Very high pressure liquid chromatography using fully porous particles: Quantitative analysis of fast gradient separations without post-run times

Using a column packed with fully porous particles, four methods for controlling the flow rates at which gradient elution runs are conducted in very high pressure liquid chromatography (VHPLC) were tested to determine whether reproducible thermal conditions could be achieved, such that subsequent analyses would proceed at nearly the same initial temperature. In VHPLC high flow rates are achieved, producing fast analyses but requiring high inlet pressures. The combination of high flow rates and high inlet pressures generates local heat, leading to temperature changes in the column. Usually in this case a post-run time is input into the analytical method to allow the return of the column temperature to its initial state. An alternative strategy involves operating the column without a post-run equilibration period and maintaining constant temperature variations for subsequent analysis after conducting one or a few separations to bring the column to a reproducible starting temperature. A liquid chromatography instrument equipped with a pressure controller was used to perform constant pressure and constant flow rate VHPLC separations. Six replicate gradient separations of a nine component mixture consisting of acetophenone, propiophenone, butyrophenone, valerophenone, hexanophenone, heptanophenone, octanophenone, benzophenone, and acetanilide dissolved in water/acetonitrile (65:35, v/v) were performed under various experimental conditions: constant flow rate, two sets of constant pressure, and constant pressure operation with a programmed flow rate. The relative standard deviations of the response factors for all the analytes are lower than 5% across the methods. Programming the flow rate to maintain a fairly constant pressure instead of using instrument controlled constant pressure improves the reproducibility of the retention times by a factor of 5, when plotting the chromatograms in time.

Graphene oxide decorated diatom silica particles as new nano-hybrids: Towards smart natural drug microcarriers

Herein, we demonstrate the fabrication of a novel nano-hybrid material based on diatom silica microparticles from diatomaceous earth (DE) and graphene oxide (GO). Two different approaches for the fabrication of nano-hybrids were used, including covalent coupling of GO sheets onto the diatom surface and electrostatic attachment. Covalent attachment was carried out through a facile amine coupling strategy via activation of carboxyl groups on GO, followed by covalent attachment to amine terminal groups of 3-aminopropyl-triethoxysilane (APTES) functionalized DE particles. Electrostatic attachment of GO (i.e. negatively charged) was carried out on positively charged APTES functionalized DE particles. The GO decorated DE nano-hybrids prepared with both the fabrication processes were extensively characterized by SEM, TEM, FTIR, and Raman spectroscopy to confirm the new chemical composition and structure. The application of the GO-DE nano-hybrid as a smart pH sensitive micro-drug carrier at pH 7.4 and pH 3.5 was demonstrated using a model drug, indomethacin (IMC). Finally, the drug release data were fitted to zero-order and Korsmeyer-Peppas models to understand the mechanism of drug release. This journal is © The Royal Society of Chemistry.

Roll-formability of cryo-rolled ultrafine aluminium sheet

Ultrafine-grain aluminium sheet was produced by rolling at cryogenic (CR) and at room temperature (RTR). Commercial purity aluminium plate was reduced in 30 passes from an initial material thickness of 10 mm to a final thickness of 2 mm (80% reduction). Tensile stress and strength were significantly increased while total elongation was drastically reduced. It was found that despite the low tensile elongation both materials are able to accommodate high localised strains in the neck leading to a high reduction in area. The formability of the material was further investigated in bending operations. A minimum bending radius of 6 mm (CR) and 5 mm (RTR) was found and pure bending tests showed homogeneous forming behaviour for both materials. In V-die bending the cryo-rolled material showed strain localisations across the final radius and kinking of the sample. It has been found that even if the total elongation in tension is close to zero leading to early failure in V-die bending, ultra-fine grained and low ductile sheet metals can be roll formed to simple section shapes with small radii using commercial roll forming equipment.

Ultrafine grain formation in a Ti-6Al-4V alloy by thermomechanical processing of a martensitic microstructure

In the current study, ultrafine equiaxed grains with a size of 150 to 800 nm were successfully produced in a Ti-6Al-4V alloy through thermomechanical processing of a martensitic starting microstructure. This was achieved through a novel mechanism of grain refinement consisting of several concurrent processes. This involves the development of substructure in the lath interiors at an early stage of deformation, which progressed into small high-angle segments with increasing strain. Consequently, the microstructure was gradually transformed to an equiaxed ultrafine grained structure, mostly surrounded by high-angle grain boundaries, through continuous dynamic recrystallization. Simultaneously, the supersaturated martensite was decomposed during deformation, leading to the progressive formation of beta phase, mainly nucleated on the intervariant lath boundaries.

Silver nanoparticles prepared by gamma irradiation across metal-organic framework templates

In this study, we demonstrate for the first time the successful fabrication of well-dispersed ultrafine silver nanoparticles inside metal-organic frameworks through a single step gamma irradiation at room temperature. HKUST-1 crystals are soaked in silver nitrate aqueous solution and irradiated with a Cobalt 60 source across a range of irradiation doses to synthesize highly uniformly distributed silver nano-particles. The average size of the silver nanoparticles across the Ag@HKUST-1 materials is found to vary between 1.4 and 3 nm for dose exposures between 1 and 200 kGy, respectively. The Ag@HKUST-1 hybrid crystals exhibit strong surface plasmon resonance and are highly durable and efficient catalytic materials for the reduction of 4-nitrophenol to 4-aminophenol (up to 14.46 × 10-3 s-1 for 1 kGy Ag@HKUST-1). The crystals can be easily recycled for at least five successive cycles of reaction with a conversion efficiency higher than 99.9%. The gamma irradiation is demonstrated to be an effective and environmental friendly process for the synthesis of nano-particles across confined metal-organic frameworks at room temperature with potential applications in environmental science.

Towards integrated anti-microbial capabilities: Novel bio-fouling resistant membranes by high velocity embedment of silver particles

Biofilm formation on membranes during water desalination operation and pre-treatments limits performance and causes premature membrane degradation. Here, we apply a novel surface modification technique to incorporate anti-microbial metal particles into the outer layer of four types of commercial polymeric membranes by cold spray. The particles are anchored on the membrane surface by partial embedment within the polymer matrix. Although clear differences in particle surface loadings and response to the cold spray were shown by SEM, the hybrid micro-filtration and ultra-filtration membranes were found to exhibit excellent anti-bacterial properties. Poly(sulfone) ultra-filtration membranes were used as for cross-flow filtration of Escherichia coli bacteria solutions to investigate the impact of the cold spray on the material[U+05F3]s integrity. The membranes were characterized by SEM-EDS, FT-IR and TGA and challenged in filtration tests. No bacteria passed through the membrane and filtrate water quality was good, indicating the membranes remained intact. No intact bacteria were found on hybrid membranes, loaded with up to 15. wt% silver, indicating the treatment was lysing bacteria on contact. However, permeation of the hybrid membranes was found to be reduced compared to control non-modified poly(sulfone) membranes due to the presence of the particles across the membrane material. The implementation of cold spray technology for the modification of commercial membrane products could lead to significant operational savings in the field of desalination and water pre-treatments.

Ultrafine PDMS fibers: Preparation from in situ curing-electrospinning and mechanical characterization

Polydimethylsiloxane (PDMS) fibers with unexpected elasticity were prepared by a modified core-shell electrospinning method using a commercially-available liquid PDMS precursor (Sylgard 184) and polyvinylpyrrolidone (PVP) as core and sheath materials, respectively. The liquid PDMS precursor was crosslinked in situ to form a solid core when the newly-electrospun core-sheath nanofibers were deposited onto a hot-plate electrode collector. After dissolving the PVP sheath layer off the fibers, net PDMS fibers showed larger average diameter than core-sheath fibers, with an average diameter around 1.35 μm. The tensile properties of both single fibers and fibrous mats were measured. Single PDMS fibers had a tensile strength and elongation at break of 6.0 MPa and 212%, respectively, which were higher than those of PDMS cast film (4.9 MPa, 93%). The PDMS fiber mat had larger elongation at break than the single PDMS fibers, which can be drawn up to 403% their original length. Cyclic loading tests indicated a Mullin effect on the PDMS fiber mats. Such a superior elastic feature was attributed to the PDMS molecular orientation within fibers and the randomly-orientated fibrous structure. Highly-elastic, ultrafine PDMS fibers may find applications in strain sensors, biomedical engineering, wound healing, filtration, catalysis, and functional textiles. © The Royal Society of Chemistry 2014.

Comparison of milling and solution approach for production of silk particles

Silk particles were produced by regenerating from silk solution, and using a milling method. In the regenerated silk particle production, two methods which are reported to render submicron silk particles were selected. Their particle sizes and structures were compared with particles of milling method already developed by us. The volume median average particle sizes (d(0.5)) of regenerated particles were much higher than what was reported previously. In contrast, milling method could produce particles with adjustable particle sizes ranging from micron to submicron level. All the milled particles had advantage of at least 15. °C higher thermal decomposition temperature than regenerated particles. They had silk II structure, and the crystallinity reduced as particle fineness increased, but remained higher than regenerated particles of similar sizes. © 2014 Elsevier B.V.

Structure and characteristics of milled silk particles

This study examined the structure, thermal property, and ion adsorption of silk particles. The particles were prepared by attritor-bead mill combination, using alkaline (pH10) charge repulsion and surfactant steric repulsion methods. Both methods produced particles with a dominant β-sheet structure, similar to the silk fibre. There was no significant difference in the decomposition temperatures for either the silk fibre or the micro/nano silk particles. An important finding from this study is clear evidence of reduction of amorphous content during the final stage of powdering using the bead mill. As a result, despite reduction in β-sheet crystallites with the progressive milling, the relative β-sheet content actually increased during this process. However, intermolecular forces between the β-sheets reduced significantly and hence the XRD results showed significant reduction in crystallinity in nano silk particles but crystal forming segments remained with β-sheet conformations after milling. The structural change influenced the ion-adsorption property where particle-size reduction resulted in a significant increase in both the rate and volume of HCrO4- adsorption. © 2014 Elsevier B.V.

Silk powder for regenerative medicine

Two approaches are used for silk particle production: bottom up and top down. In the bottom up approach, different liquid-solid phase transfer techniques are adapted to fabricate particles from silk solution. In the top down approach, silk fibres are milled by various means to prepare ultrafine silk particles. Many important properties of particles such as size, geometry, porosity, stability and biodegradability are dependent on the specific methods of particle production. These properties influence drug loading and release, delivery modes, biocompatibility and their clearance from the body. Particle properties also determine biomechanical properties of particle reinforced composite scaffolds. Thus correlation between preparation, characterisation and application of silk particles for a specific biomedical application is critical. Progress made in this direction and challenges ahead are discussed in this chapter. © 2014 Woodhead Publishing Limited. All rights reserved.

The development of ultrafine-grained hot rolling products using advanced thermomechanical processing

The aim of the work is development of industry guidance concerning production of ultrafine-grained (UFG) High Strength Low Alloy (HSLA) steels using strain-induced dynamic phase transformations during advanced thermomechanical processing. In the first part of the work, the effect of processing parameters on the grain refinement was studied. Based on the obtained results, a multiscale computer model was developed in the second part of the work that was subsequently used to predict the mechanical response of studied structures. As an overall outcome, a process window was established for the production of UFG steels that can be adopted in existing hot rolling mills. © 2014 Elsevier B.V.

Lipid merging, protrusion and vesicle release triggered by shrinking/swelling of poly(N-isopropylacrylamide) microgel particles

Cell membrane changes its morphology during many physiological processes with the assistance of a solid support, such as the cytoskeleton, under an environmental stimulus. Here, a novel type of stimuli-responsive lipogel was fabricated, mimicking the changes of cell membrane. The lipogel was prepared from poly(N-isopropylacrylamide) (pNIPAM) microgel particle and phospholipid by a solvent-exchange method. The temperature dependent volume phase transition of pNIPAM triggers reversible transformation of the lipogel between a lipid vesicle-coated sun-like structure and a contracted hybrid sphere, through lipid merging and protrusion processes, respectively. By contrast, the salt induced pNIPAM phase transition leads to an irreversible vesicle release behaviour. The lipogel creates a unique platform for studying cell membrane behaviour and provides promising candidates in drug delivery and controlled release applications. © 2014 Elsevier B.V. All rights reserved.

Nanostructured liquid crystalline particles as next generation agrochemical delivery vehicles

A new system for delivering agrichemicals to crop plants was investigated. Nano-structured lipid particles were used as an alternative to traditional surfactants for penetrating plant surfaces. In laboratory and field trials the nanoparticles delivered chemicals effectively, caused less damage to plants, required less water and resulted in lower environmental impacts.

Ultrafine wools: comfort and handle properties for next-to-skin knitwear and manufacturing performance

This study aimed to quantify the skin comfort and handle properties of a range of wool fabrics produced from ultrafine wool (13.7–15.1 µm) and in doing so determine if differences in fiber diameter and staple crimp frequency (5.3–7.1 crimps/cm) were important in these properties. The fabrics were evaluated using a range of subjective and objective measurement techniques, including the Wool ComfortMeter, the Wool HandleMeter and in wearer trials. This work indicated that single jersey fabrics made from ultrafine wool are approaching the limit of objective and subjective evaluation of next-to-skin comfort. The results from the Wool ComfortMeter, Wool HandleMeter and the wearer trial show that there were no significant effects that can be attributed to wool staple crimp (fiber curvature) in these ultrafine wool fabrics. The work also demonstrated a difference in the manufacturing response when knitted fabric made from wools of different fiber diameter (13.7–23.7 µm), and using yarns of the same count, resulted in a progressively higher fabric mass per unit area as mean fiber diameter was progressively reduced.

Drug loading and release studies for milled silk particles of different sizes

Milled silk particles with volume median particle size (d(0.5)) of 7 μm and 281 nm as well as silk snippets were used for loading of model drugs Orange G, Azophloxine, Rhodamine B, and Crystal Violet. Loading and release of these chemicals depended on the size of silk particles, pH, and the structure and properties of model drugs. Both types of silk particles reached equilibrium loading in less than 10 min due to high surface area whereas silk fibres needed more than 2-3 days to reach equilibrium, depending on the drug type. The uptake rate in fibres could be improved by increasing temperature. Both fibres and particles could slowly release the drugs over many days at 37 °C without a significant initial burst. As particle size decreased, the amount of model drug release also decreased. The release of drugs by the silk fibres was quicker than the silk particles.