaces may serve as 'fractal' seeds undergoing significant height fluctuations during plasma treatment, suggesting a pathway for the future development of advanced material interfaces with large surface areas at the nanoscale.

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.

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.

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.

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.

RpoS proteolysis is controlled directly by ATP levels in Escherichia coli.

The master regulator of stationary phase in Escherichia coli, RpoS, responds to carbon availability through changes in stability, but the individual steps in the pathway are unknown. Here we systematically block key steps of glycolysis and the citric acid cycle and monitor the effect on RpoS degradation in vivo. Nutrient upshifts trigger RpoS degradation independently of protein synthesis by activating metabolic pathways that generate small energy molecules. Using metabolic mutants and inhibitors, we show that ATP, but not GTP or NADH, is necessary for RpoS degradation. In vitro reconstitution assays directly demonstrate that ClpXP fails to degrade RpoS, but not other proteins, at low ATP hydrolysis rates. These data suggest that cellular ATP levels directly control RpoS stability.

Free-standing alumina nanobottles and nanotubes pre-integrated into nanoporous alumina membranes.

A novel interfacial structure consisting of long (up to 5 µm), thin (about 300 nm), highly-ordered, free-standing, highly-reproducible aluminum oxide nanobottles and long tubular nanocapsules attached to a rigid, thin (less than 1 µm) nanoporous anodic alumina membrane is fabricated by simple, fast, catalyst-free, environmentally friendly voltage-pulse anodization. A growth mechanism is proposed based on the formation of straight channels in alumina membrane by anodization, followed by neck formation due to a sophisticated voltage control during the process. This process can be used for the fabrication of alumina nanocontainers with highly controllable geometrical size and volume, vitally important for various applications such as material and energy storage, targeted drug and diagnostic agent delivery, controlled drug and active agent release, gene and biomolecule reservoirs, micro-biologically protected platforms, nano-bioreactors, tissue engineering and hydrogen storage.

Vertically-aligned graphene flakes on nanoporous templates: morphology, thickness, and defect level control by pre-treatment.

Various morphologies of the vertically-aligned graphene flakes were fabricated on the nanoporous templates treated with metal ions in solutions, as well as coated with a thin gold layer and activated in the low-temperature Ar plasma. The thickness and level of structural defects in the graphene flakes could be effectively controlled by a proper selection of the pre-treatment method. We have also demonstrated that various combinations of the flake thickness and defect levels can be obtained, and the morphology and density of the graphene pattern can be effectively controlled. The result obtained could be of interest for various applications requiring fabrication of large graphene networks with controllable properties.

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.

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.

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.

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.

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.

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.

Versatile modes of peptide recognition by the AAA+ adaptor protein SspB.

Energy-dependent proteases often rely on adaptor proteins to modulate substrate recognition. The SspB adaptor binds peptide sequences in the stress-response regulator RseA and in ssrA-tagged proteins and delivers these molecules to the AAA+ ClpXP protease for degradation. The structure of SspB bound to an ssrA peptide is known. Here, we report the crystal structure of a complex between SspB and its recognition peptide in RseA. Notably, the RseA sequence is positioned in the peptide-binding groove of SspB in a direction opposite to the ssrA peptide, the two peptides share only one common interaction with the adaptor, and the RseA interaction site is substantially larger than the overlapping ssrA site. This marked diversity in SspB recognition of different target proteins indicates that it is capable of highly flexible and dynamic substrate delivery.

Hierarchical Doped Gelatin-Derived Carbon Aerogels: Three Levels of Porosity for Advanced Supercapacitors.

Nitrogen-doped graphene-based aerogels with three levels of hierarchically organized pores were prepared via a simple environmentally friendly process, and successfully tested in supercapacitor applications. Mesopores and macropores were formed during the aerogel preparation followed by carbonization and its chemical activation by potassium hydroxide (KOH). These mesopores and macropores consist of amorphous carbon and a 3D graphene framework. Thermal treatment at 700 °C, 800 °C, 900 °C in N2 atmosphere was done to etch out the amorphous carbon and obtain a stable N-doped 3D graphene. Specific capacitance values obtained from the electrochemical measurements are in the range of 232-170 F× g-1. The thus fabricated structures showed excellent cyclic stability, suggesting that these materials have potential as electrodes for solid asymmetric supercapacitors.

Fabrication of Nano-Onion-Structured Graphene Films from Citrus sinensis Extract and Their Wetting and Sensing Characteristics.

Graphene and its derivatives have acquired substantial research attention in recent years because of their wide range of potential applications. Implementing sustainable technologies for fabricating these functional nanomaterials is becoming increasingly apparent, and therefore, a wide spectrum of naturally derived precursors has been identified and reformed through various established techniques for the purpose. Nevertheless, most of these methods could only be considered partially sustainable because of their complexity as well as high energy, time, and resource requirements. Here, we report the fabrication of carbon nano-onion-interspersed vertically oriented multilayer graphene nanosheets through a single-step, environmentally benign radio frequency plasma-enhanced chemical vapor deposition process from a low-cost carbon feedstock, the oil from the peel of Citrus sinensis orange fruits. C. sinensis essential oil is a volatile aroma liquid principally composed of nonsynthetic hydrocarbon limonene. Transmission electron microscopy studies on the structure unveiled the presence of hollow quasi-spherical carbon nano-onion-like structures incorporated within graphene layers. The as-fabricated nano-onion-incorporated graphene films exhibited a highly hydrophobic nature showing a water contact angle of up to 1290. The surface energies of these films were in the range of 41 to 35 mJ·m-2. Moreover, a chemiresistive sensor directly fabricated using C. sinensis-derived onion-structured graphene showed a p-type semiconductor nature and a promising response to acetone at room temperature. With its unique morphology, surface properties, and electrical characteristics, this material is expected to be useful for a wide range of applications.