Immunoaffinity extraction followed by enzymatic digestion for the isolation and identification of proteins employing automated µSPE reactors and mass spectrometry.

This work describes a novel automated and rapid method for bottom-up proteomics combining protein isolation with a micro-immobilised enzyme reactor (IMER). Crosslinking chemistry based on 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling was exploited to immobilise trypsin and antibodies onto customisable silica particles coated with carboxymethylated dextran (CMD). This novel silica-CMD solid-phase extraction material was characterised using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), conductometric titrations and enzymatic colorimetric assays. Micro-solid-phase extraction (µSPE) cartridges equipped with the modified CMD material were employed and integrated into an automated and repeatable workflow using a sample preparation workstation to achieve rapid and repeatable protein isolation and pre-concentration, followed by tryptic digestion producing peptide fragments that were identified by liquid chromatography mass spectrometry (LC-MS).

Micro solid-phase extraction for the analysis of per- and polyfluoroalkyl substances in environmental waters.

Growing concern over the environmental and health impacts of per- and polyfluoroalkyl substances (PFASs) has led to the development of increasingly stringent regulatory guidelines. To meet these guidelines for the determination of PFASs in surface-water, solid-phase extraction (SPE) is commonly implemented for clean-up and pre-concentration of samples. In this paper a micro-SPE method for the clean-up and pre-concentration of PFASs from surface-water was developed. A micro-SPE packing phase was created to retain 13 long and short chain PFAS after examining combinations of four 3 µm particle size sorbents, with the optimal phase consisting of a 50:50 mixture of C18 and aminopropyl silica. Micro-SPE achieved similar results to conventional SPE methods while reducing sample preparation time to 5 min and using only 2 mL of sample. The method was validated using spiked recoveries (100 ng L-1) from PFAS contaminated surface-water samples with recoveries ranging from 86% to 111% and relative standard deviations below 18%. Concentrations of the PFASs in the samples ranged from below the limit of quantification to 898 ± 15 ng L-1. Automation of sample preparation, including the micro-SPE extraction, was also demonstrated. These results show the potential for automated micro-SPE to replace conventional SPE, with the decreases in sample preparation time, sample and solvent volumes crucial for incorporation into routine analyses in commercial laboratories.

Patterned Polymer Coatings Increase the Efficiency of Dew Harvesting.

Micropatterned polymer surfaces, possessing both topographical and chemical characteristics, were prepared on three-dimensional copper tubes and used to capture atmospheric water. The micropatterns mimic the structure on the back of a desert beetle that condenses water from the air in a very dry environment. The patterned coatings were prepared by the dewetting of thin films of poly-4-vinylpyridine (P4VP) on top of polystyrene films (PS) films, upon solvent annealing, and consist of raised hydrophilic bumps on a hydrophobic background. The size and density distribution of the hydrophilic bumps could be tuned widely by adjusting the initial thickness of the P4VP films: the diameter of the produced bumps and their height could be varied by almost 2 orders of magnitude (1-80 µm and 40-9000 nm, respectively), and their distribution density could be varied by 5 orders of magnitude. Under low subcooling conditions (3 °C), the highest rate of water condensation was measured on the largest (80 µm diameter) hydrophilic bumps and was found to be 57% higher than that on flat hydrophobic films. These subcooling conditions are achieved spontaneously in dew formation, by passive radiative cooling of a surface exposed to the night sky. In effect, the pattern would result in a larger number of dewy nights than a flat hydrophobic surface and therefore increases water capture efficiency. Our approach is suited to fabrication on a large scale, to enable the use of the patterned coatings for water collection with no external input of energy.

Doped graphene/Cu nanocomposite: A high sensitivity non-enzymatic glucose sensor for food.

An amperometric non-enzymatic glucose sensor was developed based on nitrogen-doped graphene with dispersed copper nanoparticles (Cu-NGr). The sensing element was tested in conjunction with a modified glassy carbon electrode for glucose detection. The Cu-NGr composite was prepared by one pot synthesis from a mixture of graphene oxide, copper nitrate and uric acid, followed by thermal annealing at 900°C for 1h. Detailed characterizations showed homogeneous copper nanoparticle dispersion and the presence of significant proportion of graphitic nitrogen. The developed electrode presented high electrocatalytic activity towards glucose through synergetic effect of copper nanoparticles and nitrogen-doped graphene. Amperometric analysis confirmed high glucose sensitivity and ultra-low detection of 10nM glucose over a linear range. The sensor was tested for direct application to detect glucose in food samples for which the sensor displayed high selectivity with excellent reproducibility and recovery in complex food materials.

Boron-Functionalized Graphene Oxide-Organic Frameworks for Highly Efficient CO2 Capture.

The capture and storage of CO2 have been suggested as an effective strategy to reduce the global emissions of greenhouse gases. Hence, in recent years, many studies have been carried out to develop highly efficient materials for capturing CO2 . Until today, different types of porous materials, such as zeolites, porous carbons, N/B-doped porous carbons or metal-organic frameworks (MOFs), have been studied for CO2 capture. Herein, the CO2 capture performance of new hybrid materials, graphene-organic frameworks (GOFs) is described. The GOFs were synthesized under mild conditions through a solvothermal process using graphene oxide (GO) as a starting material and benzene 1,4-diboronic acid as an organic linker. Interestingly, the obtained GOF shows a high surface area (506 m2 g-1 ) which is around 11 times higher than that of GO (46 m2 g-1 ), indicating that the organic modification on the GO surface is an effective way of preparing a porous structure using GO. Our synthetic approach is quite simple, facile, and fast, compared with many other approaches reported previously. The synthesized GOF exhibits a very large CO2 capacity of 4.95 mmol g-1 at 298 K (1 bar), which is higher those of other porous materials or carbon-based materials, along with an excellent CO2 /N2 selectivity of 48.8.

Relationship between nanotopographical alignment and stem cell fate with live imaging and shape analysis.

The topography of a biomaterial regulates cellular interactions and determine stem cell fate. A complete understanding of how topographical properties affect cell behavior will allow the rational design of material surfaces that elicit specified biological functions once placed in the body. To this end, we fabricate substrates with aligned or randomly organized fibrous nanostructured topographies. Culturing adipose-derived stem cells (ASCs), we explore the dynamic relationship between the alignment of topography, cell shape and cell differentiation to osteogenic and myogenic lineages. We show aligned topographies differentiate cells towards a satellite cell muscle progenitor state - a distinct cell myogenic lineage responsible for postnatal growth and repair of muscle. We analyze cell shape between the different topographies, using fluorescent time-lapse imaging over 21 days. In contrast to previous work, this allows the direct measurement of cell shape at a given time rather than defining the morphology of the underlying topography and neglecting cell shape. We report quantitative metrics of the time-based morphological behaviors of cell shape in response to differing topographies. This analysis offers insights into the relationship between topography, cell shape and cell differentiation. Cells differentiating towards a myogenic fate on aligned topographies adopt a characteristic elongated shape as well as the alignment of cells.

Self-Assembled N/S Codoped Flexible Graphene Paper for High Performance Energy Storage and Oxygen Reduction Reaction.

A novel flexible three-dimensional (3D) architecture of nitrogen and sulfur codoped graphene has been successfully synthesized via thermal treatment of a liquid crystalline graphene oxide-doping agent composition, followed by a soft self-assembly approach. The high temperature process turns the layer-by-layer assembly into a high surface area macro- and nanoporous free-standing material with different atomic configurations of graphene. The interconnected 3D network exhibits excellent charge capacitive performance of 305 F g(-1) (at 100 mV s(-1)), an unprecedented volumetric capacitance of 188 F cm(-3) (at 1 A g(-1)), and outstanding energy density of 28.44 Wh kg(-1) as well as cycle life of 10 000 cycles as a free-standing electrode for an aqueous electrolyte, symmetric supercapacitor device. Moreover, the resulting nitrogen/sulfur doped graphene architecture shows good electrocatalytic performance, long durability, and high selectivity when they are used as metal-free catalyst for the oxygen reduction reaction. This study demonstrates an efficient approach for the development of multifunctional as well as flexible 3D architectures for a series of heteroatom-doped graphene frameworks for modern energy storage as well as energy source applications.

A New Raman Metric for the Characterisation of Graphene oxide and its Derivatives.

Raman spectroscopy is among the primary techniques for the characterisation of graphene materials, as it provides insights into the quality of measured graphenes including their structure and conductivity as well as the presence of dopants. However, our ability to draw conclusions based on such spectra is limited by a lack of understanding regarding the origins of the peaks. Consequently, traditional characterisation techniques, which estimate the quality of the graphene material using the intensity ratio between the D and the G peaks, are unreliable for both GO and rGO. Herein we reanalyse the Raman spectra of graphenes and show that traditional methods rely upon an apparent G peak which is in fact a superposition of the G and D' peaks. We use this understanding to develop a new Raman characterisation method for graphenes that considers the D' peak by using its overtone the 2D'. We demonstrate the superiority and consistency of this method for calculating the oxygen content of graphenes, and use the relationship between the D' peak and graphene quality to define three regimes. This has important implications for purification techniques because, once GO is reduced beyond a critical threshold, further reduction offers limited gain in conductivity.

Co-Doping of Activated Graphene for Synergistically Enhanced Electrocatalytic Oxygen Reduction Reaction.

Doping of graphene has emerged as a key strategy to improve the electrocatalytic performance of the oxygen reduction reaction (ORR). Activated graphene co-doped with iodine and nitrogen atoms (NIG) was developed in this work using a facile scalable approach. The onset potential, current density, and four-electron reduction pathway of the newly developed catalyst were significantly improved. The charge-transfer resistance of co-doped NIG was found to be much lower than nitrogen-doped graphene (NG); furthermore, the stability of NIG and its resistance to methanol crossover were also improved. The synergistically enhanced ORR performance of NIG was found to be a result of a high strain and size advantage of the larger iodine atom clusters (compared to nitrogen), which facilitate the simultaneous enrichment of anode electrons and O2 and H2 O molecule transport at catalytic sites, inducing four-electron transfer in a single step. These results are promising for application in alkaline fuel cells.

Towards the Knittability of Graphene Oxide Fibres.

Recent developments in graphene oxide fibre (GO) processing include exciting demonstrations of hand woven textile structures. However, it is uncertain whether the fibres produced can meet the processing requirements of conventional textile manufacturing. This work reports for the first time the production of highly flexible and tough GO fibres that can be knitted using textile machinery. The GO fibres are made by using a dry-jet wet-spinning method, which allows drawing of the spinning solution (the GO dispersion) in several stages of the fibre spinning process. The coagulation composition and spinning conditions are evaluated in detail, which led to the production of densely packed fibres with near-circular cross-sections and highly ordered GO domains. The results are knittable GO fibres with Young's modulus of ~7.9 GPa, tensile strength of ~135.8 MPa, breaking strain of ~5.9%, and toughness of ~5.7 MJ m(-3). The combination of suitable spinning method, coagulation composition, and spinning conditions led to GO fibres with remarkable toughness; the key factor in their successful knitting. This work highlights important progress in realising the full potential of GO fibres as a new class of textile.

Development of a Multidimensional Additive Points System for Determining Access to Rheumatology Services.

OBJECTIVE: In many countries, including New Zealand, the demand for rheumatology services exceeds their supply, resulting in some patients experiencing long delays or being denied access. The principal aim of this work was to create a validated, transparent, and fair system for determining access to rheumatology services. METHODS: A panel of 5 rheumatologists, 6 primary care physicians, and 4 nurse specialists ranked a series of 25 clinical scenarios in order of priority to see a rheumatologist. Important determining factors were weighted in an iterative process to generate a multidimensional additive point score to determine access to rheumatology service. RESULTS: The score comprises 6 domains of 2 to 4 items weighted to give a total score out of 100. The effect of the problem on the patient's life and role, the presence of an inflammatory rheumatic disease, appropriateness of current treatment, and the ability of the rheumatologist to influence the current symptoms and future prognosis were felt to be critical factors in determining access to the service. The score showed a strong correlation with the rankings agreed by the clinical panel, and the overall intraclass correlation coefficient for the rheumatologists was 0.698. CONCLUSIONS: Our score has face validity, is easy to perform, and has been assessed by an independent panel of rheumatologists as providing a fair system for determining access to rheumatology services. The system is acceptable to primary care physicians and has been adopted by our local primary care organizations.

Hypothesis: bones toughness arises from the suppression of elastic waves.

Bone and other natural material exhibit a combination of strength and toughness that far exceeds that of synthetic structural materials. Bone's toughness is a result of numerous extrinsic and intrinsic toughening mechanisms that operate synergistically at multiple length scales to produce a tough material. At the system level however no theory or organizational principle exists to explain how so many individual toughening mechanisms can work together. In this paper, we utilize the concept of phonon localization to explain, at the system level, the role of hierarchy, material heterogeneity, and the nanoscale dimensions of biological materials in producing tough composites. We show that phonon localization and attenuation, using a simple energy balance, dynamically arrests crack growth, prevents the cooperative growth of cracks, and allows for multiple toughening mechanisms to work simultaneously in heterogeneous materials. In turn, the heterogeneous, hierarchal, and multiscale structure of bone (which is generic to biological materials such as bone and nacre) can be rationalized because of the unique ability of such a structure to localize phonons of all wavelengths.

Edge-enriched graphene quantum dots for enhanced photo-luminescence and supercapacitance.

Graphene quantum dots (GQDs) with their edge-bound nanometer-size present distinctive properties owing to quantum confinement and edge effects. We report a facile ultrasonic approach with chemical activation using KOH to prepare activated GQDs or aGQDs enriched with both free and bound edges. Compared to GQDs, the aGQDs we synthesized had enhanced BET surface area by a factor of about six, the photoluminescence intensity by about four and half times and electro-capacitance by a factor of about two. Unlike their non-activated counterparts, the aGQDs having enhanced edge states emit enhanced intense blue luminescence and exhibit electrochemical double layer capacitance greater than that of graphene, activated or not. Apart from their use as part of electrodes in a supercapacitor, the superior luminescence of aGQDs holds potential for use in biomedical imaging and related optoelectronic applications.

High-performance multifunctional graphene yarns: toward wearable all-carbon energy storage textiles.

The successful commercialization of smart wearable garments is hindered by the lack of fully integrated carbon-based energy storage devices into smart wearables. Since electrodes are the active components that determine the performance of energy storage systems, it is important to rationally design and engineer hierarchical architectures atboth the nano- and macroscale that can enjoy all of the necessary requirements for a perfect electrode. Here we demonstrate a large-scale flexible fabrication of highly porous high-performance multifunctional graphene oxide (GO) and rGO fibers and yarns by taking advantage of the intrinsic soft self-assembly behavior of ultralarge graphene oxide liquid crystalline dispersions. The produced yarns, which are the only practical form of these architectures for real-life device applications, were found to be mechanically robust (Young's modulus in excess of 29 GPa) and exhibited high native electrical conductivity (2508 ± 632 S m(-1)) and exceptionally high specific surface area (2605 m(2) g(-1) before reduction and 2210 m(2) g(-1) after reduction). Furthermore, the highly porous nature of these architectures enabled us to translate the superior electrochemical properties of individual graphene sheets into practical everyday use devices with complex geometrical architectures. The as-prepared final architectures exhibited an open network structure with a continuous ion transport network, resulting in unrivaled charge storage capacity (409 F g(-1) at 1 A g(-1)) and rate capability (56 F g(-1) at 100 A g(-1)) while maintaining their strong flexible nature.

A simple gas-solid route to functionalize ordered carbon.

The reaction of nitric oxide (NO) and carbonaceous materials generates nitrogen functionalities on and in graphitic carbons and oxidizes some of the carbon. Here, we have exploited these phenomena to provide a novel route to surface-functionalized multiwalled carbon nanotubes (MWCNTs). We investigated the impacts of NO on the physical and chemical properties of industrially synthesized multiwalled carbon nanotubes to find a facile treatment that increased the specific surface area (SBET) of the MWCNTs by ∼20%, with only a minimal effect on their degree of graphitization. The technique caused less material loss (∼12 wt %) than traditional gas-based activation techniques and grafted some nitrogen functional groups (1.1 at. %) on the MWCNTs. Moreover, we found that Ni nanoparticles deposited on NO-treated MWCNTs had a crystallite size of dNi = 13.1 nm, similar to those deposited on acid-treated MWCNTs (dNi = 14.2 nm), and clearly much smaller than those deposited under the same conditions on untreated MWCNTs (dNi = 18.3 nm).

Synergistically enhanced electrochemical (ORR) activity of graphene oxide using boronic acid as an interlayer spacer.

Herein, boronic acid is incorporated into a graphene oxide (GO) structure in order to synthesise a graphene organic framework (GOF) with enhanced electrochemical performance. The results obtained indicate that the GOF favours a 4e(-) reduction pathway in the oxygen reduction reaction (ORR).

High-yield aqueous phase exfoliation of graphene for facile nanocomposite synthesis via emulsion polymerization.

Aqueous phase exfoliation was developed for producing high-yield graphene nanosheets from expanded graphite (EG). The process included ultrasonication with sodium dodecyl sulfate (SDS) emulsion in aqueous phase. The high throughput exfoliation process was characterized by UV-vis spectroscopy, transmission electron microscopy (TEM) and electrical impedance spectroscopy (EIS). Controlled sonication experiments revealed that optimum exfoliation corresponds to maxima in UV-vis spectra. TEM results showed that the exfoliated graphene comprised nanoflakes having ≤5 layers (~60%) and ≤10 layers for 90% of the product. The potential use of this highly dispersed graphene was demonstrated by one-pot synthesis of graphene/polymer composite via in situ emulsion polymerization with styrene. The integrated role of SDS included adsorption and exfoliation of graphite, dispersion of graphene produced and assisting with micelle formation in emulsion. The high surface area graphene nanosheets as dispersed phase in polymeric nanocomposites showed significant improvement in thermal stability and electrical conductivity.

Carbon nanotubes: their potential and pitfalls for bone tissue regeneration and engineering.

The extracellular environment which supports cell life is composed of a hierarchy of maintenance, force and regulatory systems which integrate from the nano- through to macroscale. For this reason, strategies to recreate cell supporting environments have been investigating the use of nanocomposite biomaterials. Here, we review the use of carbon nanotubes as part of a bottom-up approach for use in bone tissue engineering. We evaluate the properties of carbon nanotubes in the context of synthetic tissue substrates and contrast them with the nanoscale features of the extracellular environment. Key studies are evaluated with an emphasis on understanding the mechanisms through which carbon nanotubes interact with biological systems. This includes an examination of how the different properties of carbon nanotubes affect tissue growth, how these properties and variation to them might be leveraged in regenerative tissue therapies and how impurities or contaminates affect their toxicity and biological interaction. FROM THE CLINICAL EDITOR: In this comprehensive review, the authors describe the status and potential applications of carbon nanotubes in bone tissue engineering.

Scalable solid-template reduction for designed reduced graphene oxide architectures.

Herein, we report a solid-state reduction process (in contrast to solution-based approach) by using an environmentally friendly reductant, such as vitamin C (denoted VC), to be directly employed to solid-state graphene oxide (GO) templates to give the highly active rGO architecture with a sheet resistance of as low as 10 Ω sq(-1). In addition, predesigned rGO patterns/tracks with tunable resistivity can be directly "written" on a preprepared solid GO film via the inkjet-printing technique using VC/H2O as the printing-ink. This advanced reduction process allows foreign active materials to be preincorporated into the GO matrix to form quality active composite architectures.