Development of matrix-specific standards for LA-ICP-MS zinc analysis in sand flathead (Platycephalus bassensis).

The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to analyse soft tissues is limited because of the lack of suitable certified reference materials resulting in difficulties with calibration. In this study, several laboratory-prepared thin agarose sections were tested as matrix-specific standards. Our results showed 1 mm thin agarose sections were suitable as calibration standards for LA-ICP-MS Zn analyses in fish muscle, especially when the signal intensity of 66Zn was normalised to 13C. The thin agarose standard sections were used for LA-ICP-MS Zn analyses in the muscle of melanised and non-melanised sand flathead collected from a polluted estuary and assigned with different melanisation scores. Zn levels in melanised regions of fish muscle were determined to be significantly higher than non-melanised regions across all melanisation scores, though Zn levels in the melanised regions of muscle were not significantly different between sand flathead with different melanisation scores. In non-melanised regions of muscle from fish with melanisation and fish unaffected by melanisation, Zn levels were around baseline levels. Overall, this study has successfully developed matrix-specific standards for LA-ICP-MS analysis of soft tissues, thus allowing broader application of this analytical technique in future environmental pollution studies.

Recent advances in stir-bar sorptive extraction: Coatings, technical improvements, and applications.

Stir-bar sorptive extraction (SBSE) is a popular solvent-less sample preparation method, which is widely applied for the sampling and preconcentration of a wide range of non-polar solutes. A typical stir-bar for SBSE is composed of a polydimethylsiloxane (PDMS) film, coated onto a glass jacket with an incorporated magnet core. Sampling is carried out by direct immersion or by exposing the stir-bar to the headspace of the sample. To-date the majority of reported SBSE devices have used PDMS as the sorbent, with a few alternative commercially SBSE coatings available (such as polyethylene glycol and polyacrylate), which limits the applicability of SBSE to more polar and hydrophilic solutes. The interest in more selective extraction has been the driving force behind the recent development of novel SBSE coatings, particularly those exhibiting selectivity towards more polar solutes. During the last decade, a significant number of novel SBSE coatings were introduced utilising different fabrication approaches, including surface adhesion, molecular imprinting, sol-gel technology, immobilised monoliths, and solvent exchange processes. A range of nano- and micro-carbon-based materials, functional polymers, metal organic frameworks (MOFs), and inorganic nanoparticles have been employed for this purpose. Some of these SBSE coatings have exhibited higher thermal and chemical stability and delivered wider selectivity profiles. This review aims to summarise these significant developments, reported over the past six years, with specific attention to novel materials and selectivity for extending the potential applications of SBSE.

Development of polydimethylsiloxane-microdiamond composite materials for application as sorptive devices.

The development and application of non-porous and porous sorptive rods, comprised of polydimethylsiloxane-microdiamond (PDMS-MD) composites, is reported. The PDMS-MD composites were made porous using inorganic salt (NaCl and NaHCO3) particles as dissolvable templates. Materials with pore size of ~40 µm down to ~5 µm were produced. The advantages of incorporating up to ~60%microdiamond (2-4 µm) into PDMS included: (1) significant increase in the density, which saw the rods sink within the aqueous sample without addition of secondary metal or glass materials, (2) significant improvement in mechanical stability (the porous composite rods could be thermally treated multiple times before application, unlike porous PDMS), (3) increased thermal stability up to 450-500 °C with only 6% weight loss of volatile components, and (4) higher thermal conductivity, estimated to be 108% higher than for PDMS. The PDMS-MD investigated as a sorbent for extraction, followed by liquid desorption and GC-FID analysis. Recovery of the sorbent for test solutes, isoamyl acetate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, and phenethyl acetate, was found to range from ~87% to >100, with RSD of 2.10-12.50% in synthetic wine samples. Non-porous composite rods provided similar % recoveries to a commercial sorptive device (PDMS Twister), whereas porous rods showed improved % recovery for most of the test solutes (>10-20%) when applied under similar conditions. The limits of detection (LOD) for the above solutes within the developed method ranged from 0.60 to 27.30 µg L-1). Application of the PDMS-MD-LD-GC-FID method to white wine samples demonstrated how the PDMS-MD composite material can be applied as a robust and an efficient sorptive phase for trace chemical analysis.

Amide linked redox-active naphthoquinones for the treatment of mitochondrial dysfunction.

Naphthoquinones have been investigated as potential therapeutic molecules for neurodegenerative disorders, which is largely based on their anti-oxidative potential. However, a theoretical framework for the pleiotropic protective effects of naphthoquinone derivatives is largely missing. We synthesized a library of novel short chain 2,3-disubstituted naphthoquinone derivatives and measured their redox characteristics to identify a potential connection with their biological activity. Using two cell lines with different reducing potential, the compounds were tested for their inherent toxicity, acute rescue of ATP levels and cytoprotective activity. For the first time, a structure-activity-relationship for naphthoquinones has been established. Our results clearly demonstrate that it is the group on the alkyl side chain and not solely the redox characteristics of the naphthoquinone unit or lipophilicity that determines the extent of cytoprotection by individual compounds. From this, we developed a number of amide containing naphthoquinones with superior activity in ATP rescue and cell viability models compared to the clinically used benzoquinone idebenone.

Three-Dimensional Printing of Abrasive, Hard, and Thermally Conductive Synthetic Microdiamond-Polymer Composite Using Low-Cost Fused Deposition Modeling Printer.

A relative lack of printable materials with tailored functional properties limits the applicability of three-dimensional (3D) printing. In this work, a diamond-acrylonitrile butadiene styrene (ABS) composite filament for use in 3D printing was created through incorporation of high-pressure and high-temperature (HPHT) synthetic microdiamonds as a filler. Homogenously distributed diamond composite filaments, containing either 37.5 or 60 wt % microdiamonds, were formed through preblending the diamond powder with ABS, followed by subsequent multiple fiber extrusions. The thermal conductivity of the ABS base material increased from 0.17 to 0.94 W/(m·K), more than five-fold following incorporation of the microdiamonds. The elastic modulus for the 60 wt % microdiamond containing composite material increased by 41.9% with respect to pure ABS, from 1050 to 1490 MPa. The hydrophilicity also increased by 32%. A low-cost fused deposition modeling printer was customized to handle the highly abrasive composite filament by replacing the conventional (stainless-steel) filament feeding gear with a harder titanium gear. To demonstrate improved thermal performance of 3D printed devices using the new composite filament, a number of composite heat sinks were printed and characterized. Heat dissipation measurements demonstrated that 3D printed heat sinks containing 60 wt % diamond increased the thermal dissipation by 42%.

Enhanced physicochemical properties of polydimethylsiloxane based microfluidic devices and thin films by incorporating synthetic micro-diamond.

Synthetic micro-diamond-polydimethylsiloxane (PDMS) composite microfluidic chips and thin films were produced using indirect 3D printing and spin coating fabrication techniques. Microfluidic chips containing up to 60 wt% micro-diamond were successfully cast and bonded. Physicochemical properties, including the dispersion pattern, hydrophobicity, chemical structure, elasticity and thermal characteristics of both chip and films were investigated. Scanning electron microscopy indicated that the micro-diamond particles were embedded and interconnected within the bulk material of the cast microfluidic chip, whereas in the case of thin films their increased presence at the polymer surface resulted in a reduced hydrophobicity of the composite. The elastic modulus increased from 1.28 for a PDMS control, to 4.42 MPa for the 60 wt% composite, along with a three-fold increase in thermal conductivity, from 0.15 to 0.45 W m-1 K-1. Within the fluidic chips, micro-diamond incorporation enhanced heat dissipation by efficient transfer of heat from within the channels to the surrounding substrate. At a flow rate of 1000 µL/min, the gradient achieved for the 60 wt% composite chip equalled a 9.8 °C drop across a 3 cm long channel, more than twice that observed with the PDMS control chip.

Mechanistic investigation of the oxidation of hydrazides: implications for the activation of the TB drug isoniazid.

Aryl hydrazides are oxidised to acyl radicals through a mechanism involving diimide intermediates that are prone to nucleophilic acyl substitution. This oxidation occurs regardless of the oxidant involved, however there is no evidence that the acyl radical formed undergoes further oxidation to the corresponding acylium ion, even in the presence of strong oxidants. This study may provide insight into the mechanism of isoniazid resistance in Mycobacterium tuberculosis.

Lab-on-a-Chip device with laser-patterned polymer electrodes for high voltage application and contactless conductivity detection.

A laser-patterned microchip electrophoresis device with integrated polymer electrodes for DC high voltages and AC capacitively-coupled contactless conductivity detection was developed. Electrophoresis separations comparable to devices with metal electrodes were obtained, at approximately 20 times lower cost.

Manufacturing and application of a fully polymeric electrophoresis chip with integrated polyaniline electrodes.

This work describes the development of a fully polymeric microchip with integrated polymeric electrodes suitable for performing microchip electrophoresis. The polymer electrodes were fabricated in a thin film of the conducting polymer, polyaniline (PANI), by flash lithography using a studio camera flash and a transparency mask. During flash welding, exposed regions welded into non-conducting regions forming a conducting polymer circuit in the non-exposed regions. Using a structured layer of dry film photoresist for sealing, a polydimethylsiloxane (PDMS) substrate containing channels and reservoirs was bound to the PANI film to form an integrated microfluidic device. The conducting regions of the PANI film were shown to be capable of carrying the high voltages of up to 2000 V required for chip electrophoresis, and were stable for up to 30 minutes under these conditions. The PANI electrodes were used for the electrophoretic separation of three sugars labelled with 8-amino-1,3,6-pyrenetrisulfonic acid (APTS) in the dry film resist-PDMS hybrid device. Highly efficient separations comparable to those achieved in similar microchips using platinum electrodes confirm the potential of polyaniline as a new material suitable for high voltage electrodes in Lab-on-a-chip devices.

Calcium-phosphorus interactions at a nano-structured silicate surface.

Nano-structured calcium silicate (NCS), a highly porous material synthesized by controlled precipitation from geothermal fluids or sodium silicate solution, was developed as filler for use in paper manufacture. NCS has been shown to chemisorb orthophosphate from an aqueous solution probably obeying a Freundlich isotherm with high selectivity compared to other common environmental anions. Microanalysis of the products of chemisorption indicated there was significant change from the porous and nano-structured morphology of pristine NCS to fibrous and crystalline morphologies and non-porous detritus. X-ray diffraction analysis of the crystalline products showed it to be brushite, CaHPO42H2O, while the largely X-ray amorphous component was a mixture of calcium phosphates. A two-step mechanism was proposed for the chemisorption of phosphate from an aqueous solution by NCS. The first step, which was highly dependent on pH, was thought to be desorption of hydroxide ions from the NCS surface. This was kinetically favoured at lower initial pH, where the predominant form of phosphate present was H2PO(-)4, and led to decreased phosphorus uptake with increasing pH. The second step was thought to be a continuing chemisorption process after stabilization of the pH-value. The formation of brushite as the primary chemisorption product was found to be consistent with the proposed mechanism.