Australian Centre for Research on Separation Science

3D printing has the potential to significantly change the field of microfluidics. The ability to fabricate a complete microfluidic device in a single step from a computer model has obvious attractions, but it is the ability to create truly three dimensional structures that will provide new microfluidic capability that is challenging, if not impossible to make with existing approaches. This critical review covers the current state of 3D printing for microfluidics, focusing on the four most frequently used printing approaches: inkjet (i3DP), stereolithography (SLA), two photon polymerisation (2PP) and extrusion printing (focusing on fused deposition modeling). It discusses current achievements and limitations, and opportunities for advancement to reach 3D printing's full potential.

The ubiquitous pollution of the environment with microplastics, a diverse suite of contaminants, is of growing concern for science and currently receives considerable public, political, and academic attention. The potential impact of microplastics in the environment has prompted a great deal of research in recent years. Many diverse methods have been developed to answer different questions about microplastic pollution, from sources, transport, and fate in the environment, and about effects on humans and wildlife. These methods are often insufficiently described, making studies neither comparable nor reproducible. The proliferation of new microplastic investigations and cross-study syntheses to answer larger scale questions are hampered. This diverse group of 23 researchers think these issues can begin to be overcome through the adoption of a set of reporting guidelines. This collaboration was created using an open science framework that we detail for future use. Here, we suggest harmonized reporting guidelines for microplastic studies in environmental and laboratory settings through all steps of a typical study, including best practices for reporting materials, quality assurance/quality control, data, field sampling, sample preparation, microplastic identification, microplastic categorization, microplastic quantification, and considerations for toxicology studies. We developed three easy to use documents, a detailed document, a checklist, and a mind map, that can be used to reference the reporting guidelines quickly. We intend that these reporting guidelines support the annotation, dissemination, interpretation, reviewing, and synthesis of microplastic research. Through open access licensing (CC BY 4.0), these documents aim to increase the validity, reproducibility, and comparability of studies in this field for the benefit of the global community.

The formulation of new composite materials compatible with additive fabrication techniques is driving a revolution in the field of applied materials science.

Abstract Homochiral metal–organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high‐quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF–polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL‐53‐NH 2 nanocrystals by post‐synthetic modification with amino acids, such as l ‐histidine ( l ‐His) and l ‐glutamic acid ( l ‐Glu). The MIL‐53‐NH‐ l ‐His and MIL‐53‐NH‐ l ‐Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1‐phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large‐scale homochiral MOF‐based MMMs for chiral separation.

3D printing has emerged as a valuable approach for the fabrication of fluidic devices and may replace soft-lithography as the method of choice for rapid prototyping. The potential of this disruptive technology is much greater than this - it allows for functional integration in a single, highly automated manufacturing step in a cost and time effective manner. Integration of functionality with a 3D printer can be done through spatial configuration of a single material, inserting pre-made components mid-print in a print-pause-print approach, and/or through the precise spatial deposition of different materials with a multimaterial printer. This review provides an overview on the ways in which 3D printing has been exploited to create and use fluidic devices with different functionality, which provides a basis for critical reflection on the current deficiencies and future opportunities for integration by 3D printing.

A low cost 3D stereolithography based printer has been used for a new polymer composite material with enhanced thermal properties containing 30 wt% micro-particulate diamond.

Benchmark propagation rate coefficient (<italic>k</italic>_p) data for the radical polymerization of methyl acrylate are provided.

This study examines the effects of different salts as well as the influence of the relative hydrophobicities of different sorbents on the adsorption processes of proteins in hydrophobic interaction chromatography (HIC). Comparative data acquired by the equilibrium binding analysis and by isothermal titration microcalorimetry (ITC) are presented. In particular, thermodynamic parameters, including the enthalpy changes, related to the interactions between several globular proteins and various Toyopearl 650 M sorbents under solvent conditions containing either 2.0 M ammonium sulfate or 2.0 M sodium sulfate at pH 7.0 and 298.15 K have been evaluated in terms of the molecular properties of these systems. The results reveal that the dependence of the free energy change, deltaGads, for protein adsorption to HIC sorbents on the salt composition can be mainly attributed to the enthalpy changes associated with protein and sorbent dehydration and hydrophobic interactions. Differences in binding mechanisms between the n-butyl- and phenyl-HIC sorbents were evident. In the latter case, the participation of pi-pi hydrophobic interactions leads to significant differences in the associated enthalpy and entropy changes. Furthermore, an increase in the hydrophobicity of either the sorbent or the protein resulted in more negative values for the free energy change, which arose mostly from dehydration processes. Entropic effects favoring HIC adsorption increased with an increase in the exposed nonpolar surface area of the protein. Consequently, an increased contribution from the entropy change to the respective change in free energy occurs when HIC sorbents or proteins of higher hydrophobicity are employed, with these larger entropy changes consistent with a change in the interaction mechanism from a binding event dominated by adsorption to a partitioning-like process. Data extracted from the ITC measurements also provided insight into the interaction mechanisms that occur between proteins and hydrophobic solid surfaces, yielding information that can be applied to the HIC purification of proteins according to the concept of critical hydrophobicity of the system and its thermodynamic consequences.

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%.

This review presents an overview of the separation techniques applied to the complex challenge of dissolved organic matter characterisation. The review discusses methods for isolation of dissolved organic matter from natural waters, and the range of separation techniques used to further fractionate this complex material. The review covers both liquid and gas chromatographic techniques, in their various modes, and electrophoretic based approaches. For each, the challenges that the separation and fractionation of such an immensely complex sample poses is critically reviewed.

Composite particles containing the Zr-based metal-organic framework (MOF) UiO-66 were prepared using microwave-assisted solvothermal synthesis. Scanning electron microscopy, infrared spectroscopy, powder X-ray diffraction and nitrogen physisorption studies confirmed the deposition of 100-300 nm microporous particles with the UiO-66 topology on the surface of mesoporous 5 μm and non-porous 2.1 μm silica particles. The core-shell particles exhibited a unique flow-dependent separation selectivity (FDSS) effect which allows changes in both the retention and separation selectivity of small molecules by simple variation of the mobile phase flow rate under isocratic conditions. The impact of the loading of UiO-66 as well as the porosity of the underlying silica core (mesoporous and non-porous) on the FDSS effect was evaluated. The prepared adsorbents were also tested for the normal-phase (NP) and reversed-phase (RP) separation of xylene isomers, substituted benzenes and polyaromatic hydrocarbons (PAHs). Efficiencies of up to 32 400 plates per m (styrene, k 1.59) and 37 200 plates per m (anisole, k 2.90) were achieved under NP and RP modes, respectively. The results demonstrate the potential of novel MOF-based stationary phases for the separation of closely related compounds (e.g. positional isomers).

Abstract In comprehensive 2D gas chromatography, the entire sample is simultaneously subjected to analysis on two capillary columns. By using a suitable modulation interface between the primary and secondary columns, hundreds of fast, second‐dimension chromatograms are produced. The data from these chromatograms are treated such that a 3D surface plot or a 2D contour plot of the components' individual retention times, on each column, as well as peak responses, are represented. In a properly tuned comprehensive 2D chromatogram, the individual sample components are spread throughout a 2D separation space, providing a significant increase in the probability of resolving a greater number of sample components without increasing the analysis time. Comprehensive 2D–GC has proved useful for high‐resolution conventional essential oil analysis as well as high‐resolution enantioselective essential oil analysis. Combining comprehensive 2D–GC with either a quadrupole or time‐of‐flight mass spectrometer gives a powerful 3D analysis technique, which is extremely effective for complex sample analysis. The present status and opportunities arising from these ultra‐high resolution approaches are discussed herein. Copyright © 2003 John Wiley &amp; Sons, Ltd.

This review covers advances and applications of open tubular capillary liquid chromatography (OT-LC) over the period 2007-2018. Under the right conditions OT-LC columns have the potential to offer superior column efficiency, higher overall peak capacity, and higher column permeability compared to packed capillary and monolithic columns. However, such advantages are highly dependent upon column format and dimensions, and to date in liquid chromatography the advantages of open tubular format columns have been most widely discussed and applied in the field of proteomics. In this review we have focused on the wider variety of separation mechanisms and applications which can be achieved following the modification of the inner wall of the capillary with a thin-layer stationary phase. In particular the latest advances in stationary phase development and formation, together with new column formats and dimensions are reviewed. Detection options for OT-LC are also discussed and recent advances in this area highlighted. Finally, this review summarises existing applications of OT-LC and illustrates the future potential for this technique.

A UV light emitting diode (LED) with a maximum output of 372 nm was collimated using a pinhole and a small plastic tube and focused using a microscope objective onto a substrate for direct lithographic patterning of the photoresist. Movement of the substrate with a motorised linear stage (syringe pump) allowed lines in SU-8 to be pattered with a width down to 35 microm at a linear velocity of 80 microm s(-1), while in the dry film resist Ordyl SY 330, features as narrow as 17 microm were made at a linear velocity of 245 microm s(-1). At this linear velocity, a 75 mm long feature could be patterned in 5 min. Functional microfluidic devices were made by casting PDMS on a master made by LED lithography. The results show that UV LEDs are a suitable light source for direct writing lithography, offering a budget friendly, and high resolution alternative for rapid prototyping of features smaller than 20 microm.

electrical double layer enthalpy–entropy compensation energy relationship group molecular parameters hydrophobic interaction chromatography Linear free energy relationships Murphy–Privalov–Gill plots potential barries chromatography reversed-phase chromatography

The accurate characterization of molar‐mass distributions of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) by size‐exclusion chromatography (SEC) is addressed. Two methods are employed: direct aqueous‐phase SEC on P(M)AA and THF‐based SEC after esterification of P(M)AA to the associated methyl esters, P(M)MA. P(M)AA calibration standards, P(M)AA samples prepared by pulsed‐laser polymerization (PLP), and PAA samples prepared by reversible addition‐fragmentation chain transfer (RAFT) are characterized in a joint initiative of seven laboratories, with satisfactory agreement achieved between the institutions. Both SEC methods provide reliable results for PMAA. In the case of PAA, close agreement between the two SEC methods is only observed for samples prepared by RAFT polymerization with weight‐average molar mass between 80 000 and 145 000 g mol −1 and for standards with peak molar masses below 20 000 g mol −1 . For standards with higher molar masses and for PLP‐prepared PAA, the values from THF‐based SEC are as much as 40% below the molar masses determined by aqueous‐phase SEC. This discrepancy may be due to branching or degradation of branched PAA during methylation. While both SEC methods can be recommended for PMAA, aqueous‐phase SEC should be used for molar‐mass analysis of PAA unless the sample is not branched. image

Abstract Homochiral metal–organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high‐quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF–polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL‐53‐NH 2 nanocrystals by post‐synthetic modification with amino acids, such as l ‐histidine ( l ‐His) and l ‐glutamic acid ( l ‐Glu). The MIL‐53‐NH‐ l ‐His and MIL‐53‐NH‐ l ‐Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1‐phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large‐scale homochiral MOF‐based MMMs for chiral separation.

The risks posed by viral diseases have been recognised as critical threats to mankind.

In this paper, we report on investigations related to the performance characteristics of two different types of etched chemically (n-octadecyl- and cholesterol-) modified capillaries in the open tubular format of capillary electrochromatography (CEC) for the analysis of synthetic peptides. The results confirm that the nature of the surface chemistry used to modify the capillary wall and type of chemically bonded group employed can affect the selectivity as well as the resolution of peptide samples. The results are consistent with the participation of selective peptide interactions with the bonded phase, although other factors, such as the morphology of the capillary wall surfaces, appear to be also involved. Moreover, several surprising observations related to peptide-specific multi-zoning effects have been observed. Additional experimental variables that can also be utilized to affect the retention of peptides in this approach to OTCEC include the type and percentage of organic solvent modifier employed in the eluent and the pH of the buffer system. To evaluate the reproducibility of different batches of the n-octadecyl- and cholesterol-modified capillaries and the stability of the chemically modified surface, the OTCEC selectivity and peak shape behavior of two small basic molecules (serotonin and tryptamine) and two proteins (turkey and chicken lysozyme) were also investigated. Finally, the use of the "bubble" cell technology for creating the detector window has been shown to provide significantly higher detection sensitivity with peptides, as compared with the conventional capillary format.

Diblock copolymers consisting of a poly(acrylic acid) (PAA) segment and a LCST-type poly(N,N-diethylacrylamide) (PDEAAm) block were obtained by nitroxide-mediated polymerization in aqueous dispersion using a water-soluble macroalkoxyamine. The influence of several parameters on the polymerization (temperature, initial free nitroxide or macroalkoxyamine concentrations, and solids content) was evaluated in terms of kinetics, macromolecular control, and colloidal features. As determined by dynamic light scattering (DLS), stable dispersions of monodisperse particles could be obtained for solids content as high as 39 wt% without the need for any additional surfactant via a polymerization-induced self-assembly mechanism. Rendered possible by the use of a controlled/living polymerization process, the effective semi-batch incorporation of hydrophobic units (styrene) in the growing chains during the polymerization allowed the formation of physically crosslinked nanogels. The pH and temperature sensitivity were proved by means of DLS and high-sensitivity differential scanning calorimetry (HSDSC) measurements. Due to the formation of aggregates observed by size-exclusion chromatography in N,N-dimethylformamide, accurate molar masses could not be determined directly but deconvoluted hydrodynamic volume distributions suggested a good control of the polymerization.