Molecularly Imprinted Polymers for the isolation of bioactive naphthoquinones from plant extracts

Molecularly Imprinted Polymers (MIPs) targeting shikonin, a potent antioxidant and wound healing agent, have been prepared using methacrylic acid (MAA) and 2-diethylaminoethyl methacrylate (DEAEMA) as functional monomers. An investigation of solution association between shikonin and both acidic and basic functional monomers by UV-Vis titrations, suggested stronger affinity towards the basic functionality. Strong inhibition of the co-polymerisation reaction of such basic monomers was observed, but was overcome by reduction of the amount of template used during polymer synthesis. Polymer morphology was severely impacted by the template’s radical scavenging behaviour as demonstrated by solid state NMR spectroscopy measurements. HPLC evaluation of the final materials in polar conditions revealed limited imprinting effects and selectivity, with the MAA polymers exhibiting marginally better performance. During application of the polymers as MI-SPE sorbents in non-polar solvents it was found that the DEAEMA based polymer was more selective towards shikonin compared to the MAA counterpart, while shikonin recoveries of up to 72% were achieved from hexane solutions of a commercial sample of shikonin, hexane extract of Alkanna tinctoria roots and a commercial pharmaceutical ointment.

Synthesis and characterization of amphiphilic star copolymers of 2-(dimethylamino) ethyl methacrylate and methyl methacrylate: Effects of architecture and composition

Six amphiphilic star copolymers comprising hydrophilic units of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic units of methyl methacrylate (MMA) were prepared by the sequential group transfer polymerization (GTP) of the two comonomers and ethylene glycol dimethacrylate (EGDMA) cross-linker. Four star-block copolymers of different compositions, one miktoarm star, and one statistical copolymer star were synthesized. The molecular weights (MWs) and MW distributions of all the star copolymers and their linear homopolymer and copolymer precursors were characterized by gel permeation chromatography (GPC), while the compositions of the stars were determined by proton nuclear magnetic resonance (H-1 NMR) spectroscopy. Tetrahydrofuran (THF) solutions of all the star copolymers were characterized by static light scattering to determine the absolute weight-average MW ((M) over bar (w)) and the number of arms of the stars. The R, of the stars ranged between 359,000 and 565,000 g mol(-1), while their number of arms ranged between 39 and 120. The star copolymers were soluble in acidic water at pH 4 giving transparent or slightly opaque solutions, with the exception of the very hydrophobic DMAEMA(10)-b-MMA(30)-star, which gave a very opaque solution. Only the random copolymer star was completely dispersed in neutral water, giving a very opaque solution. The effective pKs of the copolymer stars were determined by hydrogen ion titration and were found to be in the range 6.5-7.6. The pHs of precipitation of the star copolymer solutions/dispersions were found to be between 8.8-10.1, except for the most hydrophobic DMA-EMA(10)-b-MMA(30)-Star, which gave a very opaque solution over the whole pH range. (c) 2006 Elsevier Ltd. All rights reserved.

EL CVn-type binaries - Discovery of 17 helium white dwarf precursors in bright eclipsing binary star systems

The star 1SWASP J024743.37-251549.2 was recently discovered to be a binary star in which an A-type dwarf star eclipses the remnant of a disrupted red giant star (WASP 0247-25 B). The remnant is in a rarely observed state evolving to higher effective temperatures at nearly constant luminosity prior to becoming a very low mass white dwarf composed almost entirely of helium, i.e. it is a pre-helium white dwarf (pre-He-WD). We have used the photometric database from theWide Angle Search for Planets (WASP) to find 17 eclipsing binary stars with orbital periods P = 0.7-2.2 d with similar light curves to 1SWASP J024743.37-251549.2. The only star in this group previously identified as a variable star is the brightest one, EL CVn, which we adopt as the prototype for this class of eclipsing binary star. The characteristic light curves of EL CVn-type stars show a total eclipse by an A-type dwarf star of a smaller, hotter star and a secondary eclipse of comparable depth to the primary eclipse. We have used new spectroscopic observations for six of these systems to confirm that the companions to the A-type stars in these binaries have very low masses (≈0.2M⊙). This includes the companion to EL CVn which was not previously known to be a pre-He-WD. EL CVn-type binary star systems will enable us to study the formation of very low mass white dwarfs in great detail, particularly in those cases where the pre-He-WD star shows non-radial pulsations similar to those recently discovered in WASP0247-25 B. © 2013 The Authors Published by Oxford University Press on behalf of the Royal Astronomical Society.

Water spray cooling of polymers

The cooling process in conventional rotomolding is relatively long due to poor thermal conductivity of plastics. The lack of internal cooling is a major limitation although rapid external cooling is possible. Various internal cooling methodologies have been studied to reduce the cycle time. These include the use of compressed air, cryogenic liquid nitrogen, chilled water coils, and cryogenic liquid carbon dioxide, all of which have limitations. However, this article demonstrates the use of water spray cooling of polymers as a viable and effective method for internal cooling in rotomolding. To this end, hydraulic, pneumatic, and ultrasonic nozzles were applied and evaluated using a specially constructed test rig to assess their efficiency. The effects of nozzle type and different parametric settings on water droplet size, velocity, and mass flow rate were analyzed and their influence on cooling rate, surface quality, and morphology of polymer exposed to spray cooling were characterized. The pneumatic nozzle provided highest average cooling rate while the hydraulic nozzle gave lowest average cooling rate. The ultrasonic nozzle with medium droplet size traveling at low velocity produced satisfactory surface finish. Water spray cooling produced smaller spherulites compared to ambient cooling whilst increasing the cooling rate decreases the percentage crystallinity. © 2011 Society of Plastics Engineers Copyright © 2011 Society of Plastics Engineers.

The spotty donor star in the X-ray transient Cen X-4

We accurately determine the fundamental system parameters of the neutron star X-ray transient Cen X-4 solely using phase-resolved high-resolution UV-Visual Echelle Spectrograph spectroscopy. We first determine the radial-velocity curve of the secondary star and then model the shape of the phase-resolved absorption line profiles using an X-ray binary model. The model computes the exact rotationally broadened, phase-resolved spectrum and does not depend on assumptions about the rotation profile, limb-darkening coefficients and the effects of contamination from an accretion disc. We determine the secondary star-to-neutron star binary mass ratio to be 0.1755 ± 0.0025, which is an order of magnitude more accurate than previous estimates. We also constrain the inclination angle to be 32^{+8}_{-2} degrees. Combining these values with the results of the radial-velocity study gives a neutron star mass of 1.94^{+0.37}_{-0.85}M⊙ consistent with previous estimates. Finally, we perform the first Roche tomography reconstruction of the secondary star in an X-ray binary. The tomogram reveals surface inhomogeneities that are due to the presence of cool starspots. A large cool polar spot, similar to that seen in Doppler images of rapidly rotating isolated stars, is present on the Northern hemisphere of the K7 secondary star and we estimate that ~4 percent of the total surface area of the donor star is covered with spots.This evidence for starspots supports the idea that magnetic braking plays an important role in the evolution of low-mass X-ray binaries.

Photodynamic antimicrobial polymers for infection control

Hospital-acquired infections pose both a major risk to patient wellbeing and an economic burden on global healthcare systems, with the problem compounded by the emergence of multidrug resistant and biocide tolerant bacterial pathogens. Many inanimate surfaces can act as a reservoir for infection, and adequate disinfection is difficult to achieve and requires direct intervention. In this study we demonstrate the preparation and performance of materials with inherent photodynamic, surface-active, persistent antimicrobial properties through the incorporation of photosensitizers into high density poly(ethylene) (HDPE) using hot-melt extrusion, which require no external intervention except a source of visible light. Our aim is to prevent bacterial adherence to these surfaces and eliminate them as reservoirs of nosocomial pathogens, thus presenting a valuable advance in infection control. A two-layer system with one layer comprising photosensitizer-incorporated HDPE, and one layer comprising HDPE alone is also described to demonstrate the versatility of our approach. The photosensitizer-incorporated materials are capable of reducing the adherence of viable bacteria by up to 3.62 Log colony forming units (CFU) per square centimeter of material surface for methicillin resistant Staphylococcus aureus (MRSA), and by up to 1.51 Log CFU/cm2 for Escherichia coli. Potential applications for the technology are in antimicrobial coatings for, or materials comprising objects, such as tubing, collection bags, handrails, finger-plates on hospital doors, or medical equipment found in the healthcare setting.

Silk-inspired polymers and proteins

The biocompatibility and biodegradability of natural silk fibres and the benign conditions under which they (with impressive mechanical properties) are produced represent a biomimetic ideal. This ideal has inspired people in both academia and industry to prepare silk-mimetic polymers and proteins by chemical and/or biotechnological means. in the present paper, we aim to give an overview of the design principles of such silk-inspired polymers/proteins, their processing into various materials morphologies, their mechanical and biological properties, and, finally, their technical and biomedical applications.

Automatic extruder for processing recycled polymers with ultrasound and temperature control system

Melt viscosity is one of the main factors affecting product quality in extrusion processes particularly with regard to recycled polymers. However, due to wide variability in the physical properties of recycled feedstock, it is difficult to maintain the melt viscosity during extrusion of polymer blends and obtain good quality product without generating scrap. This research investigates the application of ultrasound and temperature control in an automatic extruder controller, which has ability to maintain constant melt viscosity from variable recycled polymer feedstock during extrusion processing. An ultrasonic modulation system has been developed and fitted to the extruder prior to the die to convey ultrasonic energy from a high power ultrasonic generator to the polymer melt. Two separate control loops have been developed to run simultaneously in one controller: the first loop controls the ultrasonic energy or temperature to maintain constant die pressure, the second loop is used to control extruder screw speed to maintain constant throughput at the extruder die. Time response and energy consumption of the control methods in real-time experiments are also investigated and reported this paper.

Hydrogel-Forming Microneedles Prepared from ‘‘Super Swelling’’ Polymers Combined with Lyophilised Wafers for Transdermal Drug Delivery

We describe, for the first time, hydrogel-forming microneedle arrays prepared from "super swelling" polymeric compositions. We produced a microneedle formulation with enhanced swelling capabilities from aqueous blends containing 20% w/w Gantrez S-97, 7.5% w/w PEG 10,000 and 3% w/w Na2CO3 and utilised a drug reservoir of a lyophilised wafer-like design. These microneedle-lyophilised wafer compositions were robust and effectively penetrated skin, swelling extensively, but being removed intact. In in vitro delivery experiments across excised neonatal porcine skin, approximately 44 mg of the model high dose small molecule drug ibuprofen sodium was delivered in 24 h, equating to 37% of the loading in the lyophilised reservoir. The super swelling microneedles delivered approximately 1.24 mg of the model protein ovalbumin over 24 h, equivalent to a delivery efficiency of approximately 49%. The integrated microneedle-lyophilised wafer delivery system produced a progressive increase in plasma concentrations of ibuprofen sodium in rats over 6 h, with a maximal concentration of approximately 179 µg/ml achieved in this time. The plasma concentration had fallen to 71±6.7 µg/ml by 24 h. Ovalbumin levels peaked in rat plasma after only 1 hour at 42.36±17.01 ng/ml. Ovalbumin plasma levels then remained almost constant up to 6 h, dropping somewhat at 24 h, when 23.61±4.84 ng/ml was detected. This work represents a significant advancement on conventional microneedle systems, which are presently only suitable for bolus delivery of very potent drugs and vaccines. Once fully developed, such technology may greatly expand the range of drugs that can be delivered transdermally, to the benefit of patients and industry. Accordingly, we are currently progressing towards clinical evaluations with a range of candidate molecules.

Non-covalent hydrogels of cyclodextrins and poloxamines for the controlled release of proteins

Different types of gels were prepared by combining poloxamines (Tetronic), i.e. poly(ethylene oxide)/poly(propylene oxide) (PEO/PPO) octablock star copolymers, and cyclodextrins (CD). Two different poloxamines with the same molecular weight (ca. 7000) but different molecular architectures were used. For each of their four diblock arms, direct Tetronic 904 presents PEO outer blocks while in reverse Tetronic 90R4 the hydrophilic PEO blocks are the inner ones. These gels were prepared by combining alpha-CD and poloxamine aqueous solutions. The physicochemical properties of these systems depend on several factors such as the structure of the block copolymers and the Tetronic/alpha-CD ratio. These gels were characterized using differential scanning calorimetry (DSC), viscometry and X-ray diffraction measurements. The 90R4 gels present a consistency that makes them suitable for sustained drug delivery. The resulting gels were easily eroded: these complexes were dismantled when placed in a large amount of water, so controlled release of entrapped large molecules such as proteins (Bovine Serum Albumin, BSA) is feasible and can be tuned by varying the copolymer/CD ratio. 

Interacting supernovae and supernova impostors. SN 2007sv: the major eruption of a massive star in UGC 5979

We report the results of the photometric and spectroscopic monitoring campaign of the transient SN 2007sv. The observables are similar to those of Type IIn supernovae, a well-known class of objects whose ejecta interact with pre-existing circumstellar material (CSM). The spectra show a blue continuum at early phases and prominent Balmer lines in emission; however, the absolute magnitude at the discovery of SN 2007sv (M-R=-14.25 +/- 0.38) indicate it to be most likely a supernova impostor. This classification is also supported by the lack of evidence in the spectra of very high velocity material as expected in supernova ejecta. In addition, we find no unequivocal evidence of broad lines of alpha- and/or Fe-peak elements. The comparison with the absolute light curves of other interacting objects (including Type IIn supernovae) highlights the overall similarity with the prototypical impostor SN 1997bs. This supports our claim that SN 2007sv was not a genuine supernova, and was instead a supernova impostor, most likely similar to the major eruption of a luminous blue variable.

Pre-Main-Sequence Accretion in the Low Metallicity Galactic Star-forming Region Sh 2-284

We present optical spectra of pre-main-sequence (PMS) candidates around the Ha region taken with the Southern African Large Telescope in the low metallicity (Z) Galactic region Sh 2-284, which includes the open cluster Dolidze 25 with an atypical low metallicity of Z similar to 1/5 Z(circle dot). It has been suggested on the basis of both theory and observations that PMS mass-accretion rates, (M) over dot(acc), are a function of Z. We present the first sample of spectroscopic estimates of mass-accretion rates for PMS stars in any low-Z star-forming region. Our data set was enlarged with literature data of H alpha emission in intermediate-resolution R-band spectroscopy. Our total sample includes 24 objects spanning a mass range between 1 and 2 M-circle dot and with a median age of approximately 3.5 Myr. The vast majority (21 out of 24) show evidence for a circumstellar disk on the basis of Two Micron All Sky Survey and Spitzer infrared photometry. We find (M) over dot(acc) in the 1-2 M-circle dot interval to depend quasi-quadratically on stellarmass, with (M) over dot(acc) proportional to M-*(2.4 +/- 0.35), and inversely with stellar age, with (M) over dot(acc) proportional to t(*)(-0.7 +/- 0.4). Furthermore, we compare our spectroscopic (M) over dot(acc) measurements with solar Z Galactic PMS stars in the same mass range, but, surprisingly find no evidence for a systematic change in (M) over dot(acc) with Z. We show that literature accretion-rate studies are influenced by detection limits, and we suggest that (M) over dot(acc) may be controlled by factors other than Z(*), M-*, and age.

Viscosity Control for Extrusion Processes Using Recycled Polymers

The aim of this paper is to develop a new extruder control system for recycled materials which has ability to automatically maintain constant a polymer melt viscosity of mixed recycled polymers during extrusion, regardless of variations in the Melt Flow Index (MFI) of recycled mixed grade high density polyethylene (HDPE) feedstock. A closed-loop controller is developed to automatically regulate screw speed and barrel temperature profile to achieve constant viscosity and enable consistent processing of variable grade recycled HDPE materials. The experimental results of real time viscosity measurement and control using a 38mm single screw extruder with different recycled HDPEs with widely different MFIs are reported in this work