Post-polymerization functionalization of poly(ethylene oxide)–poly(β-6-heptenolactone) diblock copolymers to tune properties and self-assembly

Copolymers were synthesized and functionalized with a variety of moieties to tune self-assembly and install drugs or fluorescent dyes. , Polyester-based amphiphilic block copolymers and their nanoassemblies are of significant interest for a wide range of applications due to the degradability of the polyester block. However, the commonly used polyesters lack functional groups on their backbones, limiting the possibilities to chemically modify these polymers. Described here are new poly(ethylene oxide) (PEO)–poly(β-6-heptenolactone) (PHEL) block copolymers having pendant alkenes at each repeat unit on the PHEL block. First, the self-assembly of these block copolymers in aqueous solution was studied and it was found that they formed solid nanoparticles and vesicles depending on the relative block lengths. Next the alkene moieties of the block copolymer were modified with either hydrophilic or hydrophobic pendant groups using thiol–ene reactions, allowing the hydrophilic mass fractions and consequently the self-assembled morphologies to be tuned, accessing both smaller nanoparticles and cylindrical assemblies. It was also demonstrated that the anti-cancer drug paclitaxel or a fluorescent rhodamine dye could be easily conjugated to the block copolymers and the self-assembly of these conjugates was explored. Overall, the results of this study demonstrate that PEO-PHEL block copolymers can serve as versatile backbones for the preparation of functional, polyester-based materials

Polymer assembly encapsulation of lanthanide nanoparticles as contrast agents for in vivo micro-CT

Despite recent technological advancements in microcomputed tomography (micro-CT) and contrast agent development, pre-clinical contrast agents are still predominantly iodine-based. Higher contrast can be achieved when using elements with higher atomic numbers, such as lanthanides; lanthanides also have x-ray attenuation properties that are ideal for spectral CT. However, the formulation of lanthanide-based contrast agents at the high concentrations required for vascular imaging presents a significant challenge. In this work, we developed an erbium-based contrast agent that meets micro-CT imaging requirements, which include colloidal stability upon redispersion at high concentrations, evasion of rapid renal clearance, and circulation times of tens of minutes in small animals. Through systematic studies with poly(ethylene glycol) (PEG)-poly(propylene glycol), PEG-polycaprolactone, and PEG-poly(l-lactide) (PLA) block copolymers, the amphiphilic block copolymer PEG114-PLA53 was identified to be ideal for encapsulating oleate-coated lanthanide-based nanoparticles for in vivo intravenous administration. We were able to synthesize a contrast agent containing 100 mg/mL of erbium that could be redispersed into colloidally stable nanoparticles in saline after lyophilization. Contrast enhancement of over 250 HU was achieved in the blood pool for up to an hour, thereby meeting the requirements of live animal micro-CT

An aromatic/aliphatic polyester prepared via ring-opening polymerisation and its remarkably selective and cyclable depolymerisation to monomer

The ring-opening polymerisation of 2,3-dihydro-5H-1,4-benzodioxepin-5-one gives polyester homopolymers and copolymers that contain both aromatic and aliphatic linkages. The polymers can be easily depolymerised by Al catalysts.</p

On invisible trade relations between Mesopotamian cities during the third millennium BC

The idea that the emergence of writing was necessity due to the increase in both die number of economic transactions and political complexity has been recently emphasized by Matthews, who also underlines that writing acted as a feedback in enabling and encouraging the growth of ever more complex modes of exchange. The intertwinement of trade and writing suggests that clay tablets left by the civilizations from the third millennium B.C. in Mesopotamia, where writing was invented, may be considered as traces of trade links and transactions between cities. We estimate a gravity model based on clay tablets, as if they represented trade flows. The parameters lead us to conclude that Mesopotamia formed a strongly integrated market

Single Component Iron Catalysts for Atom Transfer and Organometallic Mediated Radical Polymerizations: Mechanistic Studies and Reaction Scope

Tetradentate amine–bis­(phenolate)­iron­(III) halide complexes containing chloro substituents on the aromatic ring are extremely efficient catalysts for controlled radical polymerization. Molecular weights are in good agreement with theoretical values, and dispersities are as low as 1.07 for substituted styrenes and methyl methacrylate polymerizations. Kinetic data reveal activity for styrene polymerization among the fastest reported to date, with the excellent control shown to be electronic rather than steric in origin. Mechanistic studies implicate a multimechanism system with cooperation between atom transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP). The <i>in situ</i> reduction of the Fe­(III) complex with ascorbic acid or tin octanoate allows polymerizations to be initiated by both 1-phenylethyl chloride (1-PECl, ATRP regime) and azobis­(isobutyronitrile) (AIBN, OMRP regime) to isolate the mechanism of control and offer unique initiation pathways

Photoinduced Degradation of Polymer Films Using Polyglyoxylate-Polyester Blends and Copolymers

© 2018 American Chemical Society. Polymeric coatings are commonly employed to alter surface properties. While some coatings are designed to remain stable over a prolonged period, in applications such as pharmaceuticals or fertilizers, the coating is designed to erode and reveal or release the underlying material. Self-immolative polymers (SIPs) undergo depolymerization following the cleavage of stimuli-responsive end-caps from their termini, enabling controlled depolymerization in the solid state and in solution. Poly(ethyl glyoxylate) (PEtG) is a promising SIP because of its depolymerization to benign products, but its amorphous structure and low glass-transition temperature make it unsuitable alone for coating applications. This study explored the blending of PEtG with polyesters including polycaprolactone (PCL), poly(l-lactic acid), and poly(R-3-hydroxybutyrate). Block copolymers of PEtG with PCL were also synthesized and studied. It was found that the phase separation behavior and consequently the thermal and mechanical properties of the materials could be tuned according to the composition of the blend, while the stimuli-responsive degradation of PEtG was retained in the blends. This work therefore provides a framework for the application of PEtG-based coatings in applications ranging from pharmaceuticals to agricultural products