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

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

Aragonite formation in confinements: A step toward understanding polymorph control

Calcium carbonate (CaCO3) is one of the most common minerals on Earth; it not only forms rocks like limestone or marble but is also a main component of biominerals such as pearls, the nacre of seashells, and sea-urchin skeletons (1). Despite many years of research, the polymorphism of CaCO3 is still far from being understood. CaCO3 has three anhydrous crystalline forms: calcite, aragonite, and vaterite, with a decreasing thermodynamic stability under aqueous ambient conditions (calcite > aragonite > vaterite) (2). While vaterite is rare in nature, calcite and aragonite are both frequently found in rocks or biominerals (1). A well-known example is the aragonite structure of nacre (3), where the organization of the crystals leads to extraordinary mechanical performance. However, in synthetic systems, crystallization experiments only generate a small fraction of aragonite compared with calcite at ambient conditions and in the absence of additives (4). So, how is the formation of aragonite facilitated in nature, especially in biominerals? In PNAS, Zeng et al. (5) shed light on this matter by showing that aragonite formation is dramatically promoted within confinements

Disordered Filaments Mediate the Fibrillogenesis of Type I Collagen in Solution

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In-situ liquid phase imaging of block copolymer vesicle assembly

Amphiphilic block copolymers in aqueous solution can assemble into various ordered molecular architectures, which have a wide range of applications in, for example, drug delivery and catalytic nanoreactors.1 While sustained efforts, both experimentally and theoretically, have been made to better understand the mechanism of self- assembly in order to gain more control over this process,2, 3 there has never been a real-time, real space investigation of the assembly process on the nanoscale. Here we show the first observation of block copolymer vesicle assembly via the solvent switch protocol4 using liquid phase transmission electron microscopy (LP-TEM). We also discuss the different mechanisms of self-assembly with the ex-situ cryo-TEM observation and compare them with self-consistent field (SCF) lattice calculations. Our findings illustrate the ability of LP-TEM to implement quantitative visualization of local formation process of the block copolymer vesicles to reveal the formation mechanism on an individual particle level Please click Additional Files below to see the full abstract

CryoTEM as an Advanced Analytical Tool for Materials Chemists

Morphology plays an essential role in chemistry through the segregation of atoms and/or molecules into different phases, delineated by interfaces. This is a general process in materials synthesis and exploited in many fields including colloid chemistry, heterogeneous catalysis, and functional molecular systems. To rationally design complex materials, we must understand and control morphology evolution. Toward this goal, we utilize cryogenic transmission electron microscopy (cryoTEM), which can track the structural evolution of materials in solution with nanometer spatial resolution and a temporal resolution of <1 s. In this Account, we review examples of our own research where direct observations by cryoTEM have been essential to understanding morphology evolution in macromolecular self-assembly, inorganic nucleation and growth, and the cooperative evolution of hybrid materials. These three different research areas are at the heart of our approach to materials chemistry where we take inspiration from the myriad examples of complex materials in Nature. Biological materials are formed using a limited number of chemical components and under ambient conditions, and their formation pathways were refined during biological evolution by enormous trial and error approaches to self-organization and biomineralization. By combining the information on what is possible in nature and by focusing on a limited number of chemical components, we aim to provide an essential insight into the role of structure evolution in materials synthesis. Bone, for example, is a hierarchical and hybrid material which is lightweight, yet strong and hard. It is formed by the hierarchical self-assembly of collagen into a macromolecular template with nano- and microscale structure. This template then directs the nucleation and growth of oriented, nanoscale calcium phosphate crystals to form the composite material. Fundamental insight into controlling these structuring processes will eventually allow us to design such complex materials with predetermined and potentially unique properties

ABA triblock copolymers: from controlled synthesis to controlled function

The ABA amphiphilic block copolymers, poly(hydroxyethyl methacrylate-hlock-methylphenylsilane-block-hydroxyethyl methacrylate) (PHEMA-PMPS-PHEMA) and poly[oligo(ethylene glycol) methyl ether methacrylate-block-methylphenylsilane-block-oligo(ethylene glycol). methyl ether methacrylate] (POEGMA-PMPS-POEGMA) were successfully synthesised via atom transfer radical polymerisation (ATRP). Macroinitiators suitable for the ATRP of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate were synthesised from the condensation reaction of alpha,omega-dihalopolymethylphenylsilane and 2'-hydroxyethyl 2-bromo-2-methylpropanoate. The copolymers were characterised using H-1 NMR and C-13 NMR spectroscopy and molecular weight characteristics were determined using size exclusion chromatography and H-1 NMR. The aggregation behaviour of some of the copolymers in water was studied using transmission and scanning electron microscopy and dynamic light scattering. These revealed the prevalent aggregate species to be micelles. Larger aggregates of 300-1000 nm diameter were also observed. The UV induced degradation of the aggregates was studied by UV-Vis spectroscopy. The thermal behaviour of selected copolymers was studied by differential scanning calorimetry and microphase separation of the two components was demonstrated