I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[10237]
Open Access
Abstract: Poly(stearyl methacrylate)–poly(benzyl methacrylate) [PSMA–PBzMA] diblock copolymer worms were synthesized directly in mineral oil via reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization at 90 °C. Free-standing gels were obtained from this polymerization-induced self-assembly (PISA) formulation when targeting PSMA13–PBzMA65 dispersions at 5% w/w to 20% w/w copolymer concentration. Gel permeation chromatography (GPC) studies indicated that almost identical copolymer chains were obtained in all cases, while transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies confirmed that highly anisotropic worms were formed with mean cross-sectional diameters of 11.9–13.1 nm. These worms undergo a thermoreversible worm-to-sphere transition on heating up to 150 °C. Rheological studies were conducted to characterize the shear rate- and concentration-dependent behaviour caused by this change in copolymer morphology, where the initial shear-thinning worm gels form spheres (i.e. a Newtonian fluid) on heating up to 150 °C. Complementary shear-induced polarized light imaging (SIPLI) experiments confirmed the formation of aligned linear worms under applied shear between 80 °C and 110 °C, with high-viscosity dispersions of branched worms being obtained at 20–60 °C and low-viscosity spheres being produced at 150 °C. This study informs the use of such block copolymer worms as rheology modifiers for non-polar oils, which is of potential interest for the automotive industry.
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Sep 2021
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I13-1-Coherence
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Open Access
Abstract: X-ray ptychography has revolutionized nanoscale phase contrast imaging at large-scale synchrotron sources in recent years. We present here the first successful demonstration of the technique in a small-scale laboratory setting. An experiment was conducted with a liquid metal-jet x-ray source and a single photon-counting detector with a high spectral resolution. The experiment used a spot size of
5
μ
m
to produce a ptychographic phase image of a Siemens star test pattern with a submicron spatial resolution. The result and methodology presented show how high-resolution phase contrast imaging can now be performed at small-scale laboratory sources worldwide.
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May 2021
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Cate T.
O'Brien
,
Tommi
Virtanen
,
Sergii
Donets
,
James
Jennings
,
Olga
Guskova
,
Anna H.
Morrell
,
Matt
Rymaruk
,
Leena
Ruusuvirta
,
Juha
Salmela
,
Harri
Setala
,
Jens-Uwe
Sommer
,
Anthony J.
Ryan
,
Oleksandr
Mykhaylyk
Abstract: Native cellulose is insoluble in water, despite the high number of hydrogen bonding sites per chain, as molecules preferably hydrogen bond to each other, preventing its use in industrial applications. The modification of cellulose has received considerable recent attention, motivated by the move away from conventional petroleum-based, water-soluble polymers, however, a systematic analysis of the effects of modification is rare. Herein a detailed study of hydroxypropyl (HP)- and (2-hydroxypropyl) trimethylammonium chloride-modified cellulose, with degrees of substitution (DS) determined by NMR, establishes modification-property relationships. TEM, small-angle X-ray scattering and rheology demonstrated that increasing DS gradually changes the aqueous solubility, resulting in the formation of different morphologies, including micron-sized aggregates, needle-like cellulose nanoparticles (CNPs) and solvated molecules. It was found that aqueous dispersions with DSHP of 50 %, assigned to a ‘sweet spot’ in cellulose modification, are suitable for the fiber formation. It is shown that this state of the material can be easily detected by rheo-optical methods based on birefringence. Using structural analysis, molecular dynamic simulation and fiber-spinning results, it is proposed that co-existing CNPs and cellulose molecules, interacting via H-bonding, form a network which orients under shear, acting as a precursor for the fiber formation from aqueous solutions.
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Mar 2021
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[15478, 14948, 12950]
Open Access
Abstract: Graphene oxide (GO) forms a well-aligned lyotropic liquid crystal (LC) phase in aqueous dispersions at relatively low concentrations. Under a remarkably wide range of shear rates, we report hitherto unobserved shear-induced polarized light image patterns, a Maltese cross combined with shear banding, recorded in real time and in situ during rheological measurements. This is shown to be a result of elastic flow instabilities that manifest as a helical flow in alternating bands of left- and right-handed helices, arising from a combination of shear flow and Taylor-type vortex flow. The instability is observed for LCs formed from large aspect ratio GO particles owing to their unique viscoelastic properties, but not for smaller aspect ratio particles. This phenomenon coincides with rheopecty and anomalous small-angle X-ray scattering patterns under shear flow, which confirm the instabilities. The results presented here could lead to advanced control over macroscopic periodic alignment in technologically relevant dispersions of two-dimensional material particles.
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Jan 2021
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[21776]
Open Access
Abstract: Over the past two decades, block copolymer vesicles have been widely used by many research groups to encapsulate small molecule drugs, genetic material, nanoparticles or enzymes. They have also been used to design examples of autonomous self-propelled nanoparticles. Traditionally, such vesicles are prepared via post-polymerization processing using a water-miscible co-solvent such as DMF or THF. However, such protocols are invariably conducted in dilute solution, which is a significant disadvantage. In addition, the vesicle size distribution is often quite broad, whereas aqueous dispersions of relatively small vesicles with narrow size distributions are highly desirable for potential biomedical applications. Alternatively, concentrated dispersions of block copolymer vesicles can be directly prepared via polymerization-induced self-assembly (PISA). Moreover, using a binary mixture of a relatively long and a relatively short steric stabilizer block enables the convenient PISA synthesis of relatively small vesicles with reasonably narrow size distributions in alcoholic media (C. Gonzato et al., JACS, 2014, 136, 11100–11106). Unfortunately, this approach has not yet been demonstrated for aqueous media, which would be much more attractive for commercial applications. Herein we show that this important technical objective can be achieved by judicious use of two chemically distinct, enthalpically incompatible steric stabilizer blocks, which ensures the desired microphase separation across the vesicle membrane. This leads to the formation of well-defined vesicles of around 200 nm diameter (size polydispersity = 13–16%) in aqueous media at 10% w/w solids as judged by transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering.
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Jun 2020
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[17255]
Abstract: A series of poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nano-objects has been synthesized via reversible addition–fragmentation chain-transfer (RAFT) dispersion polymerization in n-dodecane at 20 wt%. This polymerization-induced self-assembly (PISA) formulation was modified by the incorporation of an anionic monomer, tetradodecylammonium 3-sulfopropyl methacrylate ([NDod4]+[SPMA]−) into the oil-insoluble PBzMA block. According to the literature (M. J. Derry, et al., Chem. Sci., 2016, 7, 5078–5090), PSMA18–PBzMA diblock copolymers only form spheres using this formulation for any core degree of polymerization. Unexpectedly, incorporating just a small fraction (<6 mol%) of [NDod4]+[SPMA]− comonomer into the structure-directing block resulted in the formation of non-spherical diblock copolymer nano-objects, including pure worm-like and vesicular morphologies. However, only spherical micelles could be formed using a longer PSMA34 stabilizer. These diblock copolymer nano-objects were characterized by transmission electron microscopy, small-angle X-ray scattering, and dynamic light scattering. The bulky nature of the ionic comonomer appears to make it possible to avoid the kinetically-trapped sphere morphology. This study reveals a new approach for tuning the morphology of diblock copolymer nano-objects in non-polar media.
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Apr 2020
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[12950, 15246]
Open Access
Abstract: Hydrogels’ hydrated fibrillar nature makes them the material of choice for the design and engineering of 3D-scaffolds for cell culture, tissue engineering and drug delivery applications. One particular class of hydrogels that has been the focus of significant research is self-assembling peptide hydrogels. In the present work we were interested in exploring how fibre-fibre edge interactions affect the self-assembly and gelation properties of amphipathic peptides. For this purpose we investigated two β-sheet forming peptides, FEFKFEFK (F8) and KFEFKFEFKK (KF8K), the latter one having the fibre edges covered by lysine residues. Our results showed that the addition of the two lysine residues did not affect the ability of the peptides to form β-sheet rich fibres provided that the overall charge carried by the two peptides was kept constant. It did though significantly reduce edge driven hydrophobic fibre-fibre associative interactions resulting in a reduced tendency for KF8K fibres to associate / aggregate laterally and form large fibre bundles and consequently network crosslinks. This effect resulted in the formation of hydrogels with lower moduli but faster dynamics. As a result KF8K fibres could be aligned only under high shear and at high concentration while F8 hydrogel fibres were found to align readily at low shear and low concentration. In addition F8 hydrogels were found to fragment at high concentration due to the high aggregation state stabilising the fibre bundles resulting in fibre breakage rather than disentanglement and alignment.
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Apr 2020
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[19852]
Open Access
Abstract: Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g. spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of RAFT dispersion polymerizations have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci., 2016, 7, 5078-5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherent-ly heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer drop-lets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precur-sor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the pre-cise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproduc-ibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved with-in 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ small angle X-ray scattering (SAXS) studies using a stirrable SAXS reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellar nucleation and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the nucleation event and the subsequent evolution in the diblock co-polymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our under-standing of the PISA mechanism during RAFT aqueous emulsion polymerization.
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Jul 2019
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: It is well-known that the Dengue fever virus undergoes a distinct morphological transition from topologically smooth particles to ‘bumpy’ particle on increasing the temperature from that of the mosquito carrier (28 °C) to that of the human host (37 °C). This virus also possesses pH-sensitive surface domains that undergo conformational changes during infection which facilitates exit from the endosomes. Herein we take a bio-inspired approach to design synthetic Dengue virus-mimicking nanoparticles to target triple-negative (TN) breast cancer cells that overexpress SR-B1 scavenger receptors. Thus, sterile pH-responsive methacrylic ABC triblock copolymer vesicles were prepared in aqueous solution via polymerization-induced self-assembly. Microphase separation between two enthalpically-incompatible hydrophobic membrane-forming blocks produced a well-defined framboidal morphology, with surface globules of ∼28 nm diameter protruding from the membrane. The hydrophilic stabilizer block comprises 97% hydroxyl-functionalized chains and 3% phosphorylcholine-functionalized chains, with the latter being critical for selective intracellular uptake. These framboidal vesicles remain intact at neutral pH but become swollen and cationic at pH 5–6 because the tertiary amine residues in the hydrophobic C block become protonated. We demonstrate that such nanoparticles enable selective targeting of TN breast cancer cells. This is because such malignant cells overexpress SR-B1 receptors for naturally-occurring phospholipids and hence take up the phosphorylcholine-decorated framboidal vesicles preferentially. In contrast, negligible cell uptake is observed over the same time period for both human dermal fibroblasts and normal breast cancer cells that minimally express the SR-B1 receptor. Moreover, we show that genetic material within such pH-responsive framboidal vesicles can be efficiently delivered to the cell nuclei while maintaining high cell viability.
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May 2019
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: Reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate was used to prepare three poly(glycerol monomethacrylate)x–poly(2-hydroxypropyl methacrylate)y (denoted Gx-Hy or PGMA-PHPMA) diblock copolymers, namely G37-H80, G54-H140, and G71-H200. A master phase diagram was used to select each copolymer composition to ensure that a pure worm phase was obtained in each case, as confirmed by transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS) studies. The latter technique indicated a mean worm cross-sectional diameter (or worm width) ranging from 11 to 20 nm as the mean degree of polymerization (DP) of the hydrophobic PHPMA block was increased from 80 to 200. These copolymer worms form soft hydrogels at 20 °C that undergo degelation on cooling. This thermoresponsive behavior was examined using variable temperature DLS, oscillatory rheology, and SAXS. A 10% w/w G37-H80 worm dispersion dissociated to afford an aqueous solution of molecularly dissolved copolymer chains at 2 °C; on returning to ambient temperature, these chains aggregated to form first spheres and then worms, with the original gel strength being recovered. In contrast, the G54-H140 and G71-H200 worms each only formed spheres on cooling to 2 °C, with thermoreversible (de)gelation being observed in the former case. The sphere-to-worm transition for G54-H140 was monitored by variable temperature SAXS: these experiments indicated the gradual formation of longer worms at higher temperature, with a concomitant reduction in the number of spheres, suggesting worm growth via multiple 1D sphere–sphere fusion events. DLS studies indicated that a 0.1% w/w aqueous dispersion of G71-H200 worms underwent an irreversible worm-to-sphere transition on cooling to 2 °C. Furthermore, irreversible degelation over the time scale of the experiment was also observed during rheological studies of a 10% w/w G71-H200 worm dispersion. Shear-induced polarized light imaging (SIPLI) studies revealed qualitatively different thermoreversible behavior for these three copolymer worm dispersions, although worm alignment was observed at a shear rate of 10 s–1 in each case. Subsequently conducting this technique at a lower shear rate of 1 s–1 combined with ultra small-angle x-ray scattering (USAXS) also indicated that worm branching occurred at a certain critical temperature since an upturn in viscosity, distortion in the birefringence, and a characteristic feature in the USAXS pattern were observed. Finally, SIPLI studies indicated that the characteristic relaxation times required for loss of worm alignment after cessation of shear depended markedly on the copolymer molecular weight.
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Oct 2018
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