A Facile Strategy for the High Yielding, Quantitative Conversion of Polyglycol End-Groups to Amines.

Amino end-group functionalised polyglycols are important intermediates in the synthesis of sophisticated polymeric architectures and biomaterials. Herein, we report a facile strategy for the end-group conversion of hydroxyl-terminated polyglycols to amino-terminated polyglycols in high isolated yields and with excellent end-group fidelity. Following traditional conversion of polyglycol hydroxyl end-groups to azides via the corresponding mesylate, reduction with zinc in the presence of ammonium chloride afforded a range of amino end-group functionalised poly(ethylene glycol) and poly(propylene glycol) homopolymers and copolymers with isolated yields of 82-99% and end-group conversions of >99% as determined by NMR spectroscopy and MALDI ToF MS. Furthermore, this process is applicable to a sequential reagent addition approach without intermediate polymer isolation steps with only a slight reduction in yield and end-group conversion (95%). Importantly, a simple work-up procedure provides access to high purity polyglycols without contamination from other reagents.

Thermoresponsive polysaccharides with tunable thermoresponsive properties via functionalisation with alkylamide groups.

Polysaccharides have been used widely in many industries, from food technology and mining to cosmetics and biomedical applications. Over recent years there has been growing interest in the development of responsive polysaccharides with unique and switchable properties, particularly systems that display lower-critical solution temperatures (LCSTs). Therefore, in this study we aimed to investigate a novel strategy that would allow the conversion of non-responsive polysaccharides into thermoresponsive polysaccharides with tuneable LCSTs. Through the functionalisation of dextran with alkylamide groups (isopropyl amide, diethyl amide, piperidinyl and diisobutyl amide) using a carbodiimide coupling approach in conjunction with amic acid derivatives, we prepared a library of novel dextrans with various degrees of substitution (DS), which were characterised via nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The alkylamide-functionalised dextrans were found to have good solubility in aqueous solutions, with the exception of those having a high DS of large hydrophobic substituents. Determination of the thermoresponsive characteristics of the polymer solutions via UV-vis spectroscopy revealed that the LCST of the alkylamide-functionalised dextrans was highly dependent on the type of alkylamide group and the DS and could be tuned over a large range (5-35 °C). Above the LCST, all of the thermoresponsive alkylamide-functionalised dextrans formed colloidal dispersions with particles sizes ranging from 400 -600 nm, as determined by dynamic light scattering (DLS). In addition, the polymers were found to exhibit a fast and reversible phase transition in solution with narrow hysteresis (∼ 1-5 °C). Finally, the injectability and biocompatibility of the novel thermoresponsive dextrans was confirmed in vivo via subcutaneous and intracranial ventricle injections, with no local or systemic toxicity noted over a 14 d period. Overall, the alkylamide-functionalised dextrans display interesting thermoresponsive properties and trends that may make them useful in biomedical applications, such as drug-delivery.

Challenges of plastic waste generation and management in sub-Saharan Africa: A review.

Recently, the issues of land-based plastics and their associated challenges in the marine world have been widely publicised in the media and scientific literature. Thus far, despite these communications, there have been few reports that have focused on the issues that acute plastic waste generation and its poor management pose to human health and the global environment. Also, articles on ways to mitigate these issues particularly in sub-Saharan Africa have not been documented. Indeed, there is significant scope for improvements in plastic waste management in developing countries, which offer a wide range of economic and environmental benefits. Plastic waste generation in sub-Saharan Africa is dependent on many factors like urbanization, etc. Currently, the population of sub-Saharan Africa is around 1 billion as of the year 2019, the amount of generated waste is 180 million tonnes at the rate of 0.5% per capita per day, the amount that is openly dumped is 70% and the plastic waste generated annually is 17 million tonnes. Therefore, this study aims to provide an overview of the plastic lifecycle and problems associated with plastic waste management in sub-Saharan Africa, including current practices, public participation and opinion, and government regulations. In addition, this highlight aims to outline the impact of plastic waste proliferation on man and the environment; and the economic and environmental benefits of proper plastic waste management. Critical discussion of current processes and the suitability of potential solutions provide the basis for proposition on mitigation measures to avert the negative impact of plastic waste.

Thermoresponsive polysaccharides and their thermoreversible physical hydrogel networks.

Thermoresponsive polymers have been used extensively for various applications including food additives, pharmaceutical formulations, therapeutic delivery, cosmetics and environmental remediation, to mention a few. Many thermoresponsive polymers have the ability to form physical hydrogel networks in response to temperature changes, which are particularly useful for emerging biomedical applications, including cell therapies, drug delivery systems, tissue engineering, wound healing and 3D bioprinting. In particular, the use of polysaccharides with thermoresponsive properties has been of interest due to their wide availability, versatile functionality, biodegradability, and in many cases, inherent biocompatibility. Naturally thermoresponsive polysaccharides include agarose, carrageenans and gellan gum, which exhibit upper critical solution temperatures, transitioning from a solution to a gel state upon cooling. Arguably, this limits their use in biomedical applications, particularly for cell encapsulation as they require raised temperatures to maintain a solution state that may be detrimental to living systems. Conversely, significant progress has been made over recent years to develop synthetically modified polysaccharides, which tend to exhibit lower critical solution temperatures, transitioning from a solution to a gel state upon warming. Of particular interest are thermoresponsive polysaccharides with a lower critical solution temperature in between room temperature and physiological temperature, as their solutions can conveniently be manipulated at room temperature before gelling upon warming to physiological temperature, which makes them ideal candidates for many biological applications. Therefore, this review provides an introduction to the different types of thermoresponsive polysaccharides that have been developed, their resulting hydrogels and properties, and the exciting applications that have emerged as a result of these properties.

Van der Waals Emulsions: Emulsions Stabilized by Surface-Inactive, Hydrophilic Particles via van der Waals Attraction.

Surface-inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil-in-water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil-water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion-based technologies in practice.

Directed self-assembly of gold nanoparticles into plasmonic chains.

The plasmonic behavior of metals at the nanoscale is not only appealing for fundamental studies, but also very useful for the development of innovative photonic devices. The past few decades have witnessed great progress in colloidal synthesis of monodisperse metal nanoparticles with defined shapes. This has significantly fueled up the research of directing the metal nanoparticles to self-assemble into tailored extended structures, especially low dimensional ones, for a better control and manipulation of the interactions of the metal nanoparticles with light. In parallel, theories for a better description of nanoplasmonics have been increasingly developed and improved. Thus, the present review is focused on the overview of current experimental and theoretical developments in the directed self-assembly of metal nanoparticles with tailored plasmonic properties, which, hopefully, will provide useful guidelines for future research studies and applications of nanoplasmonics.