Manganese-Catalyzed Synthesis of Polyketones Using Hydrogen-Borrowing Approach.

We report here a method of making polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access various polyketones (polyarylalkylketone) containing aryl, alkyl, and ether functionalities, bridging the gap between the two classes of commercially available polyketones: aliphatic polyketones and polyaryletherketones. Using this methodology, 12 polyketones have been synthesized and characterized using various analytical techniques to understand their chemical, physical, morphological, and mechanical properties. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones.

Enhancement of infrared absorption through a patterned thin film of magnetic field and spin-coating directed self-assembly of gold nanoparticle stabilised ferrofluid emulsion.

Molecular vibration signals were amplified by the gold strip gratings as a result of grating resonances and nearby electric field hotspots. Colloidal gold island films exhibit similar enhancement; however, the uneven geometrical characteristics of these films restrict the tunability of the vibrational enhancement. Infrared absorption is enhanced by regular metallic patterns such as arrays of strips fabricated using a top-down approach such as nanolithography, although this technology is expensive and difficult. The significant infrared absorption may serve as tuneable antenna sensitization to improve the sensor performance. In this article, we present a simple one-step process for fabricating optically sensitive ordered arrays of a gold nanoparticle ferrofluid emulsion in polyvinyl alcohol (PVA) using a magnetic field-directed and spin-coating self-assembly (MDSCSA) process. Techniques such as UV-visible absorption, scanning electron microscopy, and grazing-angle infrared spectroscopy were used to evaluate various parameters associated with the nanostructures. Unlike the gold strips, the chain-like features in the iron oxide nanoparticle arrays were discontinuous. The fabricated chain-like ordered arrays have been shown to increase the local field to enhance the infrared absorption corresponding to the symmetric vibration of the -CH2 (2918 cm-1) group present in PVA by ∼667% at a 45° grazing angle, as the chain thickness (CT) increased by 178%. This scalable and simple method can potentially generate low-cost patterns for antenna sensitisation.

Tuneable magnetic nanocomposites for remote self-healing.

When polymer composites containing magnetic nanoparticles (MNPs) are exposed to an alternating magnetic field, heat is generated to melt the surrounding polymer locally, partially filling voids across any cracks or deformities. Such materials are of interest for structural applications; however, structural polymers with high melting temperatures pose the challenge of generating high localised temperatures enabling self-healing. A method to prepare a multiferroic-Polyamide 6 (PA6) nanocomposite with tuneable magnetocaloric properties is reported. Tunability arises from varying the MNP material (and any coating, its dispersion, and agglomerate sizes in the nanocomposite). The superparamagnetic MNPs (SMNPs) and iron oxide MNPs with and without surface functionalization were dispersed into PA6 through in situ polymerization, and their magnetic properties were compared. Furthermore, computer simulations were used to quantify the dispersion state of MNPs and assess the influence of the interaction radius on the magnetic response of the self-healable magnetic nanoparticle polymer (SHMNP) composite. It was shown that maintaining the low interaction radius through the dispersion of the low coercivity MNPs could allow tuning of the bulk magnetocaloric properties of the resulting mesostructures. An in-situ polymerization method improved the dispersion and reduced the maximum interaction radius value from ca. 806 to 371 nm and increased the magnetic response for the silica-coated SMNP composite. This sample displayed ca. three orders of magnitude enhancement for magnetic saturation compared to the unfunctionalized Fe3O4 MNP composite.

Experimental Investigation on Micro Milling of Polyester/Halloysite Nano-Clay Nanocomposites.

Efficient machining of the polyester nanocomposite components requires a better understanding of machinability characteristics of such material, which has become an urgent requirement for modern industrial production. In this research, the micro-milling of polyester/halloysite nano-clay (0.1, 0.3, 0.7, 1.0 wt%) nanocomposites were carried out and the outcomes in terms of tool wear, cutting force, the size effect, surface morphology, and surface roughness were compared with those for plain polyester. In order to accomplish the machining of the material in ductile mode, the required feed per tooth was found to be below 0.3 µm. The degree of surface breakage was also found to decrease in ductile mode. A maximum flank wear VB of 0.012 mm after removing 196 mm3 of workpiece material was measured.

High Yielding Microbubble Production Method.

Microfluidic approaches to microbubble production are generally disadvantaged by low yield and high susceptibility to (micro)channel blockages. This paper presents an alternative method of producing microbubbles of 2.6 µm mean diameter at concentrations in excess of 30 × 10(6) mL(-1). In this method, the nitrogen gas flowing inside the liquid jet is disintegrated into spray of microbubble when air surrounding this coflowing nitrogen gas-liquid jet passes through a 100 µm orifice at high velocity. Resulting microbubble foam has the polydispersity index of 16%. Moreover, a ratio of mean microbubble diameter to channel width ratio was found to be less than 0.025, which substantially alleviates the occurrence of blockages during production.

Microbubble-liposome conjugate: Payload evaluation of potential theranostic vehicle.

Liposome-microbubble conjugates are considered as better targeted drug delivery vehicles compared to microbubbles alone. The microbubble in the integrated drug delivery system delivers the drug intracellularly on the target, whereas the liposome component allows loading of high drug dose and extravasation through leaky vasculature. In this work, a new high yielding microbubble production method was used to prepare microbubbles for formulation of the liposome-conjugated drug delivery system. In formulation process, the prepared liposome of 200 nm diameter was attached to the microbubble surface using the avidin-biotin interaction. The analysis of the confocal scanning laser microscope images showed that approximately 8 × 108 microbubbles per millilitre (range: 2-7 µm, mean size 5 ± 0.5 µm) can be efficiently conjugated to the liposomes. The method of conjugation was found to be effective in attaching liposome to microbubbles.

A review of imaging methods for measuring drug release at nanometre scale: a case for drug delivery systems.

INTRODUCTION: Current drug delivery research is focused on improving the efficacy of drug delivery systems, with emphasis on precise targeting, accurate dose delivery, strategies for overcoming the tissue barrier and monitoring the effects of drugs on their targets. To realize these goals, it is essential to determine the spatio-temporal bio-distribution of particles in the whole animal. Enabling such a measurement at the nanometer scale helps in the design of efficient systems. AREAS COVERED: This article discusses the need for molecular imaging in drug delivery development and also reviews promising imaging methods. Moreover, the physics behind each method is explained and evaluated to derive advantages and limitations. The review enables the readers to select, use and modify the existing methods to implement imaging protocols for studying drug release from particular drug delivery. EXPERT OPINION: Currently, the difference in pharmacodynamics obtained via various imaging modalities cannot be verified and hinders clinical use. To establish imaging as a scientific tool, its translation into clinical use is vital. Presently, there is no single imaging method suitable for drug-release studies. However, hybrid imaging has the potential to provide the desired imaging system.

In vitro method to characterize diffusion of dye from polymeric particles: a model for drug release.

The release profile of a drug delivery system is a key factor in determining its efficacy. In the case of a polymeric particle based system, the release profile is a function of several parameters including particle diameter and porosity. The effects of these parameters are usually investigated experimentally using UV-spectroscopy. Predicting the drug release profile from particles as a result of the interaction of many parameters is desirable in order to facilitate the design of more efficient drug delivery particles. In this work, a quantitative method of determining the diffusion profile is developed which removes the need for repetitive experimentation. Particles of polymethylsilsesquioxane were prepared using coaxial electrohydrodynamic atomization and collected in solutions containing different concentrations of Evans blue dye (6, 0.6, and 0.06 mg/mL) which was used to simulate a drug. The dye release profile was calculated by solving the unsteady state diffusion equation for parameters used in the experiments. It was demonstrated that the dye release profile from particles with diameters ranging from 400 nm to 9 mum can be calculated using a simple equation without addition of a dissolution term, if the volume ratio of surrounding liquid to particle in the unsteady second order solution is substituted by the surface area of particles to liquid volume ratio. The calculated data are found to be in good agreement with the experimental, indicating that this method can be used to determine the diffusion coefficient as a function of particle diameter and material. This study represents a crucial step toward developing a full drug release model.

Novel electrohydrodynamic preparation of porous chitosan particles for drug delivery.

Uniform spherical chitosan particles of size <10 microm in diameter are important in drug delivery applications due to their excellent biocompability and biodegradability. A high concentration of chitosan in the particles can help to control the release of drugs and methods for processing high viscosity chitosan solutions are therefore required. In principle, any type of polymer, whether hydrophobic or hydrophilic, can be electrosprayed to obtain monodisperse particles of diameter <10 microm. In practice, however, electrospraying of biopolymers having viscosities of >100 mPa s results in particles >10 microm diameter. In this study, by reducing surface tension of a high viscosity chitosan suspension, it was found that smaller diameter particles could be prepared. Chitosan solutions were electrosprayed in the stable cone-jet mode to systematically study the relationship between particle diameter, viscosity and surface tension. Increasing viscosity resulted in larger diameter particles with a broad size distribution, but decreasing surface tension had the opposite effect. Results show that a chitosan solution having a viscosity of approximately 80 mPa s can be used to prepare chitosan particles of diameter approximately 2.5 microm which on drying reduced to particles of 500 nm.

Generation of microbubbles for diagnostic and therapeutic applications using a novel device.

Developments in both diagnostic and therapeutic applications of microbubbles have greatly increased the need for more advanced preparation technologies which provide a well-defined, narrow microbubble size-distribution. In this paper, we demonstrate the use of a new device, consisting of a T-junction whose outlet capillary is fitted with an electrohydrodynamic spraying arrangement, to prepare phospholipid-coated air microbubbles, making significant advances in controlling and decreasing the size and size-distribution, and increasing the stability/lifetime of the bubbles prepared. The microbubbles were characterised via optical microscopy to determine the relationship between the size-distribution obtained and the process variables, specifically the flow rates of the phospholipid suspension and air (Q(l) and Q(g)), and the applied voltage (V). The formation of microbubbles in the device was also studied using high-speed photography. For the range of parameters investigated, the bubble diameter was found to scale with the product of the flow rate ratio (Q(l)/Q(g)) and the applied voltage, with a consistent bubble diameter of 5.1 +/- 2 microm being obtained at Q(l)/Q(g) = 1.7 and V = 18 kV. The bubbles prepared using this method were found to be stable for at least 2 h at ambient temperature and pressure.

Dynamics of bubble formation in highly viscous liquids.

There has recently been considerable interest in the development of devices for the preparation of monodisperse microbubble suspensions for use as ultrasound contrast agents and drug delivery vehicles. These applications require not only a high degree of bubble uniformity but also a maximum bubble size of 8 mum, and this provides a strong motivation for developing an improved understanding of the process of bubble formation in a given device. The aim of this work was to investigate bubble formation in a T-junction device and determine the influence of the different processing parameters upon bubble size, in particular, liquid viscosity. Images of air bubble formation in a specially designed T-junction were recorded using a high-speed camera for different ratios of liquid to gas flow rate (Ql/Qg) and different liquid viscosities (microl). It was found that theoretical predictions of the flow profile in the focal region based on analysis of axisymmetric Stokes flow were accurate to within 6% when compared with the experimental data, indicating that this provided a suitable means of describing the bubble formation process. Both the theoretical and experimental results showed that Ql/Qg and mul had a significant influence upon bubble formation and eventual size, with higher flow rates and higher viscosities producing smaller bubbles. There were, however, found to be limiting values of Ql/Qg and mul beyond which no further reduction in bubble size was achieved.