Influence of the coagulation bath on the nanostructure of cellulose films regenerated from an ionic liquid solution.

Cellulose membranes were prepared from an EMIMAc ionic liquid solution by nonsolvent-induced phase separation (NIPS) in coagulation baths of water-acetone mixtures, ethanol-water mixtures and water at different temperatures. High water volume fractions in the coagulation bath result in a highly reproducible gel-like structure with inhomogeneities observed by small-angle neutron scattering (SANS). A structural transition of cellulose takes place in water-acetone baths at very low water volume fractions, while a higher water bath temperature increases the size of inhomogeneities in the gel-like structure. These findings demonstrate the value of SANS for characterising and understanding the structure of regenerated cellulose films in their wet state. Such insights can improve the engineering and structural tuning of cellulose membranes, either for direct use or as precursors for carbon molecular sieve membranes.

Structure Property Relationship of Micellar Waterborne Poly(Urethane-Urea): Tunable Mechanical Properties and Controlled Release Profiles with Amphiphilic Triblock Copolymers.

Waterborne polyurethane (WPU) has attracted significant interest as a promising alternative to solvent-based polyurethane (SPU) due to its positive impact on safety and sustainability. However, significant limitations of WPU, such as its weaker mechanical strength, limit its ability to replace SPU. Triblock amphiphilic diols are promising materials to enhance the performance of WPU due to their well-defined hydrophobic-hydrophilic structures. Yet, our understanding of the relationship between the hydrophobic-hydrophilic arrangements of triblock amphiphilic diols and the physical properties of WPU remains limited. In this study, we show that by controlling the micellar structure of WPU in aqueous solution via the introduction of triblock amphiphilic diols, the postcuring efficiency and the resulting mechanical strength of WPU can be significantly enhanced. Small-angle neutron scattering confirmed the microstructure and spatial distribution of hydrophilic and hydrophobic segments in the engineered WPU micelles. In addition, we show that the control of the WPU micellar structure through triblock amphiphilic diols renders WPU attractive in the applications of controlled release, such as drug delivery. Here, curcumin was used as a model hydrophobic drug, and the drug release behavior from WPU-micellar-based drug delivery systems was characterized. It was found that curcumin-loaded WPU drug delivery systems were highly biocompatible and exhibited antibacterial properties in vitro. Furthermore, the sustained release profile of the drug was found to be dependent on the structure of the triblock amphiphilic diols, suggesting the possibility of controlling the drug release profile via the selection of triblock amphiphilic diols. This work shows that by shedding light on the structure-property relationship of triblock amphiphilic diol-containing WPU micelles, we may enhance the applicability of WPU systems and move closer to realizing their promising potential in real-life applications.

Re-investigating the structure-property relationship of the solid electrolytes Li 3-x In1-x Zr x Cl6 and the impact of In-Zr(iv) substitution.

Chloride-based solid electrolytes are considered interesting candidates for catholytes in all-solid-state batteries due to their high electrochemical stability, which allows the use of high-voltage cathodes without protective coatings. Aliovalent Zr(iv) substitution is a widely applicable strategy to increase the ionic conductivity of Li3M(iii)Cl6 solid electrolytes. In this study, we investigate how Zr(iv) substitution affects the structure and ion conduction in Li3-x In1-x Zr x Cl6 (0 ≤ x ≤ 0.5). Rietveld refinement using both X-ray and neutron diffraction is used to make a structural model based on two sets of scattering contrasts. AC-impedance measurements and solid-state NMR relaxometry measurements at multiple Larmor frequencies are used to study the Li-ion dynamics. In this manner the diffusion mechanism and its correlation with the structure are explored and compared to previous studies, advancing the understanding of these complex and difficult to characterize materials. It is found that the diffusion in Li3InCl6 is most likely anisotropic considering the crystal structure and two distinct jump processes found by solid-state NMR. Zr-substitution improves ionic conductivity by tuning the charge carrier concentration, accompanied by small changes in the crystal structure which affect ion transport on short timescales, likely reducing the anisotropy.

Investigation of Structure, Ionic Conductivity, and Electrochemical Stability of Halogen Substitution in Solid-State Ion Conductor Li3YBr x Cl6-x.

Li3YX6 (X = Cl, Br) materials are Li-ion conductors that can be used as solid electrolytes in all solid-state batteries. Solid electrolytes ideally have high ionic conductivity and (electro)chemical compatibility with the electrodes. It was proven that introducing Br to Li3YCl6 increases ionic conductivity but, according to thermodynamic calculations, should also reduce oxidative stability. In this paper, the trade-off between ionic conductivity and electrochemical stability in Li3YBr x Cl6-x halogen-substituted compounds is investigated. The compositions of Li3YBr1.5Cl4.5 and Li3YBr4.5Cl1.5 are reported for the first time, along with a consistent analysis of the whole Li3YBr x Cl6-x (x = 0-6) tie-line. The results show that, while Br-rich materials are more conductive (5.36 × 10-3 S/cm at 30 °C for x = 4.5), the oxidative stability is lower (∼3 V compared to ∼3.5 V). Small Br content (x = 1.5) does not affect oxidative stability but substantially increases ionic conductivity compared to pristine Li3YCl6 (2.1 compared to 0.049 × 10-3 S/cm at 30 °C). This work highlights that optimization of substitutions in the anion framework provide prolific and rational avenues for tailoring the properties of solid electrolytes.

Exploring Nanoscale Structure in Perovskite Precursor Solutions Using Neutron and Light Scattering.

Tailoring the solution chemistry of metal halide perovskites requires a detailed understanding of precursor aggregation and coordination. In this work, we use various scattering techniques, including dynamic light scattering (DLS), small angle neutron scattering (SANS), and spin-echo SANS (SESANS) to probe the nanostructures from 1 nm to 10 µm within two different lead-halide perovskite solution inks (MAPbI3 and a triple-cation mixed-halide perovskite). We find that DLS can misrepresent the size distribution of the colloidal dispersion and use SANS/SESANS to confirm that these perovskite solutions are mostly comprised of 1-2 nm-sized particles. We further conclude that if there are larger colloids present, their concentration must be <0.005% of the total dispersion volume. With SANS, we apply a simple fitting model for two component microemulsions (Teubner-Strey), demonstrating this as a potential method to investigate the structure, chemical composition, and colloidal stability of perovskite solutions, and we here show that MAPbI3 solutions age more drastically than triple cation solutions.

Hyperpolarised gas filling station for medical imaging using polarised 129Xe and 3He.

We report the design, construction, and initial tests of a hyperpolariser to produce polarised 129Xe and 3He gas for medical imaging of the lung. The hyperpolariser uses the Spin-Exchange Optical Pumping method to polarise the nuclear spins of the isotopic gas. Batch mode operation was chosen for the design to produce polarised 129Xe and polarised 3He. Two-side pumping, electrical heating and a piston to transfer the polarised gas were some of the implemented techniques that are not commonly used in hyperpolariser designs. We have carried out magnetic resonance imaging experiments demonstrating that the 3He and 129Xe polarisation reached were sufficient for imaging, in particular for in vivo lung imaging using 129Xe. Further improvements to the hyperpolariser have also been discussed.

Mesoporous Silica Formation Mechanisms Probed Using Combined Spin-Echo Modulated Small-Angle Neutron Scattering (SEMSANS) and Small-Angle Neutron Scattering (SANS).

The initial formation stages of surfactant-templated silica thin films which grow at the air-water interface were studied using combined spin-echo modulated small-angle neutron scattering (SEMSANS) and small-angle neutron scattering (SANS). The films are formed from either a cationic surfactant or nonionic surfactant (C16EO8) in a dilute acidic solution by the addition of tetramethoxysilane. Previous work has suggested a two stage formation mechanism with mesostructured particle formation in the bulk solution driving film formation at the solution surface. From the SEMSANS data, it is possible to pinpoint accurately the time associated with the formation of large particles in solution that go on to form the film and to show their emergence is concomitant with the appearance of Bragg peaks in the SANS pattern, associated with the two-dimensional hexagonal order. The combination of SANS and SEMSANS allows a complete depiction of the steps of the synthesis that occur in the subphase.

Different agglomeration properties of PC61BM and PC71BM in photovoltaic inks - a spin-echo SANS study.

Fullerene derivatives are used in a wide range of applications including as electron acceptors in solution-processable organic photovoltaics. We report agglomeration of fullerene derivatives in optically opaque solutions of PC61BM and PC71BM, with concentrations ranging from 30 mg mL-1 up to 90 mg mL-1, in different solvents with relevance to organic photovoltaics, using a novel neutron scattering technique, Spin-Echo Small Angle Neutron Scattering (SESANS). From SESANS, agglomerates with correlation lengths larger than 1 µm are found in some PC61BM solutions, in contrast no agglomerates are seen in PC71BM solutions. These results clearly show that PC71BM is fundamentally more soluble than PC61BM in the solvents commonly used in photovoltaic inks and corroborating similar observations previously achieved using other experimental techniques. Computer models are presented to study the energetics of solution and agglomeration of both species, ascribing the difference to a kinetic effect probably related to the larger anisotropy of PC71BM. Also, this work showcases the power of SESANS to probe agglomerates of fullerene derivatives in completely opaque solutions for agglomerates of the order of one to several microns.

Data Correction of Intensity Modulated Small Angle Scattering.

To investigate long length scale structures using neutron scattering, real space techniques have shown certain advantages over the conventional methods working in reciprocal space. As one of the real space measurement techniques, spin echo modulated small angle neutron scattering (SEMSANS) has attracted attention, due to its relaxed constraints on sample environment and the possibility to combine SEMSANS and a conventional small angle neutron scattering instrument. In this report, we present the first implementation of SEMSANS at a pulsed neutron source and discuss important corrections to the data due to the sample absorption. These corrections allow measurements made with different neutron wavelengths and SEMSANS configurations to be overlaid and give confidence that the measurements provide an accurate representation of the density correlations in the sample.

High resolution neutron Larmor diffraction using superconducting magnetic Wollaston prisms.

The neutron Larmor diffraction technique has been implemented using superconducting magnetic Wollaston prisms in both single-arm and double-arm configurations. Successful measurements of the coefficient of thermal expansion of a single-crystal copper sample demonstrates that the method works as expected. The experiment involves a new method of tuning by varying the magnetic field configurations in the device and the tuning results agree well with previous measurements. The difference between single-arm and double-arm configurations has been investigated experimentally. We conclude that this measurement benchmarks the applications of magnetic Wollaston prisms in Larmor diffraction and shows in principle that the setup can be used for inelastic phonon line-width measurements. The achievable resolution for Larmor diffraction is comparable to that using Neutron Resonance Spin Echo (NRSE) coils. The use of superconducting materials in the prisms allows high neutron polarization and transmission efficiency to be achieved.

Coassembled nanostructured bioscaffold reduces the expression of proinflammatory cytokines to induce apoptosis in epithelial cancer cells.

The local inflammatory environment of the cell promotes the growth of epithelial cancers. Therefore, controlling inflammation locally using a material in a sustained, non-steroidal fashion can effectively kill malignant cells without significant damage to surrounding healthy cells. A promising class of materials for such applications is the nanostructured scaffolds formed by epitope presenting minimalist self-assembled peptides; these are bioactive on a cellular length scale, while presenting as an easily handled hydrogel. Here, we show that the assembly process can distribute an anti-inflammatory polysaccharide, fucoidan, localized to the nanofibers within the scaffold to create a biomaterial for cancer therapy. We show that it supports healthy cells, while inducing apoptosis in cancerous epithelial cells, as demonstrated by the significant down-regulation of gene and protein expression pathways associated with epithelial cancer progression. Our findings highlight an innovative material approach with potential applications in local epithelial cancer immunotherapy and drug delivery.

Simultaneous imaging of lung structure and function with triple-nuclear hybrid MR imaging.

PURPOSE: To re-engineer a standard clinical magnetic resonance (MR) imaging system to enable the acquisition, in the same breath hold, of lung images from two hyperpolarized gases (helium 3 [(3)He] and xenon 129 [(129)Xe]) with simultaneous registered anatomic proton (hydrogen 1 [(1)H]) MR images of lung structure. MATERIALS AND METHODS: Studies with (3)He and (129)Xe were performed with National Research Ethics Committee approval, with informed consent from the volunteer. (1)H-(3)He-(129)Xe MR imaging was achieved in the same breath by using mutually decoupled nested radiofrequency coil hardware capable of transmit and receive on each respective nucleus without power cross talk. MR pulse sequences were also developed for rapid switching between each nucleus. The system is demonstrated with triple-nuclear lung images in a healthy individual following inhalation of a mixture of (3)He and (129)Xe gases. RESULTS: Spatially and temporally registered images of all three nuclei were obtained with high signal to noise ratio and high spatial resolution in the same breath. CONCLUSION: The multinuclear technique is capable of providing registered lung images with mutually complementary functional and structural spatial information.

Hyperpolarized 129Xe gas lung MRI-SNR and T2* comparisons at 1.5 T and 3 T.

In this study, the signal-to-noise ratio of hyperpolarized (129)Xe human lung magnetic resonance imaging was compared at 1.5 T and 3 T. Experiments were performed at both B(0) fields with quadrature double Helmholtz transmit-receive chest coils of the same geometry with the same subject loads. Differences in sensitivity between the two field strengths were assessed from the signal-to-noise ratio of multi-slice 2D (129)Xe ventilation lung images obtained at the two field strengths with a spatial resolution of 15 mm × 4 mm × 4 mm. There was a systematically higher signal-to-noise ratio observed at 3 T than at 1.5 T by a factor of 1.25. Mean image signal-to-noise ratio was in the range 27-44 at 1.5 T and 36-51 at 3 T. T 2* of (129)Xe gas in the partially inflated lungs was measured to be 25 ms and 18 ms at 1.5 T and 3 T, respectively. T 2* of (129)Xe gas in fully inflated lungs was measured to be 52 ms and 24 ms at 1.5 T and 3 T, respectively.

Synchronous acquisition of hyperpolarised 3He and 1H MR images of the lungs - maximising mutual anatomical and functional information.

The development of hybrid medical imaging scanners has allowed imaging with different detection modalities at the same time, providing different anatomical and functional information within the same physiological time course with the patient in the same position. Until now, the acquisition of proton MRI of lung anatomy and hyperpolarised gas MRI of lung function required separate breath-hold examinations, meaning that the images were not spatially registered or temporally synchronised. We demonstrate the spatially registered concurrent acquisition of lung images from two different nuclei in vivo. The temporal and spatial registration of these images is demonstrated by a high degree of mutual consistency that is impossible to achieve in separate scans and breath holds.

Compressed sensing in hyperpolarized 3He lung MRI.

In this work, the application of compressed sensing techniques to the acquisition and reconstruction of hyperpolarized (3)He lung MR images was investigated. The sparsity of (3)He lung images in the wavelet domain was investigated through simulations based on fully sampled Cartesian two-dimensional and three-dimensional (3)He lung ventilation images, and the k-spaces of 2D and 3D images were undersampled randomly and reconstructed by minimizing the L1 norm. The simulation results show that temporal resolution can be readily improved by a factor of 2 for two-dimensional and 4 to 5 for three-dimensional ventilation imaging with (3)He with the levels of signal to noise ratio (SNR) (approximately 19) typically obtained. The feasibility of producing accurate functional apparent diffusion coefficient (ADC) maps from undersampled data acquired with fewer radiofrequency pulses was also demonstrated, with the preservation of quantitative information (mean ADC(cs) approximately mean ADC(full) approximately 0.16 cm(2) sec(-1)). Prospective acquisition of 2-fold undersampled two-dimensional (3)He images with a compressed sensing k-space pattern was then demonstrated in a healthy volunteer, and the results were compared to the equivalent fully sampled images (SNR(cs) = 34, SNR(full) = 19).

Susceptibility effects in hyperpolarized (3)He lung MRI at 1.5T and 3T.

PURPOSE: To compare susceptibility effects in hyperpolarized (3)He lung MRI at the clinically relevant field strengths of 1.5T and 3T. MATERIALS AND METHODS: Susceptibility-related B(0) inhomogeneity was evaluated on a macroscopic scale by B(0) field mapping via phase difference. Subpixel susceptibility effects were quantified by mapping T2. Comparison was made between ventilation images obtained from the same volunteers at both field strengths. RESULTS: The B(0) maps at 3T show enhanced off-resonance effects close to the diaphragm and the ribs due to susceptibility differences. The average T2 from a voxel (20 x 4 x 4) mm(3) was determined as T2 = 27.8 msec +/- 1.2 msec at 1.5T compared to T2 = 14.4 msec +/- 2.6 msec at 3T. In ventilation images the most prominent effect is increased signal attenuation close to the intrapulmonary blood vessels at higher B(0). CONCLUSION: Image homogeneity and T2 are lower at 3T due to increased B(0) inhomogeneity as a consequence of susceptibility differences. These findings indicate that (3)He imaging at 3T has no obvious benefit over imaging at 1.5T, as signal-to-noise ratio (SNR) was comparable for both fields in this work.