Understanding and Controlling Electrostatic Discharge in Triboelectric Nanogenerators.

Triboelectric nanogenerators (TENGs) have been widely used to harness various forms of mechanical energy for conversion to electrical energy. However, the contentious challenge in characterising TENGs is the lack of standard protocols for assessing mechanical-to-electrical energy conversion processes. Herein, macroscopic signal analysis is used to identify three key charging events within triboelectric signals: charge induction (CI), contact electrification (CE), and electrostatic discharge (ESD). By considering two phases of motion during contact-separation (approach and departure of the contact materials), CI arising from the motion of bound surface charge (varying electric field) between opposing contact materials is shown to dominate the measured displacement current signal, rather than the process of CE itself. Furthermore, the conventional signal (i. e., voltage, current, charge) interpretation of CE and CI during approach and departure phases is re-assessed, to indicate that the sudden spike of current often observed immediately prior to contact (or after separation) arises from polarity inverting electrostatic discharge (ESD). This aspect of the measured triboelectric effect, which is often ignored, is crucial for the design of TENGs and hence, techniques to enhance the understanding and control over the stochastic occurrence of ESDs is explored. The methods proposed for the deconvolution of the macroscopic signal components of TENGs, and mitigation of ESD occurrences, will allow for precise quantification of the associated charging events. The applications of this study will template the design and development of future super-TENGs with optimised energy conversion capabilities.

The Impact of Activating Agents on Non-Enzymatic Nucleic Acid Extension Reactions.

Non-enzymatic template-directed primer extension is increasingly being studied for the production of RNA and DNA. These reactions benefit from producing RNA or DNA in an aqueous, protecting group free system, without the need for expensive enzymes. However, these primer extension reactions suffer from a lack of fidelity, low reaction rates, low overall yields, and short primer extension lengths. This review outlines a detailed mechanistic pathway for non-enzymatic template-directed primer extension and presents a review of the thermodynamic driving forces involved in entropic templating. Through the lens of entropic templating, the rate and fidelity of a reaction are shown to be intrinsically linked to the reactivity of the activating agent used. Thus, a strategy is discussed for the optimization of non-enzymatic template-directed primer extension, providing a path towards cost-effective in vitro synthesis of RNA and DNA.

Quantifying environmental emissions of microplastics from urban rivers in Melbourne, Australia.

This study aims to understand the amount and type of microplastics flowing into Port Phillip Bay from urban rivers around Melbourne. Water samples were collected from the Patterson, Werribee, Maribyrnong, and Yarra Rivers, which contribute 97 % to the total flow into Port Phillip Bay. On average, the rivers contained a mean of 9 ± 15 microplastics/L and ranged from 4 ± 3 microplastics/L (Patterson) to 22 ± 11 microplastics/L (Werribee). Of the eight polymers investigated, polyamide and polypropylene were the most frequently detected polymers. Using the mean concentration of each river, the flow of microplastics into Port Philip Bay was estimated to be 7.5 × 106 microplastics per day and 3.7 × 1010 microplastics per year. To fully understand the fate and transport of microplastics into Port Phillip Bay, this study would be the foundation for a more in-depth investigation. Here, further samples will be collected at more points along the river and at the midpoint of each season.

Macro-Size Regenerated Cellulose Fibre Embedded with Graphene Oxide with Antibacterial Properties.

Macro-size regenerated cellulose fibres (RCFs) with embedded graphene oxide (GO) were fabricated by dissolving cellulose in a pre-cooled sodium hydroxide (NaOH)/urea solution and regenerated in sulphuric acid (H2SO4) coagulant. Initially, GO was found to disperse well in the cellulose solution due to intercalation with the cellulose; however, this cellulose-GO intercalation was disturbed during the regeneration process, causing agglomeration of GO in the RCF mixture. Agglomerated GO was confirmed at a higher GO content under a Dino-Lite microscope. The crystallinity index (CrI) and thermal properties of the RCFs increased with increasing GO loadings, up to 2 wt.%, and reduced thereafter. Cellulose-GO intercalation was observed at lower GO concentrations, which enhanced the crystallinity and thermal properties of the RCF-GO composite. It was shown that the GO exhibited antibacterial properties in the RCF-GO composite, with the highest bacterial inhibition against E. coli and S. aureus.

Electrospinning Triboelectric Laminates: A Pathway for Scaling Energy Harvesters.

Herein, a new paradigm of triboelectric polymers-the triboelectric laminate-a volumetric material with electromechanical response comparable to the benchmark soft piezoelectric material polyvinylidene difluoride is reported. The electromechanical response in the triboelectric laminate arises from aligned dipoles, generated from the orientation of contact electrification in the laminates bulk volume. The dipoles form between sequential bilayers consisting of two different electrospun polymer fibers of different diameter. The loose interface between the fiber bilayers ensures friction and triboelectric charging between two polymers. The electric output from the electrospun triboelectric laminate increases with increasing density of the bilayers. This system design has clear benefits over other flexible devices for mechanical energy harvesting as it does not require any poling procedures, and the electromechanical response is stable over 24 h of continuous operation. Moreover, the electromechanically responsive electrospun laminate can be made from all types of polymers, thus providing ample room for further improvements or functionalities such as stretchability, biodegradability, or biocompatibility. The concept of a triboelectric laminate can be introduced into existing triboelectric nanogenerator form factors, to dramatically increase charge harvesting of a variety of devices.

Evaluation of a lanthanide nanoparticle-based contrast agent for microcomputed tomography of porous channels in subchondral bone.

Osteoarthritis (OA) is a chronic joint disease that causes disability and pain. The osteochondral interface is a gradient tissue region that plays a significant role in maintaining joint health. It has been shown that during OA, increased neoangiogenesis creates porous channels at the osteochondral interface allowing the transport of molecules related to OA. Importantly, the connection between these porous channels and the early stages of OA development is still not fully understood. Microcomputed tomography (microCT) offers the ability to image the porous channels at the osteochondral interface, however, a contrast agent is necessary to delineate the different X-ray attenuations of the tissues. In this study BaYbF5 -SiO2 nanoparticles are synthesized and optimized as a microCT contrast agent to obtain an appropriate contrast attenuation for subsequent segmentation of structures of interest, that is, porous channels, and mouse subchondral bone. For this purpose, BaYbF5 nanoparticles were synthesized and coated with a biocompatible silica shell (SiO2 ). The optimized BaYbF5 -SiO2 27 nm nanoparticles exhibited the highest average microCT attenuation among the biocompatible nanoparticles tested. The BaYbF5 -SiO2 27 nm nanoparticles increased the mean X-ray attenuation of structures of interest, for example, porous channel models and mouse subchondral bone. The BaYbF5 -SiO2 contrast attenuation was steady after diffusion into mouse subchondral bone. In this study, we obtained for the first time, the average microCT attenuation of the BaYbF5 -SiO2 nanoparticles into porous channel models and mouse subchondral bone. In conclusion, BaYbF5 -SiO2 nanoparticles are a potential contrast agent for imaging porous channels at the osteochondral interface using microCT.

Enhancement of DNAzymatic activity using iterative in silico maturation.

DNAzyme-based (catalytic nucleic acid) biosensing technology is recognised as a valuable biosensing tool in diagnostic medicine and seen as a cheaper, more stable alternative to antibodies or enzymes. However, like enzyme discovery, no method exists to predict DNAzyme sequences that result in high catalytic activity using computer software (in silico). In this work, iterative in silico maturation and in vitro evaluation were applied to a DNAzyme oligodeoxynucleotide (ODN) sequence to elucidate novel synthetic sequences with enhanced DNAzyme activity. An already well-known model DNAzyme, the G-quadruplex/hemin complex, was iterated over eight generations to elucidate synthetic sequences that were up to five times faster than the original parent sequence. By combining molecular dynamics simulations, we found that the POD-mimicking activities were largely affected by docking modes and the tightness of locking between complexes. Ultimately, the theoretical models showed significant sequence-dependencies.

Energy Interplay in Materials: Unlocking Next-Generation Synchronous Multisource Energy Conversion with Layered 2D Crystals.

Layered 2D crystals have unique properties and rich chemical and electronic diversity, with over 6000 2D crystals known and, in principle, millions of different stacked hybrid 2D crystals accessible. This diversity provides unique combinations of properties that can profoundly affect the future of energy conversion and harvesting devices. Notably, this includes catalysts, photovoltaics, superconductors, solar-fuel generators, and piezoelectric devices that will receive broad commercial uptake in the near future. However, the unique properties of layered 2D crystals are not limited to individual applications and they can achieve exceptional performance in multiple energy conversion applications synchronously. This synchronous multisource energy conversion (SMEC) has yet to be fully realized but offers a real game-changer in how devices will be produced and utilized in the future. This perspective highlights the energy interplay in materials and its impact on energy conversion, how SMEC devices can be realized, particularly through layered 2D crystals, and provides a vision of the future of effective environmental energy harvesting devices with layered 2D crystals.

Assessing exposure of the Australian population to microplastics through bottled water consumption.

The presence of microplastics in the environment is substantially documented; however, the pathways of dietary exposure to microplastics are not yet well understood. This is the first study to document the presence of microplastics in bottled water sold in Australia from commercial outlets. In total, 16 brands of bottled water (Australian Sourced: n = 11, Imported: n = 5) sold in the two largest supermarkets in Australia were analysed in triplicate (n = 48) for the presence of polyethylene, PE; polystyrene, PS; polypropylene, PP; polyvinyl chloride, PVC; polyethylene terephthalate, PET; polycarbonate, PC; polymethylmethacrylate, PMMA; and polyamide, PA. Microplastics were detected in 94% (n = 15) of the samples, with PP (n = 14, 88%), PET (n = 10, 63%), PA (n = 7, 44%), and PE (n = 6, 38%) the most frequently detected. On average, a litre of bottled water contained 13 ± 19 (St Dev) microplastics, ranging from 0 to 80 microplastics/L. The average size of the microplastics identified in this study was 77 ± 22 µm. It was found that bottled water sourced and packaged overseas contained four times as many microplastics compared to bottled water sourced in Australia. It was estimated that in 2017, 28.3% of the Australian population consumed on average 30.8 L of bottled water; therefore, using the result from this study it is estimated that Australians are exposed to 400 microplastics annually through the consumption of bottled water. To understand the total amount of microplastics that Australians could be exposed to through dietary routes, further work is required to observe the presence of microplastics in other beverages and food.

Microplastic contamination of an unconfined groundwater aquifer in Victoria, Australia.

This is the first study to show microplastics contamination in an alluvial sedimentary aquifer that has been capped from the atmosphere. Microplastics are often reported in biotic and abiotic environments, but little is known about their occurrence in groundwater systems. In this study, eight of the most commonly found microplastics in the environment (polyethylene, PE; polystyrene, PS; polypropylene, PP; polyvinyl chloride, PVC; polyethylene terephthalate, PET; polycarbonate, PC; polymethylmethacrylate, PMMA; and polyamide, PA) were analysed in triplicate groundwater samples (n = 21) from five sampling sites across seven capped groundwater monitoring bores from Bacchus Marsh (Victoria, Australia) using Agilent's novel Laser Direct Infra-Red (LDIR) imaging system. Microplastics were detected in all samples, with PE, PP, PS and PVC detected in all seven bores. The average size of the microplastics identified was 89 ± 55 µm (St.Dev.), ranging from 18 to 491 µm. The average number of microplastics detected across all sites was 38 ± 8 microplastics/L, ranging from 16 to 97 particles/L. PE and PVC in total contributed to 59% of the total sum of microplastics detected. PE was consistently detected in all seven bores (average: 11 particles/L), while PVC was more pronounced in a bore adjacent to a meat processor (52 particles/L) compared to that of its overall average of 12 particles/L. A statistically significant positive correlation was observed between PVC and PS (R = 0.934, p ≤0.001). As this study collected samples from capped groundwater bores, the most probable avenue for microplastics was permeation through soil. Therefore, to further understand the fate and transport of microplastics within a groundwater system, it is necessary to analyse a greater range of groundwater bores not only from Australia but throughout the world.

Biofunctionality with a twist: the importance of molecular organisation, handedness and configuration in synthetic biomaterial design.

The building blocks of life - nucleotides, amino acids and saccharides - give rise to a large variety of components and make up the hierarchical structures found in Nature. Driven by chirality and non-covalent interactions, helical and highly organised structures are formed and the way in which they fold correlates with specific recognition and hence function. A great amount of effort is being put into mimicking these highly specialised biosystems as biomaterials for biomedical applications, ranging from drug discovery to regenerative medicine. However, as well as lacking the complexity found in Nature, their bio-activity is sometimes low and hierarchical ordering is missing or underdeveloped. Moreover, small differences in folding in natural biomolecules (e.g., caused by mutations) can have a catastrophic effect on the function they perform. In order to develop biomaterials that are more efficient in interacting with biomolecules, such as proteins, DNA and cells, we speculate that incorporating order and handedness into biomaterial design is necessary. In this review, we first focus on order and handedness found in Nature in peptides, nucleotides and saccharides, followed by selected examples of synthetic biomimetic systems based on these components that aim to capture some aspects of these ordered features. Computational simulations are very helpful in predicting atomic orientation and molecular organisation, and can provide invaluable information on how to further improve on biomaterial designs. In the last part of the review, a critical perspective is provided along with considerations that can be implemented in next-generation biomaterial designs.

A bright future for engineering piezoelectric 2D crystals.

The piezoelectric effect, mechanical-to-electrical and electrical-to-mechanical energy conversion, is highly beneficial for functional and responsive electronic devices. To fully exploit this property, miniaturization of piezoelectric materials is the subject of intense research. Indeed, select atomically thin 2D materials strongly exhibit the piezoelectric effect. The family of 2D crystals consists of over 7000 chemically distinct members that can be further manipulated in terms of strain, functionalization, elemental substitution (i.e. Janus 2D crystals), and defect engineering to induce a piezoelectric response. Additionally, most 2D crystals can stack with other similar or dissimilar 2D crystals to form a much greater number of complex 2D heterostructures whose properties are quite different to those of the individual constituents. The unprecedented flexibility in tailoring 2D crystal properties, coupled with their minimal thickness, make these emerging highly attractive for advanced piezoelectric applications that include pressure sensing, piezocatalysis, piezotronics, and energy harvesting. This review summarizes literature on piezoelectricity, particularly out-of-plane piezoelectricity, in the vast family of 2D materials as well as their heterostructures. It also describes methods to induce, enhance, and control the piezoelectric properties. The volume of data and role of machine learning in predicting piezoelectricity is discussed in detail, and a prospective outlook on the 2D piezoelectric field is provided.

Spatially isolated redox processes enabled by ambipolar charge transport in multi-walled carbon nanotube mats.

This work demonstrates a simple dual-well device which enables spatially isolated solutions to undergo complementary redox reactions. The device functions by the ambipolar transport of charge carriers between two spatially isolated poly(dimethylsiloxane) (PDMS) microwells through an underlying multi-walled carbon nanotube (MWCNT) mat. This MWCNT mat enables charge carriers, produced from the decomposition of an analyte in one solution, to drive a redox reaction in a spatially isolated second colorimetric read-out solution via a potential difference between the wells. As proof-of-concept a visible colorimetric read-out was shown using an enzyme, cytochrome c (reduced in 16 h), and the visualizing reagent 3,3',5,5'-tetramethylbenzidine (TMB) (oxidized in 2.5 h) for the detection of dithionite and hydrogen peroxide, respectively, without any external energy input. We discuss the origin of this phenomenon and highlight the ability of MWCNTs to accept and transport both electrons and holes efficiently between spatially isolated solutions giving rise to a highly versatile sensor suitable for use in simple, low-cost point-of-care diagnostics.

Probing Contact Electrification: A Cohesively Sticky Problem.

Contact electrification and the triboelectric effect are complex processes for mechanical-to-electrical energy conversion, particularly for highly deformable polymers. While generating relatively low power density, contact electrification can occur at the contact-separation interface between nearly any two polymer surfaces. This ubiquitousness of surfaces enables contact electrification to be an important phenomenon to understand energy conversion and harvesting applications. The mechanism of charge generation between polymeric materials remains ambiguous, with electron transfer, material (also known as mass) transfer, and adsorbed chemical species transfer (including induced ionization of water and other molecules) all being proposed as the primary source of the measured charge. Often, all sources of charge, except electron transfer, are dismissed in the case of triboelectric energy harvesters, leading to the generation of the "triboelectric series", governed by the ability of a polymer to lose, or accept, an electron. Here, this sole focus on electron transfer is challenged through rigorous experiments, measuring charge density in polymer-polymer (196 polymer combinations), polymer-glass (14 polymers), and polymer-liquid metal (14 polymers) systems. Through the investigation of these interfaces, clear evidence of material transfer via heterolytic bond cleavage is provided. Based on these results, a generalized model considering the cohesive energy density of polymers as the critical parameter for polymer contact electrification is discussed. This discussion clearly shows that material transfer must be accounted for when discussing the source of charge generated by polymeric mechanical energy harvesters. Thus, a correlated physical property to understand the triboelectric series is provided.

Interfacial piezoelectric polarization locking in printable Ti3C2Tx MXene-fluoropolymer composites.

Piezoelectric fluoropolymers convert mechanical energy to electricity and are ideal for sustainably providing power to electronic devices. To convert mechanical energy, a net polarization must be induced in the fluoropolymer, which is currently achieved via an energy-intensive electrical poling process. Eliminating this process will enable the low-energy production of efficient energy harvesters. Here, by combining molecular dynamics simulations, piezoresponse force microscopy, and electrodynamic measurements, we reveal a hitherto unseen polarization locking phenomena of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) perpendicular to the basal plane of two-dimensional (2D) Ti3C2Tx MXene nanosheets. This polarization locking, driven by strong electrostatic interactions enabled exceptional energy harvesting performance, with a measured piezoelectric charge coefficient, d33, of -52.0 picocoulombs per newton, significantly higher than electrically poled PVDF-TrFE (approximately -38 picocoulombs per newton). This study provides a new fundamental and low-energy input mechanism of poling fluoropolymers, which enables new levels of performance in electromechanical technologies.

Grapevine waste in sustainable hybrid particleboard production.

Grapevine prunings are an ideal sustainable additive to wood-based composites, providing a powerful resource stream, reducing the demand of logging of forests. Valorisation of grapevine prunings into commercial products further reduces greenhouse gas emissions caused by waste vegetation break-down. Particleboard is a ubiquitous wood-based composite with over 97 million m3 produced annually from soft wood. Agricultural crop waste is ideal for incorporation into particleboard, however maintaining the density and mechanical properties with these additives is imperative. Herein, mixed grapevine/pine cores comprising of 100%, 25% and 10% grapevine particles were produced and the mechanical and density properties of 16 mm thick moisture resistant particleboards were evaluated. Hybrid particleboards based on 10% grapevine and 90% pine showed great promise, surpassing global industry standards for key mechanical properties. Hybrid particleboards displayed a higher surface density and a steeper vertical density gradient than the 100% pine control boards, due to grapevine particles filling voids between the pine, thereby improving the mechanical properties. This work forms a foundation for the continued study of agricultural waste into wood-based composites.

Measuring Piezoelectric Output-Fact or Friction?

Piezoelectric polymers are emerging as exceptionally promising materials for energy harvesting. While the theoretical figures of merit for piezoelectric polymers are comparable to ceramics, the measurement techniques need to be retrofitted to account for the different mechanical properties of the softer polymeric materials. Here, how contact electrification, including friction and contact separation, is often mistaken for piezoelectric charge is examined, and a perspective for how to separate these effects is provided. The state of the literature is assessed, and recommendations are made for clear and simple guidelines in reporting, for both sample geometry and testing methods, to enable accurate determination of piezoelectric figures of merit in polymers. Such improvements will allow an understanding of what types of material manipulation are required in order to enhance the piezoelectric output from polymers and enable the next generation of polymer energy harvester design.

Personalized, Mechanically Strong, and Biodegradable Coronary Artery Stents via Melt Electrowriting.

Biodegradable coronary artery stents are sought-after alternatives to permanent stents. These devices are designed to degrade after the blood vessel heals, leaving behind a regenerated artery. The original generation of clinically available biodegradable stents required significantly thicker struts (∼150 µm) than nondegradable ones to ensure sufficient mechanical strength. However, these thicker struts proved to be a key contributor to the clinical failure of the stents. A current challenge lies in the fabrication of stents that possess both thin struts and adequate mechanical strength. In this contribution, we describe a method for the bottom-up, additive manufacturing of biodegradable composite stents with ultrathin fibers and superior mechanical properties compared to the base polymer. Specifically, we illustrate that melt electrowriting (MEW) can be used to 3D print composite structures with thin struts (60-80 µm) and a high degree of geometric complexity required for stenting applications. Additionally, this technology allows additive manufacture of personalized stents that are customized to a patient's unique anatomy and disease state. Furthermore, we illustrate that polycaprolactone-reduced graphene oxide nanocomposites have superior mechanical properties compared to original polycaprolactone without detriment to the material's cytocompatibility and that customizable stent-like structures can be fabricated from these materials with struts as thin as 60 µm, well below the target value for clinical use of 80 µm.

Opportunities and Challenges in DNA-Hybrid Nanomaterials.

Nature has inspired the development of many life-like materials. Although still simplistic, key biological functionalities have been incorporated, enabling a wide variety of applications. DNA-based systems, in particular, show high promise due to their ability to merge specific Watson-Crick base pairing with unique properties that are also programmable, scalable, or dynamic. By combining the fields of DNA-based covalent polymers, DNA origami, and DNA-functionalized supramolecular polymers, new frontiers in next-generation DNA-based hybrid materials that can outperform current bioartificial systems will be realized. Many challenges must still be overcome before this emerging technology can be materialized.