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.

Elastomer nanocomposites containing MXene for mechanical robustness and electrical and thermal conductivity.

A novel 2D nanomaterial, Ti3C2Tx MXene, added conductivity and reinforcement to a common elastomer, nitrile butadiene rubber (NBR). X-ray diffraction revealed the intercalation of lithium ions and elastomer chains into the MXene interlayer spacing, which enabled exfoliation in the elastomer. The reaction between MXene and NBR was proved by a stepwise Fourier transform infrared spectroscopy. With increase in MXene fractions, electrical and thermal conductivity of the composite increased to 9 × 10-5 S cm-1 and 0.69 W m-1 K-1, respectively. At only 2.8 vol% MXene, a swelling ratio of 1.61 was achieved, representing a 75% reduction compared to NBR containing either graphene or carbon nanotubes at the same filler fraction. Tensile tests showed that with the increase in MXene content, Young's modulus increased while both tensile strength and elongation at break first increased and then decreased. Overall, latex compounding proved to be an efficient technique for forming NBR/MXene nanocomposites. The revealed reaction between MXene and NBR to create functional polymer nanocomposites could provide a platform for utilising MXene for other polymers.

Cell sheets in cell therapies.

This review aims to provide a broad introduction to the use of cell sheets and the role of materials in the delivery of cell sheets to patients within a clinical setting. Traditionally, cells sheets have been, and currently are, fabricated using established and accepted cell culture methods within standard formats (e.g., petri dishes) utilizing biological substrates. Synthetic surfaces provide a far more versatile system for culturing and delivering cell sheets. This has the potential to positively affect quality, and efficient, localized cell delivery has a significant impact on patient outcome and on the overall cost of goods. We highlight current applications of these advanced carriers and future applications of these surfaces and cell sheets with an emphasis both on clinical use and regulatory requirements.

Promiscuous hydrogen in polymerising plasmas.

Historically, there have been two opposing views regarding deposition mechanisms in plasma polymerisation, radical growth and direct ion deposition, with neither being able to fully explain the chemistry of the resultant coating. Deposition rate and film chemistry are dependent on the chemistry of the plasma phase and thus the activation mechanisms of species in the plasma are critical to understanding the relative contributions of various chemical and physical routes to plasma polymer formation. In this study, we investigate the roles that hydrogen plays in activating and deactivating reactive plasma species. Ethyl trimethylacetate (ETMA) is used as a representative organic precursor, and additional hydrogen is added to the plasma in the form of water and deuterium oxide. Optical emission spectroscopy confirms that atomic hydrogen is abundant in the plasma. Comparison of the plasma phase mass spectra of ETMA/H2O and ETMA/D2O reveals that (1) proton transfer from hydronium is a common route to charging precursors in plasma, and (2) hydrogen abstraction (activation) and recombination (deactivation) processes are much more dynamic in the plasma than previously thought. Consideration of the roles of hydrogen in plasma chemistry may then provide a more comprehensive view of deposition processes and bridge the divide between the two disparate schools of thought.

Synthesis of highly functionalised plasma polymer films from protonated precursor ions via the plasma α-γ transition.

Chemically functionalized surfaces may be produced via plasma polymerization, however a high degree of functional group retention is often difficult to achieve. Here, the plasma polymerization of three structurally related ester precursors, ethyl isobutyrate (EIB), methyl isobutyrate (MIB) and ethyl trimethylacetate (ETMA) is compared at low and high pressure. In moving from a low pressure to higher pressure regime, significant changes in the plasma chemistry and resulting plasma polymer deposit were observed with much higher retention of chemical functionality at the higher pressure observed. Until now these changes would have been attributed to a decrease in the energy/molecule, however we show by direct measurement of the chemistry and physics of the plasma that there is fundamental shift in the properties of the plasma and surface interactions which explain the results. At low pressure (α regime) precursor fragmentation and neutral deposition dominate resulting in poor functional group retention. Increasing the pressure such that the sheath region close to surfaces becomes collisional (γ regime) favours production of protonated precursor ions which retain functionality and dominate the deposition process rather than radical species.

Chemical and physical processes in the retention of functional groups in plasma polymers studied by plasma phase mass spectroscopy.

Surface engineering of functionalised polymer films is a rapidly expanding field of research with cross disciplinary implications and numerous applications. One method of generating functionalised polymer films is radio frequency induced plasma polymerisation which provides a substrate independent coating. However, there is currently limited understanding surrounding chemical interactions in the plasma phase and physical interactions at the plasma-surface interface, and their effect on functional group retention in the thin film. Here we investigate functionalised plasma polymer films generated from four precursors containing primary amines. Using XPS and fluorine tagging with 4-(trifluoromethyl)benzaldehyde, the primary amine content of plasma polymer films was measured as a function of applied power at constant precursor pressure. The results were then correlated with analysis of the plasma phase by mass spectrometry which showed loss of amine functionality for both neutral and ionic species. Surface interactions are also shown to decrease primary amine retention due to abstraction of hydrogen by high energy ion impacts. The stability of the plasma polymers in aqueous solution was also assessed and is shown to be precursor dependent. Increased understanding of the chemical and physical processes in the plasma phase and at the surface are therefore critical in designing improved plasma polymerisation processes.

Processable 3-nm thick graphene platelets of high electrical conductivity and their epoxy composites.

Graphene platelets (GnPs) are a class of novel 2D nanomaterials owing to their very small thickness (∼3 nm), high mechanical strength and electric conductivity (1460 S cm(-1)), and good compatibility with most polymers as well as cost-effectiveness. In this paper we present a low-cost processing technique for producing modified GnPs and an investigation of the electrical and mechanical properties of the resulting composites. After dispersing GnPs in solvent N-methyl-2-pyrrolidone, a long-chain surfactant (Jeffamine D 2000, denoted J2000) was added to covalently modify GnPs, yielding J2000-GnPs. By adjusting the ratio of GnPs to the solvent, the modified GnPs show different average thickness and thus electrical conductivity ranging from 694 to 1200 S cm(-1). To promote the exfoliation and dispersion of J2000-GnPs in a polymeric matrix, they were dispersed in the solvent again and further modified using diglycidyl ether of bisphenol A (DGEBA) producing m-GnPs, which were then compounded with an epoxy resin for the development of epoxy/m-GnP composites. A percolation threshold of electrical volume resistivity for the resulting composites was observed at 0.31 vol%. It was found that epoxy/m-GnP composites demonstrated far better mechanical properties than those of unmodified GnPs of the same volume fraction. For example, m-GnPs at 0.25 vol% increased the fracture energy release rate G1c from 0.204 ± 0.03 to 1.422 ± 0.24 kJ m(-2), while the same fraction of unmodified GnPs increased G1c to 1.01 ± 0.24 kJ m(-2). The interface modification also enhanced the glass transition temperature of neat epoxy from 58.9 to 73.8 °C.

On the effect of monomer chemistry on growth mechanisms of nonfouling PEG-like plasma polymers.

It has been shown that both ions and neutral species may contribute to plasma polymer growth. However, the relative contribution from these mechanisms remains unclear. We present data elucidating the importance of considering monomer structure with respect to which the growth mechanism dominates for nonfouling PEG-like plasma polymers. The deposition rate for saturated monomers is directly linked with ion flux to the substrate. For unsaturated monomers, the neutral flux also plays a role, particularly at low power. Increased fragmentation of the monomer at high power reduces the ability of unsaturated monomers to grow via neutral grafting. Chemical characterization by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirm the role that plasma phase fragmentation plays in determining the deposition rate and surface chemistry of the deposited film. The simple experimental method used here may also be used to determine which mechanisms dominate plasma deposition for other monomers. This knowledge may enable significant improvement in future reactor design and process control.

Melt compounding with graphene to develop functional, high-performance elastomers.

Rather than using graphene oxide, which is limited by a high defect concentration and cost due to oxidation and reduction, we adopted cost-effective, 3.56 nm thick graphene platelets (GnPs) of high structural integrity to melt compound with an elastomer-ethylene-propylene-diene monomer rubber (EPDM)-using an industrial facility. An elastomer is an amorphous, chemically crosslinked polymer generally having rather low modulus and fracture strength but high fracture strain in comparison with other materials; and upon removal of loading, it is able to return to its original geometry, immediately and completely. It was found that most GnPs dispersed uniformly in the elastomer matrix, although some did form clusters. A percolation threshold of electrical conductivity at 18 vol% GnPs was observed and the elastomer thermal conductivity increased by 417% at 45 vol% GnPs. The modulus and tensile strength increased by 710% and 404% at 26.7 vol% GnPs, respectively. The modulus improvement agrees well with the Guth and Halpin-Tsai models. The reinforcing effect of GnPs was compared with silicate layers and carbon nanotube. Our simple fabrication would prolong the service life of elastomeric products used in dynamic loading, thus reducing thermosetting waste in the environment.

Establishing the Australian National Endometriosis Clinical and Scientific Trials (NECST) Registry: A protocol paper.

Endometriosis is a common yet under-recognised chronic inflammatory disease, affecting 176 million women, trans and gender diverse people globally. The National Endometriosis Clinical and Scientific Trials (NECST) Registry is a new clinical registry, collecting and tracking diagnostic and treatment data, and patient-reported outcomes on people with endometriosis. The registry is a research priority action item from the 2018 National Action Plan for Endometriosis and aims to provide, large-scale, national and longitudinal population-based data on endometriosis. Working groups (consisting of patients with endometriosis, clinicians and researchers) developing the NECST Registry data dictionary and data collection platform started in 2019. Our data dictionary was developed based on existing and validated questionnaires, tools, meta-data and data cubes - World Endometriosis Research Foundation (WERF) Endometriosis Phenome and Biobanking Harmonisation Project (EPHect), endometriosis CORE outcomes set, patient-reported outcome measures, the International Statistical Classification of Diseases-10th Revision Australian Modification diagnosis codes, and Australian Government datasets: Australian Institute for Health and Welfare (for sociodemographic data), Medicare Benefits Schedule (MBS; for medical procedures) and the Pharmaceutical Benefits Scheme (PBS; for medical therapies). The resulting NECST Registry is an online, secure cloud-based database; prospectively collecting minimum core clinical and health data across eight patient and clinician modules and longitudinal data tracking disease life course. The NECST Registry has ethics approval (HREC/62508/MonH-2020) and is registered on the Australian New Zealand Clinical Trials Registry (ACTRN12622000987763).

Role of positive ions in determining the deposition rate and film chemistry of continuous wave hexamethyl disiloxane plasmas.

New data shed light on the mechanisms of film growth from low power, low pressure plasmas of organic compounds. These data rebalance the widely held view that plasma polymer formation is due to radical/neutral reactions only and that ions play no direct role in contributing mass at the surface. Ion reactions are shown to play an important role in both the plasma phase and at the surface. The mass deposition rate and ion flux in continuous wave hexamethyl disiloxane (HMDSO) plasmas have been studied as a function of pressure and applied RF power. Both the deposition rate and ion flux were shown to increase with applied power; however, the deposition rate increased with pressure while the ion flux decreased. Positive ion mass spectrometry of the plasma phase demonstrates that the dominant ionic species is the (HMDSO-CH(3))(+) ion at m/z 147, but significant fragmentation and subsequent oligomerization was also observed. Chemical analysis of the deposits by X-ray photoelectron spectroscopy and secondary ion mass spectrometry show that the deposits were consistent with deposits reported by previous workers grown from plasma and hyperthermal (HMDSO-CH(3))(+) ions. Increasing coordination of silicon with oxygen in the plasma deposits reveals the role of ions in the growth of plasma polymers. Comparing the calculated film thicknesses after a fixed total fluence of 1.5 × 10(19) ions/m(2) to results for hyperthermal ions shows that ions can contribute significantly to the total absorbed mass in the deposits.

Versatile gradients of chemistry, bound ligands and nanoparticles on alumina nanopore arrays.

Nanoporous alumina (PA) arrays produced by self-ordering growth, using electrochemical anodization, have been extensively explored for potential applications based upon the unique thermal, mechanical and structural properties, and high surface-to-volume ratio of these materials. However, the potential applications and functionality of these materials may be further extended by molecular-level engineering of the surface of the pore rims. In this paper we present a method for the generation of chemical gradients on the surface of PA arrays based upon plasma co-polymerization of two monomers. We further extend these chemical gradients, which are also gradients of surface charge, to those of bound ligands and number density gradients of nanoparticles. The latter represent a highly exotic new class of materials, comprising aligned PA, capped by gold nanoparticles around the rim of the pores. Gradients of chemistry, ligands and nanoparticles generated by our method retain the porous structure of the substrate, which is important in applications that take advantage of the inherent properties of these materials. This method can be readily extended to other porous materials.

Improved recovery of cryopreserved cell monolayers with a hyaluronic acid surface treatment.

Cryopreservation is an essential part of tissue banking and effective cryopreservation methods are critical for the development of cost-effective cell therapy products. Cell sheets are an attractive subset of cell therapy types, and cryopreservation has the potential to further drive down costs of allogeneic cell sheet therapy. This is currently a challenge as adhered cell monolayers are more susceptible to membrane damage during the freezing process. In this article, we investigate the performance of a surface-modified dressing for the cryopreservation of cells and strategies to improve cell recovery. Cryopreservation of multipotent adult progenitor cells (MAPC®) was performed on cells following their attachment to a surface for different periods of time. MAPC cells, given just 1 h to attach, washed off and were not recovered on the surface following thawing. Cells attached for longer periods, elongated further, and were more susceptible to damage from cryopreservation. A temporal window was identified that could allow cryopreservation on adherent surfaces where cells had attached to a surface without full elongation. By functionalizing the surface with coupled hyaluronic acid, cell spreading was initially retarded, thereby widening this temporal window. This approach demonstrates a novel method for enhancing the recovery of cryopreserved cell sheets on surfaces.

Substrate influence on the initial growth phase of plasma-deposited polymer films.

In this communication we demonstrate that in the initial stages of deposition of ultrathin plasma polymer films, both the growth rate and the chemical composition of the films are affected by the nature of the substrate which is an important question surprisingly neglected until now.

The Physics of Plasma Ion Chemistry: A Case Study of Plasma Polymerization of Ethyl Acetate.

Deposition chemistry from plasma is highly dependent on both the chemistry of the ions arriving at surfaces and the ion energy. Typically, when measuring the energy distribution of ions arriving at surfaces from plasma, it is assumed that the distributions are the same for all ionic species. Using ethyl acetate as a representative organic precursor molecule, we have measured the ion chemistry and ion energy as a function of pressure and power. We show that at low pressure (<2 Pa) this assumption is valid; however, at elevated pressures ion-molecule collisions close to the deposition surface affect both the energy and chemistry of these ions. Smaller ions are formed close to the surface and have lower energy than larger ionic species which are formed in the bulk of the plasma. The changes in plasma chemistry therefore are closely linked to the physics of the plasma-surface interface.

Label-Free Bacterial Toxin Detection in Water Supplies Using Porous Silicon Nanochannel Sensors.

Lipopolysaccharides (LPS) are the major component of the outer membrane of all Gram-negative bacteria and some cyanobacteria and are released during growth and cell death. LPS pose a potential health risk in water, causing acute respiratory illnesses, inhalation fever, and gastrointestinal disorders. The need for rapid and accurate detection of LPS has become a major priority to facilitate more timely and efficacious intervention and, hence, avoid unsafe water distribution. In this context, a porous silicon membrane (pSiM)-based electrochemical biosensor was developed for direct and sensitive detection of LPS. pSiM, featuring arrays of nanochannels, was modified with polymyxin B (PmB), an antimicrobial peptide with strong affinity to LPS. Detection of LPS was based on measuring the changes in the diffusion through the nanochannels of an electroactive species added in solution, caused by the nanochannel blockage upon LPS binding to PmB. Results showed a limit of detection of 1.8 ng/mL, and a linear response up to 10,000 ng/mL spiked in buffer. Selectivity of the sensor toward potential interfering species in water supplies was also assessed. Sensor performance was then evaluated in water samples from a water treatment plant (WTP), and detection of LPS well below the levels encountered in episodes of water contamination and in humidifiers was demonstrated. The same platform was also tested for bacterial detection including Pseudomonas aeruginosa and Escherichia coli spiked in water samples from a WTP. Considering its performance characteristics, this platform represents a promising screening tool to identify the presence of LPS in water supplies and provide early warning of contamination events.

Nanostructured Electrochemical Biosensors for Label-Free Detection of Water- and Food-Borne Pathogens.

The emergence of nanostructured materials has opened new horizons in the development of next generation biosensors. Being able to control the design of the electrode interface at the nanoscale combined with the intrinsic characteristics of the nanomaterials engenders novel biosensing platforms with improved capabilities. The purpose of this review is to provide a comprehensive and critical overview of the latest trends in emerging nanostructured electrochemical biosensors. A detailed description and discussion of recent approaches to construct label-free electrochemical nanostructured electrodes is given with special focus on pathogen detection for environmental monitoring and food safety. This includes the use of nanoscale materials such as nanotubes, nanowires, nanoparticles, and nanosheets as well as porous nanostructured materials including nanoporous anodic alumina, mesoporous silica, porous silicon, and polystyrene nanochannels. These platforms may pave the way toward the development of point-of-care portable electronic devices for applications ranging from environmental analysis to biomedical diagnostics.

Particle aggregates formed during furfuryl methacrylate plasma polymerization affect human mesenchymal stem cell behaviour.

Human Mesenchymal Stem cells (hMSCs) are becoming a major focus in biomedical fields. Application of in vitro expanded hMSCs to treat numerous ailments has led to a commercial emphasis on improving hMSC growth ex vivo. Production of substrate independent, novel thin films is one potential tool for production of commercial viable hMSC expansion. Plasma polymerization allow controlled chemical optimisation of large scale surface areas in a substrate independent manner. Previous study shown that plasma polymerized Furfuryl Methacrylate (ppFMA) surfaces allowed primary fibroblast cells adhesion and proliferation. However, under some deposition conditions, particle aggregates formation was observed. These aggregates had the effect of disrupting cell attachment, despite being chemically indistinguishable from the underlying surface. Herein, hMSCs were cultured on ppFMA surfaces to determine their suitability for stem cell culture and observe the effect of particle aggregates on hMSC attachment and growth. Both metabolic and DNA quantification assays showed that surfaces with particle aggregates had lower numbers of attached cells and slower growth. Uniform surfaces without aggregates showed higher cell attachment and growth levels, which were comparable to Thermanox. Phenotypic analysis showed that there was no change to hMSCs phenotype after 7 & 14days of culture on uniform ppFMA surface. Further investigation using time-lapse image analysis indicated that particle aggregates reduced cell attachment by presenting a physically weak boundary layer, which was damaged by intracellular tension during cell spreading. ppFMA surface can provide a stable substrate independent hMSCs expansion interface that could be applied to larger scale bioreactors, beads or scaffolds.

A Novel Fabrication Approach for Multifunctional Graphene-based Thin Film Nano-composite Membranes with Enhanced Desalination and Antibacterial Characteristics.

A practical fabrication technique is presented to tackle the trade-off between the water flux and salt rejection of thin film composite (TFC) reverse osmosis (RO) membranes through controlled creation of a thinner active selective polyamide (PA) layer. The new thin film nano-composite (TFNC) RO membranes were synthesized with multifunctional poly tannic acid-functionalized graphene oxide nanosheets (pTA-f-GO) embedded in its PA thin active layer, which is produced through interfacial polymerization. The incorporation of pTA-f-GOL into the fabricated TFNC membranes resulted in a thinner PA layer with lower roughness and higher hydrophilicity compared to pristine membrane. These properties enhanced both the membrane water flux (improved by 40%) and salt rejection (increased by 8%) of the TFNC membrane. Furthermore, the incorporation of biocidal pTA-f-GO nanosheets into the PA active layer contributed to improving the antibacterial properties by 80%, compared to pristine membrane. The fabrication of the pTA-f-GO nanosheets embedded in the PA layer presented in this study is a very practical, scalable and generic process that can potentially be applied in different types of separation membranes resulting in less energy consumption, increased cost-efficiency and improved performance.

Development of Advanced Dressings for the Delivery of Progenitor Cells.

Culture surfaces that substantially reduce the degree of cell manipulation in the delivery of cell sheets to patients are described. These surfaces support the attachment, culture, and delivery of multipotent adult progenitor cells (MAPC). It was essential that the processes of attachment/detachment to the surface did not affect cell phenotype nor the function of the cultured cells. Both acid-based and amine-based surface coatings were generated from acrylic acid, propanoic acid, diaminopropane, and heptylamine precursors, respectively. While both functional groups supported cell attachment/detachment, amine coated surfaces gave optimal performance. X-ray photoelectron spectroscopy (XPS) showed that at a primary amine to carbon surface ratio of between 0.01 and 0.02, greater than 90% of attached cells were effectively transferred to a model wound bed. A dependence on primary amine concentration has not previously been reported. After 48 h of culture on the optimized amine surface, PCR, functional, and viability assays showed that MAPC retained their stem cell phenotype, full metabolic activity, and biological function. Consequently, in a proof of concept experiment, it was shown that this amine surface when coated onto a surgical dressing provides an effective and simple technology for the delivery of MAPC to murine dorsal excisional wounds, with MAPC delivery verified histologically. By optimizing for cell delivery using a combination of in vitro and in vivo techniques, we developed an effective surface for the delivery of MAPC in a clinically relevant format.