The polymerisation of oligo(ethylene glycol methyl ether) methacrylate from a multifunctional poly(ethylene imine) derived amide: a stabiliser for the synthesis and dispersion of magnetite nanoparticles

A facile synthetic route to poly(ethylene imine)-graft-poly(oligo(ethylene glycol methyl ether)) (PEI-graft-POEGMA) functionalised superparamagnetic magnetite nanoparticles is described. The polymerisation of OEGMA from a model molecular amide demonstrated the feasibility of POEGMA synthesis under mild ATRP conditions (20 °C in ethanol) albeit with low initiator efficiencies. DFT studies suggest that the amide functionality is intrinsically of lower activity than ester functional monomers and initiators for atom transfer polymerisation (ATRP) as a consequence of higher bond dissociation energies and bond dissociation free energies (BDFE). However these studies further highlighted that use of an appropriate solvent could reduce the free energy of dissociation thereby reducing the relative difference in BDFE between the ester and amide groups. A commercial branched PEI sample was functionalised by reaction with 2-bromo-2-methylpropanoyl bromide giving an amide macroinitiator suitable for the atom transfer radical polymerisation (ATRP) of oligo(ethylene glycol methyl ether) methacrylate. The resulting PEI-graft-POEGMA copolymers were characterised by SEC, FT-IR and 1H and 13C NMR spectroscopy. PEI-graft-POEGMA coated magnetite nanoparticles were synthesised by a basic aqueous co-precipitation method and were characterised by transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometry and dynamic light scattering. These copolymer coated magnetite nanoparticles were demonstrated to be effectively stabilised in an aqueous medium. Overall the particle sizes and magnetic and physical properties of the coated samples were similar to those of uncoated samples

Autocatalytic ring opening of N-acylaziridines : Complete control over regioselectivity by orientation at interfaces

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Strategy for optimizing experimental settings for studying low atomic number colloidal assemblies using liquid phase scanning transmission electron microscopy

Observing processes of nanoscale materials of low atomic number is possible using liquid phase electron microscopy (LP-EM). However, the achievable spatial resolution (d) is limited by radiation damage. Here, we examine a strategy for optimizing LP-EM experiments based on an analytical model and experimental measurements, and develop a method for quantifying image quality at ultra low electron dose De using scanning transmission electron microscopy (STEM). As experimental test case we study the formation of a colloidal binary system containing 30 nm diameter SiO2 nanoparticles (SiONPs), and 100 nm diameter polystyrene microspheres (PMs). We show that annular dark field (DF) STEM is preferred over bright field (BF) STEM for practical reasons. Precise knowledge of the material's density is crucial for the calculations in order to match experimental data. To calculate the detectability of nano-objects in an image, the Rose criterion for single pixels is expanded to a model of the signal to noise ratio obtained for multiple pixels spanning the image of an object. Using optimized settings, it is possible to visualize the radiation-sensitive, hierarchical low-Z binary structures, and identify both components

Copper(II) complexes of a dicephalic imidazole surfactant. Tunable organization of metalloaggregates

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Surface induced selective delamination of amphiphilic ABA block copolymer thin films

This is the result of an ongoing collaboration with Dr. N. Sommerdijk’s Biomaterials group at the University of Eindhoven (the Netherlands) and illustrates the close collaboration that exists in pursuing the design and application of novel polymeric materials between the two groups. This details work on a physical phenomenon (selective delamination) and key materials (amphiphilic block copolymers) that have subsequently been applied in the design of novel biomaterials. These results have appeared in a larger body of work including Advanced Materials, Angewandtie Chemie International Edition and the Journal of Materials Chemistry

Controlling Internal Pore Sizes in Bicontinuous Polymeric Nanospheres

Complex polymeric nanospheres were formed in water from comb-like amphiphilic block copolymers. Their internal morphology was determined by three-dimensional cryo-electron tomographic analysis. Varying the polymer molecular weight (MW) and the hydrophilic block weight content allowed for fine control over the internal structure. Construction of a partial phase diagram allowed us to determine the criteria for the formation of bicontinuous polymer nanosphere (BPN), namely for copolymers with MW of up to 17?kDa and hydrophilic weight fractions of ?0.25; and varying the organic solvent to water ratio used in their preparation allowed for control over nanosphere diameters from 70 to 460?nm. Significantly, altering the block copolymer hydrophilic–hydrophobic balance enabled control of the internal pore diameter of the BPNs from 10 to 19?nm

Self-assembly of collagen molecules into fibrils in solution

Type I collagen is a major constituent of many biological tissues, including skin, bone, tendon and cartilages. Its main functions are to shape extracellular matrices, promote cell attachment and provide tissues with strength, flexibility and elasticity. At the core these functions is its remarkable ability of collagen to form highly organized fibrils through the self-assembly of the molecules. The fibrilogenesis involves the lateral association of collagen triple helices into staggered parallel arrays that give rise to the characteristic D-band periodicity of 67 nm. Currently, the mechanisms of collagen self-assembly are poorly understood. Here, we combine the nanometer-scale resolution of cryo-transmission electron microscopy (cryoTEM) with molecular dynamics to investigate the self-assembly of collagen molecules into fibrils in solution

Oriented crystallization of calcium carbonate under self-organized monolayers of amide-containing phospholipids

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Simulation of Calcium Phosphate Pre-Nucleation Clusters in Aqueous Solution: Association Beyond Ion Pairing

© 2019 American Chemical Society. Classical molecular dynamics simulations and free energy methods have been used to obtain a better understanding of the molecular processes occurring prior to the first nucleation event for calcium phosphate biominerals. The association constants for the formation of negatively charged complexes containing calcium and phosphate ions in aqueous solution have been computed, and these results suggest that the previously proposed calcium phosphate building unit, [Ca(HPO4)3]4-, should only be present in small amounts under normal experimental conditions. However, the presence of an activation barrier for the removal of an HPO42- ion from this complex indicates that this species could be kinetically trapped. Aggregation pathways involving CaHPO4, [Ca(HPO4)2]2-, and [Ca(HPO4)3]4- complexes have been explored with the finding that dimerization is favorable up to a Ca/HPO4 ratio of 1:2

Synthesis and crystal structure of (+)-(2R,3R)-N, N '-bis-trityl-2,3-bis-aziridine

Contains fulltext : 14200.pdf (publisher's version ) (Open Access