A new approach to high resolution, high contrast electron microscopy of macromolecular block copolymer assemblies

Determining the structure of macromolecular samples is vital for understanding and adapting their function. Transmission electron microscopy (TEM) is widely used to achieve this, but, owing to the weak electron scattering cross-section of carbon, TEM images of macromolecular samples are generally low contrast and low resolution. Here we implement a fast and practically simple routine to achieve high-contrast imaging of macromolecular samples using exit wave reconstruction (EWR), revealing a new level of structural detail. This is only possible using ultra-low contrast supports such as the graphene oxide (GO) used here and as such represents a novel application of these substrates. We apply EWR on GO membranes to study self-assembled block copolymer structures, distinguishing not only the general morphology or nanostructure, but also evidence for the substructure (i.e. the polymer chains) which gives insight into their formation mechanisms and functional properties

Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation

YesCo-crystallization of polymers with different configurations/tacticities provides access to materials with enhanced performance. The stereocomplexation of isotactic poly(L-lactide) and poly(D-lactide) has led to improved properties compared with each homochiral material. Herein, we report the preparation of stereocomplex micelles from a mixture of poly(L-lactide)-b-poly(acrylic acid) and poly(D-lactide)-b-poly(acrylic acid) diblock copolymers in water via crystallization-driven self-assembly. During the formation of these stereocomplex micelles, an unexpected morphological transition results in the formation of dense crystalline spherical micelles rather than cylinders. Furthermore, mixture of cylinders with opposite homochirality in either THF/H2O mixtures or in pure water at 65 °C leads to disassembly into stereocomplexed spherical micelles. Similarly, a transition is also observed in a related PEO-b-PLLA/PEO-b-PDLA system, demonstrating wider applicability. This new mechanism for morphological reorganization, through competitive crystallization and stereocomplexation and without the requirement for an external stimulus, allows for new opportunities in controlled release and delivery applications.University of Warwick, Swiss National Science Foundation and the EPSRC. The Royal Society - an Industry Fellowship to A.P.D. The Engineering and Physical Sciences Research Council (EP/G004897/1) - funding to support postdoctoral fellowships for A.P.B. as well as funding for J.S. and M.A.D. through the Warwick Centre for Analytical Science (EP/F034210/1). The Science City Research Alliance and the HEFCE Strategic Development Fund - funding support. Some items of equipment that were used in this research were funded by Birmingham Science City, with support from Advantage West Midlands and part-funded by the European Regional Development Fund

Review of the Palaearctic species of Ismaridae Thomson, 1858 (Hymenoptera: Diaprioidea)

This is an open access article, available to all readers online, published under a Creative Commons BY-NC-ND license: https://creativecommons.org/licenses/by-nc-nd/3.0/. The attached file is the published version of the article

Aqueous worm gels can be reconstituted from freeze-dried diblock copolymer powder.

Worm-like diblock copolymer nanoparticles comprising poly(glycerol monomethacrylate) (PGMA) as a stabilizer block and poly(2-hydroxypropyl methacrylate) (PHPMA) as a core-forming block were readily synthesized at 10% w/w solids via aqueous dispersion polymerization at 70 °C using Reversible Addition-Fragmentation chain Transfer (RAFT) chemistry. On cooling to 20 °C, soft transparent free-standing gels are formed due to multiple inter-worm interactions. These aqueous PGMA-PHPMA diblock copolymer worms were freeze-dried, then redispersed in water with cooling to 3-5 °C before warming up to 20 °C; this protocol ensures molecular dissolution of the copolymer chains, which aids formation of a transparent aqueous gel. Rheology, SAXS and TEM studies confirm that such reconstituted gels comprise formed PGMA-PHPMA copolymer worms and they possess essentially the same physical properties determined for the original worm gels prior to freeze-drying. Such worm gel reconstitution is expected to be highly beneficial in the context of various biomedical applications, since it enables worm gels to be readily prepared using a wide range of cell growth media as the continuous aqueous phase

Bespoke cationic nano-objects via RAFT aqueous dispersion polymerisation

A range of cationic diblock copolymer nanoparticles are synthesised via polymerisation-induced self-assembly (PISA) using a RAFT aqueous dispersion polymerisation formulation. The cationic character of these nanoparticles can be systematically varied by utilising a binary mixture of two macro-CTAs, namely non-ionic poly(glycerol monomethacrylate) (PGMA) and cationic poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride (PQDMA), with poly(2-hydroxypropyl methacrylate) (PHPMA) being selected as the hydrophobic core-forming block. Thus a series of cationic diblock copolymer nano-objects with the general formula ([1 - n] PGMAx + [n] PQDMAy) - PHPMAz were prepared at 20% w/w solids, where n is the mol fraction of the cationic block and x, y and z are the mean degrees of polymerisation of the non-ionic, cationic and hydrophobic blocks, respectively. These cationic diblock copolymer nanoparticles were analysed in terms of their chemical composition, particle size, morphology and cationic character using 1H NMR spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), and aqueous electrophoresis, respectively. Systematic variation of the above PISA formulation enabled the formation of spheres, worms or vesicles that remain cationic over a wide pH range. However, increasing the cationic character favors the formation of kinetically-trapped spheres, since it leads to more effective steric stabilisation which prevents sphere-sphere fusion. Furthermore, cationic worms form a soft free-standing gel at 25 °C that undergoes reversible degelation on cooling, as indicated by variable temperature oscillatory rheology studies. Finally, the antimicrobial activity of this thermo-responsive cationic worm gel towards the well-known pathogen Staphylococcus aureus is examined via direct contact assays

Bi-fractional transforms in phase space

The displacement operator is related to the displaced parity operator through a two dimensional Fourier transform. Both operators are important operators in phase space and the trace of both with respect to the density operator gives the Wigner functions (displaced parity operator) and Weyl functions (displacement operator). The generalisation of the parity-displacement operator relationship considered here is called the bi-fractional displacement operator, O(α, β; θα, θβ). Additionally, the bi-fractional displacement operators lead to the novel concept of bi-fractional coherent states. The generalisation from Fourier transform to fractional Fourier transform can be applied to other phase space functions. The case of the Wigner-Weyl function is considered and a generalisation is given, which is called the bi-fractional Wigner functions, H(α, β; θα, θβ). Furthermore, the Q−function and P−function are also generalised to give the bi-fractional Q−functions and bi-fractional P−functions respectively. The generalisation is likewise applied to the Moyal star product and Berezin formalism for products of non-commutating operators. These are called the bi-fractional Moyal star product and bi-fractional Berezin formalism. Finally, analysis, applications and implications of these bi-fractional transforms to the Heisenberg uncertainty principle, photon statistics and future applications are discussed

Thermo-responsive Diblock Copolymer Worm Gels in Non-polar Solvents

Benzyl methacrylate (BzMA) is polymerized using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) using reversible addition–fragmentation chain transfer (RAFT) polymerization at 70 °C in n-dodecane. This choice of solvent leads to an efficient dispersion polymerization, with polymerization-induced self-assembly (PISA) occurring via the growing PBzMA block to produce a range of PLMA–PBzMA diblock copolymer nano-objects, including spheres, worms, and vesicles. In the present study, particular attention is paid to the worm phase, which forms soft free-standing gels at 20 °C due to multiple inter-worm contacts. Such worm gels exhibit thermo-responsive behavior: heating above 50 °C causes degelation due to the onset of a worm-to-sphere transition. Degelation occurs because isotropic spheres interact with each other much less efficiently than the highly anisotropic worms. This worm-to-sphere thermal transition is essentially irreversible on heating a dilute solution (0.10% w/w) but is more or less reversible on heating a more concentrated dispersion (20% w/w). The relatively low volatility of n-dodecane facilitates variable-temperature rheological studies, which are consistent with eventual reconstitution of the worm phase on cooling to 20 °C. Variable-temperature 1H NMR studies conducted in d26-dodecane confirm partial solvation of the PBzMA block at elevated temperature: surface plasticization of the worm cores is invoked to account for the observed change in morphology, because this is sufficient to increase the copolymer curvature and hence induce a worm-to-sphere transition. Small-angle X-ray scattering and TEM are used to investigate the structural changes that occur during the worm-to-sphere-to-worm thermal cycle; experiments conducted at 1.0 and 5.0% w/w demonstrate the concentration-dependent (ir)reversibility of these morphological transitions

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, whereas the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained

Titanium-mediated [CpTiCl2(OEt)] ring-opening polymerization of lactides: a novel route to well-defined polylactide-based complex macromolecular architectures

Among three cyolopentadienyl titanium complexes studied, CpTiCl 2(OEt), containing a 5% excess CpTiCl3, has proven to be a very efficient catalyst for the ring-opening polymerization (ROP) of L-lactide (LLA) in toluene at 130 °C Kinetic studies revealed that the polymerization yield (up to 100%) and the molecular weight increase linearly with time, leading to well-defined PLLA with narrow molecular weight distributions [M w/Mn ≤ 1.1). Based on the above results, PS-b-PLLA, PI-b-PLLA, PEO-b-PLLA block copolymers, and a PS-b-PI-b-PLLA triblock terpolymer were synthesized. The synthetic strategy involved: (a) the preparation of OH-end-functionalized homopolymers or diblock copolymers by anionic polymerization, (b) the reaction of the OH-functionalized polymers with CpTiCl3 to give the corresponding Ti-macrocatalyst, and (c) the ROP of LLA to afford the final block copolymers. PMMA-gPLLA [PMMA: poly(methyl methacrylate)] was also synthesized by: (a) the reaction of CpTiCl3 with 2-hydroxy ethyl methacrylate, HEMA, to give the Ti-HEMA-catalyst, (b) the ROP of LLA to afford a PLLA methacrylic-macromonomer, and (c) the copolymerization (conventional and ATRP) of the macromonomer with MMA to afford the final graft copolymer. Intermediate and final products were characterized by NMR spectroscopy and size exclusion chromatography, equipped with refractive index and two-angle laser light scattering detectors. © 2010 Wiley Periodicals, Inc