Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field

Aerodynamic load distributions at transonic speeds for a close-coupled wing-canard configuration: Tabulated pressure data

Wind tunnel studies are reported on both the canard and wing surfaces of a model that is geometrically identical to one used in several force and moment tests to provide insight into the various aerodynamic interference effects. In addition to detailed pressures measurements, the pressures were integrated to illustrate the effects of Mach number, canard location, and canard-wing interference on various aerodynamic parameters. Transonic pressure tunnel Mach numbers ranged from 0.70 to 1.20 for data taken from 0 deg to approximately 16 deg angle-of-attack at 0 deg sideslip

A First Amendment Failure: Surrendering to Science Misinformation for Bioengineered Foods

Government-compelled commercial disclosures are not unfamiliar to consumers. Common labels include nutrition facts and ingredient information. The National Bioengineered Food Disclosure Standard, which took full force at the start of 2022, is of a different nature. The new law requires all manufacturers, all importers, and certain retailers of bioengineered foods to disclose on the food’s packaging that it has been produced with bioengineering technology. Even so, a large swath of the public is ignorant of “bioengineering’s” true meaning and bioengineering technology’s true quality. The politically charged and fact-lacking debate on bioengineered foods renders this standard an impermissible coercion of speech in violation of the First Amendment. If stricter regulation of potentially harmful food products is truly desired, a more appropriate target for compelled disclosure is pesticide use. Using science communication principles and factual information on the outcomes of bioengineered foods as a backdrop, this Note argues against the labeling of bioengineered foods and for alternative pesticide disclosures

Morphological control in the solution crystallisation of polymeric nanoparticles

Chapter One gives a broad introduction to the research described herein, initially discussing the reasons for morphology control, polymerisation techniques and self- assembly methods. A general introduction to solution crystallisation of polymers is given, with a focus on block copolymers with a crystalline core-forming block. Chapter Two discusses the use of various poly(L-lactide) based amphiphiles to propose a unimer solubility-based shape selectivity mechanism for the formation of 1D and 2D nanostructures, leading to a single component solution phase protocol for the preparation of uniform diamond-shaped platelets. Chapter Three considers the use of three different morphologies, namely spheres, cylinders and platelets, as nanocomposites in calcium alginate hydrogels, where a greater shear strength is measured for platelet-composite hydrogels. Chapter Four utilises the proposed unimer solubility approach to create 2D diamond-shaped platelets of controlled size and shape. The use of different size platelets as water-in-water Pickering emulsifiers is explored, where larger plates are shown to give more stable emulsions. Chapter Five employs the use of a poly(ɛ-caprolactone) crystallisable core-forming block for the preparation of 1D cylindrical structures of controlled length and dispersity. Direct epitaxial growth in water is shown, leading to the preparation of strong hydrogel materials. Chapter Six summarises the research presented, giving general conclusions as well as discussing the scope for future investigations in this area of research

Automation in Moderation

This Article assesses recent efforts to encourage online platforms to use automated means to prevent the dissemination of unlawful online content before it is ever seen or distributed. As lawmakers in Europe and around the world closely scrutinize platforms’ “content moderation” practices, automation and artificial intelligence appear increasingly attractive options for ridding the Internet of many kinds of harmful online content, including defamation, copyright infringement, and terrorist speech. Proponents of these initiatives suggest that requiring platforms to screen user content using automation will promote healthier online discourse and will aid efforts to limit Big Tech’s power.In fact, however, the regulations that incentivize platforms to use automation in content moderation come with unappreciated costs for civil liberties and unexpected benefits for platforms. The new automation techniques exacerbate existing risks to free speech and user privacy and create ripe new sources of information for surveillance, aggravating threats to free expression, associational rights, religious freedoms, and equality. Automation also worsens transparency and accountability deficits. Far from curtailing private power, the new regulations endorse and expand platform authority to police online speech, with little in the way of oversight and few countervailing checks. New regulations of online intermediaries should therefore incorporate checks on the use of automation to avoid exacerbating these dynamics. Carefully drawn transparency obligations, algorithmic accountability mechanisms, and procedural safeguards can help to ameliorate the effects of these regulations on users and competition