ORCID Profile
0000-0003-4799-2935
Current Organisation
Australian Nuclear Science and Technology Organisation
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Structural Chemistry and Spectroscopy | Photodetectors, Optical Sensors and Solar Cells | Materials Engineering | Organic Semiconductors
Expanding Knowledge in the Physical Sciences | Scientific Instruments | Environmentally Sustainable Manufacturing not elsewhere classified |
Publisher: Elsevier BV
Date: 2019
DOI: 10.1016/J.JCIS.2018.09.046
Abstract: A model zwitterionic surfactant, oleyl amidopropyl betaine (OAPB), that spontaneously forms viscoelastic wormlike micelles in aqueous solution is mixed with a variety of structurally erse organic additives. By systematically varying the nature of these additives, insight into the effects of their aromaticity and polarity on the bulk assembly and fluid behaviour of these micelles is gained by the complementary use of small-angle neutron scattering and viscosity measurements. Inclusion of non-polar additives causes the wormlike aggregates to transition into microemulsions above a critical additive concentration the precise partitioning within the micelle is determined using contrast variation. Alternatively, polar additives do not appear to cause evolution from the wormlike structure, but instead influence the fluid rheology, with some serving to significantly increase viscosity above that of the pure surfactant solution. Addition of these molecules is accompanied by an increase in fluid viscosity when the oxygenated group of the additive is resonance stabilised or acidic. This effect is thought to be a result of surfactant-additive synergism, in which charge screening of the surfactant head-groups causes stronger attractions between molecules, increasing the scission energy of the micelles (i.e. reducing their ability to break apart and reform). Further doping of acidic additives past a critical concentration causes phase separation of the wormlike mixtures. According to ultra-small-angle neutron scattering measurements, the incorporation of all additives (polar or non-polar, aromatic or non-aromatic) results in the formation of 'branched' wormlike networks. These findings emphasise the significant impact of impurities or additives on the properties of aqueous wormlike micellar systems formed by zwitterionic surfactants, and could also inform selection of solutes for controlling fluid rheology.
Publisher: Elsevier BV
Date: 11-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3TB21069C
Publisher: Wiley
Date: 23-04-2016
DOI: 10.1111/EJH.12561
Abstract: Exercise has beneficial effects on cancer prevention as well as on prognosis of patients with cancer. To optimize the outcomes of exercise programs, more knowledge about the underlying mechanisms is needed. This study investigates the short-term effects of a half marathon on immune cell proportions, pro-inflammatory cytokine levels, and recovery behavior of patients with breast cancer in the aftercare compared to healthy controls. Nine patients with breast cancer in the aftercare and 9 healthy age-matched controls participated in a half marathon. Blood s les were collected before, after, and 24 h after the run. Immune status was measured by flow cytometer analysis, while serum levels of the pro-inflammatory cytokines TNF-α, IL-6, and MIF were assessed using ELISA. Recovery behavior was determined using an ADL monitor. Both groups showed a similar recovery behavior and time courses in changes of granulocytes, monocytes, lymphocytes, and cytokine serum levels. Patients revealed increased proportions of cytotoxic and memory T cells, whereas helper and naïve T cells were decreased compared to healthy controls. Naïve and memory T-cell proportions were not affected by the intervention. Patients with breast cancer in the aftercare and healthy subjects show a similarly recovery behavior and immune response to the intervention. The detected differences in T-cell subsets need further investigation. Based on the results of the study, we hypothesize that immune cell subsets with known relevance in cancer were mobilized through the intervention. We confirm that the hypothesis of a midterm anti-inflammatory effect of exercise is also valid for patients with breast cancer in the aftercare.
Publisher: American Chemical Society (ACS)
Date: 05-08-2020
Publisher: Informa UK Limited
Date: 02-04-2016
Publisher: International Union of Crystallography (IUCr)
Date: 02-2019
DOI: 10.1107/S1600576718018009
Abstract: BILBY is a recently constructed and commissioned time-of-flight small-angle neutron scattering instrument, operated by the Australian Centre for Neutron Scattering at the Australian Nuclear Science and Technology Organisation (ANSTO). BILBY provides a wide accessible q range ( q ≃ 1.0 × 10 −3 Å −1 to ∼1.8 Å −1 ) and variable wavelength resolution (Δλ/λ ≃ 3–30%) to complement the other small-angle and ultra-small-angle neutron scattering capabilities available at ANSTO. Since its construction, BILBY has been used to study s les from a wide range of scientific disciplines, including biology, chemistry, physics and materials science. This article describes the BILBY design and components, and shows data collected from a number of reference s les.
Publisher: American Chemical Society (ACS)
Date: 21-06-2013
DOI: 10.1021/LA305052Q
Abstract: The phase behavior of the ternary unsaturated monoglycerides (UMG)-DL-α-tocopheryl acetate-water system has been studied. The effects of lipid composition in both bulk and dispersed lyotropic liquid crystalline phases and microemulsions were investigated. In excess water, progressive addition of DL-α-tocopheryl acetate to a binary UMG mixture results in the following phase sequence: reversed bicontinuous cubic phase, reversed hexagonal (H(II)) phase, and a reversed microemulsion. The action of DL-α-tocopheryl acetate is then compared to that of other lipids such as triolein, limonene, tetradecane, and DL-α-tocopherol. The impact of solubilizing these hydrophobic molecules on the UMG-water phase behavior shows some common features. However, the solubilization of certain molecules, like DL-α-tocopherol, leads to the presence of the reversed micellar cubic phase (space group number 227 and symmetry Fd3m) while the solubilization of others does not. These differences in phase behavior are discussed in terms of physical-chemical characteristics of the added lipid molecule and its interaction with UMG and water. From an applications point of view, phase behavior as a function of the solubilized content of guest molecules (lipid additive in our case) is crucial since macroscopic properties such as molecular release depend strongly on the phase present. The effect of two hydrophilic emulsifiers, used to stabilize the aqueous dispersions of UMG, was studied and compared. Those were Pluronic F127, which is the most commonly used stabilizer for these kinds of inverted type structures, and the partially hydrolyzed emulsifier lecithin (Emultop EP), which is a well accepted food-grade emulsifier. The phase behavior of particles stabilized by the partially hydrolyzed lecithin is similar to that of bulk s le at full hydration, but this emulsifier interacts significantly with the internal structure and affects it much more than F127.
Publisher: Elsevier BV
Date: 03-2018
Publisher: American Chemical Society (ACS)
Date: 23-01-2015
DOI: 10.1021/CM503981T
Publisher: American Chemical Society (ACS)
Date: 12-12-2017
Publisher: Elsevier BV
Date: 10-2021
Publisher: American Chemical Society (ACS)
Date: 04-08-2011
DOI: 10.1021/LA201718A
Abstract: We report that a specific realization of Schwarz's triply periodic hexagonal minimal surface is isotropic with respect to the Doi-Ohta interface tensor and simultaneously has minimal packing and stretching frustration similar to those of the commonly found cubic bicontinuous mesophases. This hexagonal surface, of symmetry P6(3)/mmc with a lattice ratio of c/a = 0.832, is therefore a likely candidate geometry for self-assembled lipid/surfactant or copolymer mesophases. Furthermore, both the peak position ratios in its powder diffraction pattern and the elastic moduli closely resemble those of the cubic bicontinuous phases. We therefore argue that a genuine possibility of experimental misidentification exists.
Publisher: American Chemical Society (ACS)
Date: 14-02-2019
Abstract: The electrocatalyst layer (ECL) of the proton-exchange membrane fuel cell (PEMFC) is commonly fabricated from colloidal catalyst ink containing carbon-supported catalyst nanoparticles (NPs), ionomer stabilizer, and dispersion medium (DM). The structure, stability, and aggregate size distribution of fuel cell catalyst ink are critically dependent on the quality of DM. However, understanding of the influence of the quality of DM on the hierarchical structure of the ECL is lacking. This work presents a systematic investigation of the effects of reducing alcohol content in isopropyl alcohol/water (IPA/H
Publisher: Public Library of Science (PLoS)
Date: 06-02-2017
Publisher: Elsevier BV
Date: 06-2004
Publisher: Trans Tech Publications, Ltd.
Date: 12-2012
DOI: 10.4028/WWW.SCIENTIFIC.NET/MSF.736.301
Abstract: The effects of aqueous delithiation of lithium cobalt oxide crystals on the crystal texture and etching patterns has been studied by electron microscopy, x-ray and neutron diffraction at high resolution. The delithiation proceeds to exfoliation and in the process textural patterns that appear have been associated with periodic strains in the crystals developed by the delithiation.
Publisher: American Chemical Society (ACS)
Date: 17-12-2004
DOI: 10.1021/LA0482711
Abstract: Self-assembled nanostructures, such as inverted type mesophases of the cubic or hexagonal geometry or reverse microemulsion phases, can be dispersed using a polymeric stabilizer, such as the PEO-PPO-PEO triblock copolymer Pluronic F127. The particles, which are described in the present study, are based on monolinolein (MLO)-water mixtures. When adding tetradecane (TC) to the MLO-water-F127 system at constant temperature, the internal nanostructure of the kinetically stabilized particles transforms from a Pn3m (cubosomes) to a H2 (hexosomes) and to a water-in-oil (W/O, L2) microemulsion phase (emulsified microemulsion (EME)). To our knowledge, this is the first time that the formation of stable emulsified microemulsion (EME) systems has been described and proven to exist even at room temperature. The same structural transitions can also be induced by increasing temperature at constant tetradecane content. The internal nanostructure of the emulsified particles is probed using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). At each investigated composition and temperature, the internal structure of the dispersions is observed to be identical to the corresponding structure of the nondispersed, fully hydrated bulk phase. This is clear evidence for the fact that the self-assembled inner particle nanostructure is preserved during the dispersion procedure. In addition, the internal structure of the particles is in thermodynamic equilibrium with the surrounding water phase. The internal structure of the dispersed, kinetically stabilized particles is a "real" and stable self-assembled nanostructure. To emphasize this fact, we denoted this new family of colloidal particles (cubosomes, hexosomes, and EMEs) as "ISASOMES" (internally self-assembled particles or "somes").
Publisher: American Chemical Society (ACS)
Date: 14-08-2019
DOI: 10.1021/ACS.LANGMUIR.9B01966
Abstract: Droplet-stabilized emulsions (DSEs) were made from oil droplets coated with whey protein microgel (WPM) particles. The WPM particles with
Publisher: AIP Publishing
Date: 08-2022
DOI: 10.1063/5.0103065
Abstract: Wormlike micelles (WLMs) are vital components of many consumer products and industrial fluids, adding a shear-dependent viscous texture through their entanglement in solutions. It is now well accepted from experiments such as coupling rheology and scattering that, similar to many polymer solutions and dispersions of highly anisotropic particles, WLM behavior during shear arises from the alignment of the “worms” with the shear field, resulting in ordering that is rapidly lost in the cessation of shear. Most studies of such systems have been limited to dilute systems that are far below concentrations used industrially and commercially, due to the complexity of analyzing shear-induced many-body effects in high volume fraction dispersions. Here, we explore the shear alignment of concentrated WLM solutions comprising sodium laureth sulfate and cocamidopropyl betaine in 0.38 M aqueous sodium chloride. By analyzing only scattering data at high values of the scattering vector (i.e., correlations at short length scales that are dominant in such concentrated systems), we explore whether useful information can be obtained by naïvely approximating the WLMs as an ensemble of unconnected short rods representing sections of the worms. By taking this reductionist approach to analyzing the obtained two-dimensional scattering patterns from these systems under shear, we find that in this regime, such concentrated worms can be approximated as cylinders that become more aligned with the direction of shear as volume fraction and shear rate increase.
Publisher: American Chemical Society (ACS)
Date: 23-10-2014
DOI: 10.1021/MA5016352
Publisher: Wiley
Date: 22-11-2019
Publisher: Elsevier BV
Date: 2023
Publisher: Inderscience Publishers
Date: 2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B822814K
Publisher: Elsevier BV
Date: 07-2021
Publisher: American Chemical Society (ACS)
Date: 23-01-2015
DOI: 10.1021/LA5044969
Abstract: Supramolecular self-assembling hiphiles have been widely used in drug delivery and diagnostic imaging. In this report, we present the self-assembly of Gd (III) chelated DTPA-monophytanyl (Gd-DTPA-MP) hiphiles incorporated within phytantriol (PT), an inverse bicontinuous cubic phase forming matrix at various compositions. The dispersed colloidal nanoassemblies were evaluated as potential MRI contrast agents at various magnetic field strengths. The homogeneous incorporation of Gd-DTPA-MP in PT was confirmed by polarized optical microscopy (POM) and synchrotron small-angle X-ray scattering (SAXS) of the bulk phases of the mixtures. The liquid crystalline nanostructures, morphology, and the size distribution of the nanoassemblies were studied by SAXS, cryogenic transmission electron microscopy (cryo-TEM), and dynamic light scattering (DLS). The dispersions with up to 2 mol % of Gd-DTPA-MP in PT retained inverse cubosomal nanoassemblies, whereas the rest of the dispersions transformed to liposomal nanoassemblies. In vitro relaxivity studies were performed on all the dispersions at 0.54, 9.40, and 11.74 T and compared to Magnevist, a commercially available contrast agent. All the dispersions showed much higher relaxivities compared to Magnevist at both low and high magnetic field strengths. Image contrast of the nanoassemblies was also found to be much better than Magnevist at the same Gd concentration at 11.74 T. Moreover, the Gd-DTPA-MP/PT dispersions showed improved relaxivities over the pure Gd-DTPA-MP dispersion at high magnetic fields. These stable colloidal nanoassemblies have high potential to be used as combined delivery matrices for diagnostics and therapeutics.
Publisher: The Royal Society
Date: 10-2020
DOI: 10.1098/RSOS.201507
Abstract: By using a combination of experimental neutron scattering techniques, it is possible to obtain a statistical perspective on red blood cell (RBC) shape in suspensions, and the inter-relationship with protein interactions and dynamics inside the confinement of the cell membrane. In this study, we examined the ultrastructure of RBC and protein–protein interactions of haemoglobin (Hb) in them using ultra-small-angle neutron scattering and small-angle neutron scattering (SANS). In addition, we used the neutron backscattering method to access Hb motion on the ns time scale and Å length scale. Quasi-elastic neutron scattering (QENS) experiments were performed to measure diffusive motion of Hb in RBCs and in an RBC lysate. By using QENS, we probed both internal Hb dynamics and global protein diffusion, on the accessible time scale and length scale by QENS. Shape changes of RBCs and variation of intracellular Hb concentration were induced by addition of the Na + -selective ionophore monensin and the K + -selective one, valinomycin. The experimental SANS and QENS results are discussed within the framework of crowded protein solutions, where free motion of Hb is obstructed by mutual interactions.
Publisher: Springer Science and Business Media LLC
Date: 14-10-2022
DOI: 10.1038/S41598-022-21715-1
Abstract: Nanoparticles and nano-delivery systems are constantly being refined and developed for biomedical applications such as imaging, gene therapy, and targeted delivery of drugs. Nanoparticles deliver beneficial effects by both release of their cargo and by liberation of their constitutive structural components. The N- acylethanolamines linoleoyl ethanolamide (LEA) and oleoyl ethanolamide (OEA) both exhibit endocannabinoid-like activity. Here, we report on their ability to form nanoparticles that when conjugated with tissue-specific molecules, are capable of localizing to specific areas of the body and reducing inflammation. The facilitation of pharmacological effects by endocannabinoids at targeted sites provides a novel biocompatible drug delivery system and a therapeutic approach to the treatment, patient management and quality of life, in conditions such as arthritis, epilepsy, and cancer.
Publisher: American Chemical Society (ACS)
Date: 23-10-2018
DOI: 10.1021/ACS.LANGMUIR.7B02830
Abstract: Long-chain amidopropyl betaines are known for their ability to self-assemble into viscoelastic wormlike micellar structures. Here, we explore the effect of tailgroup molecular architecture on this process, comparing five molecules, each with C18 chains but different levels of unsaturation and branching. The surfactants are synthesized from stearic, oleic, linoleic, linolenic, and isostearic acids. The self-assembly of these molecules in aqueous solutions is explored using small- and ultra-small-angle neutron scattering (SANS and USANS). It is seen that optimum wormlike micelle formation is achieved for the oleic-chained surfactant, and the alignment of self-assembled structures is further explored using rheo-SANS. The more highly unsaturated molecules form rodlike micelles, whereas the stearic-tailed molecule shows a pronounced Krafft point and the isostearic-chained surfactant is entirely water-insoluble. These results demonstrate the critical importance of tailgroup geometry on surfactant properties and self-assembly for this industrially important class of surfactants.
Publisher: American Chemical Society (ACS)
Date: 09-06-2022
DOI: 10.1021/ACS.LANGMUIR.2C00523
Abstract: Azobenzene-containing surfactants (azo-surfactants) have garnered significant attention for their use in generating photoresponsive foams, interfaces, and colloidal systems. The photoresponsive behavior of azo-surfactants is driven by the conformational and electronic changes that occur when the azobenzene chromophore undergoes light-induced
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6NJ03934K
Abstract: A novel paramagnetic hiphile designed to form nanoassemblies of highly ordered nanostructures was explored as an advanced MRI contrast agent.
Publisher: MDPI AG
Date: 07-09-2018
Abstract: This study investigated the use of solvent contrast (H2O/D2O ratio) as a means to optimize the ultra-small-angle neutron scattering (USANS) signal. By optimizing the signal, it was possible to reduce the undesirable effects of coherent multiple scattering while still maintaining a measurable scattered intensity. This result will further enable the use of USANS as a probe of the interactions between colloidal particles and their structures within concentrated suspensions as well as particle dispersion/aggregation. As a model system, we prepared silica colloidal particle suspensions at different solid concentrations. USANS curves were measured using the classical Bonse–Hart double crystal diffractometer while varying the scattering length density of the aqueous phase, thus varying the contrast to the silica particles. As a means of assessing the impact of multiple scattering effects on different q-values, we analyzed the scattered intensity at different contrasts at three different q values. The data were then used to determine the match point of the silica particle suspensions from the expected square root dependence of the scattered intensity with solvent composition, to analyze any differences associated with the solid concentration change, and to determine the optimum H2O/D2O ratio in terms of high transmission (TSAS 80%) and high enough scattering intensity associated with the contrast of the system. Through this investigation series, we confirmed that adjusting the contrast of the solvent (H2O/D2O) is a good methodology to reduce multiple scattering while maintaining a strong enough scattering signal from a concentrated suspension of silica particles for both USANS and rheometric USANS (rheo-USANS) experiments.
Publisher: American Chemical Society (ACS)
Date: 12-04-2023
Publisher: American Chemical Society (ACS)
Date: 03-06-2020
Publisher: International Union of Crystallography (IUCr)
Date: 26-07-2013
Publisher: Elsevier BV
Date: 11-2018
DOI: 10.1016/J.JCIS.2018.05.060
Abstract: Carbohydrates are appealing non-ionic surfactant head-groups as they are naturally abundant, generally biocompatible and biodegradable, and readily functionalized. Here, seven novel carbohydrate based surfactants (CBS) have been synthesized that contain a tri-ethylene glycol (TEG) linker between a glucose head-group and alkyl tail-group, with linear saturated (C8-18) and unsaturated (C18:1) alkyl chains. The aqueous adsorption and self-assembly of these surfactants was explored using tensiometry and small- and ultra-small-angle neutron scattering (SANS and USANS). With SANS we observed elongation from spherical to cylindrical micelles with increasing alkyl chain length. C16 and C18 chains exhibited pronounced Krafft points, yet formed worm-like micelles as single components upon heating to 43 and 48 °C respectively. The introduction of mono-unsaturation in the form of a C18:1 chain reduced the Krafft point and gave a surfactant that produced worm-like micelles in water without additives at room temperature. We also observed micellar elongation for C12 and C14 chains at 50 °C due to dehydration of the TEG linker. The room temperature worm-like micelles were further characterized using rheo-SANS and rheology, revealing the C18:1 surfactant to exhibit near ideal Maxwell behavior at low concentrations (2.9 wt.%). These results provide insight into structure-function relationships for CBS, and demonstrate a promising molecular candidate for the formation of viscoelastic worm-like micellar solutions.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CP02738B
Abstract: Aqueous dispersions of graphene oxide and reduced graphene oxide are combined with carefully chosen surfactants and polymers to investigate adsorption and bulk properties in these systems.
Publisher: American Chemical Society (ACS)
Date: 27-10-2006
DOI: 10.1021/LA061303V
Abstract: This work describes the effect of two different surfactants on the internal nanostructure of the kinetically stabilized isasomes (internally self-assembled particles or "somes"), which are a new family of colloidal particles (cubosomes, hexosomes, micellar cubosomes, and emulsified microemulsions, EME). The stabilization of these systems is performed by using the polymeric stabilizer F127. We demonstrate that the internal structure of these oil-free and oil-loaded dispersed particles can be modulated by varying the lipid composition. To achieve this goal, we replaced part of our primary lipid monolinolein (MLO) with diglycerol monooleate (DGMO) or soybean phosphatidylcholine (PC). We found that DGMO has a counter effect to that of tetradecane (TC) and allows us to tune back the self-assembled nanostructure in the TC-loaded dispersions from H2 (hexosomes) to Im3m (cubosomes). Although TC has a higher impact on confined structures than does DGMO, we demonstrate that the addition of DGMO significantly affects the internal structure of the TC-solubilized dispersions and favors the formation of large water channels. PC can also be used to modify the internal structure for MLO-based systems. It is somehow different from DGMO due to the fact that the fully hydrated Pn3m cubic structure in the presence of PC for the TC-free dispersion is preserved after dispersing. The results also indicate that PC is less effective than DGMO for tuning back the TC-loaded internal structure from H2 to cubic phase, in which it makes the confined structure less ordered. In addition, we found that DGMO has a significant effect on the internal structure of isasomes. It increases the water solubilization capacity for dispersed and nondispersed bulk phases. In contrast to the MLO-based dispersions, the present results indicate that F127 plays an important role in the internal structure of these dispersions due to its penetration into the oil-free cubic phase changing the symmetry from Pn3m to Im3m.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5RA22744E
Abstract: The linear and nonlinear rheology of physically-crosslinked-gelatin gel-multiwalled carbon nanotube (MWNT), chemically-crosslinked-gelatin gel-MWNT, and chemically–physically-crosslinked-gelatin gel-MWNT composites, are investigated.
Publisher: American Chemical Society (ACS)
Date: 23-01-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0SM00586J
Publisher: American Chemical Society (ACS)
Date: 11-05-2020
Publisher: Elsevier BV
Date: 02-2022
Publisher: American Chemical Society (ACS)
Date: 22-04-2019
Publisher: Proceedings of the National Academy of Sciences
Date: 13-01-2014
Abstract: Chirality and hierarchical ordering are two fundamental properties found in many of nature’s most complex self-assembled structures such as living cells. Simultaneous control over these properties in synthetic systems is vital to mimic or even surpass nature’s designs. Via numerical simulations, we describe a class of complex morphologies that afford radically new architectures for self-assembled shapes. Specifically, a mixture of two star block-copolymers are shown to form multiple interwoven 2D and 3D labyrinths—all chiral—and hierarchically ordered on two different length scales. Furthermore, we show that such intricate network morphologies forming at a confined, hyperbolic interface can be classified and modeled in terms of a much simpler isotropic model of packing based on tilings of the hyperbolic plane.
Publisher: American Chemical Society (ACS)
Date: 26-11-2018
Abstract: Aqueous dispersions of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) nanoparticles (NPs) have been fabricated using a thiophene-based surfactant 2-(3-thienyl)ethyloxybutylsulfonate sodium salt (TEBS) for the first time via the mini-emulsion process. The use of TEBS resulted in a stable colloidal dispersion of P3HT:PCBM NPs, of which the effect of various fabrication parameters is investigated. The fabricated NPs were characterized by dynamic light scattering, scanning electron microscopy, UV-visible spectroscopy, contrast-variation small and ultra-small angle neutron scattering, and cyclic voltammetry. The internal structure and electrochemical performance of TEBS-stabilized P3HT:PCBM NPs were compared to those of sodium dodecyl sulfate-stabilized core-shell (PCBM-P3HT) NPs at the same surfactant concentration. Neutron scattering and cyclic voltammetry results reveal a homogeneous distribution of small de-mixed P3HT and PCBM domains in the internal structure of TEBS-stabilized P3HT:PCBM NPs, reminiscent of cast film. Moreover, electron microscopy images show evidence of diffused NP surface/interface upon drying (without annealing), which indicates that the thiophene-containing TEBS may improve compatibility and film-forming properties of fabricated P3HT:PCBM NPs, and consequently be more suited for conventional film-processing methods for organic solar cell applications.
Publisher: The Royal Society
Date: 16-06-2017
Abstract: Star-shaped molecules with three mutually immiscible arms self-assemble to form a variety of novel structures, with conformations that attempt to minimize interfacial area between the domains composed of the different arms. The geometric frustration caused by the joining of these arms at a common centre limits the size and shape of each domain, encouraging the creation of complex and interesting solutions. Some solutions are tricontinuous, and these solutions (and others) share aspects of bicontinuous structures with hiphilic assemblies as similar molecular segregation factors are at work. We describe both highly symmetric and balanced structures, as well as unbalanced solutions that take the form of intricately striped hiphilic membranes. All these patterns can result in chiral assemblies with multiple networks.
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B314625C
Publisher: Elsevier BV
Date: 08-2007
DOI: 10.1016/J.JCIS.2006.06.033
Abstract: SANS is a powerful tool to characterise microemulsions, which can have a discontinuous droplet-like structure (oil in water (O/W), water in oil (W/O)) or a bicontinuous one. In the present study, we try to distinguish O/W, W/O and bicontinuous microemulsions by SANS measurements under practical conditions and by a certain evaluation technique. For this reason we chose the well characterised ternary system water-non-ionic surfactant (C(12)E(5))-oil (n-octane), at a fixed surfactant concentration and performed SANS measurements throughout its one-phase channel where droplet-like phases as well as bicontinuous phases are well established. We evaluated the scattering data via the 'Generalised Indirect Fourier Transformation' method (GIFT) which is based on a particulate picture. It should therefore give good results in the droplet domains while a poor fit could be expected for the bicontinuous regime. For comparison we also applied the model of Teubner and Strey (TS) which was developed especially for bicontinuous phases, here a bad fit can be expected for the particulate regime. The data evaluation via GIFT leads to relatively good fits throughout the one-phase channel. The results are physically meaningful and are comparable to those of the TS model. We show that the scattering pattern of a bicontinuous microemulsion can be represented by that of a polydisperse particulate system. This is in clear contradiction to the expectation that the particle picture used in the GIFT method must fail when the bicontinuous regime is reached.
Publisher: Elsevier BV
Date: 02-2018
Publisher: Frontiers Media SA
Date: 09-02-2021
DOI: 10.3389/FCHEM.2020.619470
Abstract: This perspective describes advances in determining membrane protein structures in lipid bilayers using small-angle neutron scattering (SANS). Differentially labeled detergents with a homogeneous scattering length density facilitate contrast matching of detergent micelles this has previously been used successfully to obtain the structures of membrane proteins. However, detergent micelles do not mimic the lipid bilayer environment of the cell membrane in vivo . Deuterated vesicles can be used to obtain the radius of gyration of membrane proteins, but protein-protein interference effects within the vesicles severely limits this method such that the protein structure cannot be modeled. We show herein that different membrane protein conformations can be distinguished within the lipid bilayer of the bicontinuous cubic phase using contrast-matching. Time-resolved studies performed using SANS illustrate the complex phase behavior in lyotropic liquid crystalline systems and emphasize the importance of this development. We believe that studying membrane protein structures and phase behavior in contrast-matched lipid bilayers will advance both biological and pharmaceutical applications of membrane-associated proteins, biosensors and food science.
Publisher: Royal Society of Chemistry (RSC)
Date: 17-02-2014
DOI: 10.1039/C3BM60235D
Publisher: Elsevier BV
Date: 09-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CP04908H
Abstract: The effects of adding silica nanoparticles of varying size and surface chemistry to a liquid crystal system were analysed using small-angle scattering and polarising light microscopy, with varying temperature and applied shear.
Publisher: Elsevier BV
Date: 12-2018
Publisher: American Chemical Society (ACS)
Date: 12-06-2019
DOI: 10.1021/ACS.LANGMUIR.9B00647
Abstract: For evolving biological and biomedical applications of hybrid protein?lipid materials, understanding the behavior of the protein within the lipid mesophase is crucial. After more than two decades since the invention of the in meso crystallization method, a protein-eye view of its mechanism is still lacking. Numerous structural studies have suggested that integral membrane proteins preferentially partition at localized flat points on the bilayer surface of the cubic phase with crystal growth occurring from a local fluid lamellar L
Publisher: American Chemical Society (ACS)
Date: 17-11-2020
Publisher: Elsevier BV
Date: 12-2014
Publisher: Elsevier BV
Date: 12-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0NR08372K
Abstract: Iron oxide nanoparticle formation in DES was studied in situ across multiple length scales. Initial chloride-containing iron complexes react to form oxygen-rich species which precipitate. Morphology and growth time are defined by solvent composition.
Publisher: American Chemical Society (ACS)
Date: 06-07-2016
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9CP05463D
Abstract: Light-responsive binary (azobenzene + solvent) lyotropic liquid crystals (LCs) were investigated by structural modification of simple azobenzene molecules.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1CP05354J
Abstract: The polycation has an expanded conformation in the polymeric ionic liquid poly(3MAPIm)TFSI consistent with good solvency.
Publisher: Wiley
Date: 02-2006
DOI: 10.1111/J.1365-2818.2006.01544.X
Abstract: Low molecular weight surfactants, for ex le monoglycerides and phospholipids, form a multitude of self-assembled structures, such as inverted cubic or hexagonal mesophases, if brought into contact with water/oil. These mesophases can be dispersed in water using adequate surface-active materials such as low molecular weight surfactants or surface active polymers. In order to use such mesophase particles for incorporating drugs and aromas, it is essential to determine their internal crystallographic structure and to understand their mechanism of stabilization. Cryo-transmission electron microscopy was used to investigate the internal structure of different dispersed particles at various temperatures and oil contents. It is shown here that cryo-transmission electron microscopy, in combination with fast Fourier transform and tilting experiments, is effective in obtaining information on crystallographic structure, space group and morphology of particles with reversed bicontinuous cubic and hexagonal structures. In particular, using the presence or the absence of the {111} reflections and viewing the same particle under different axes of observation allows one to discriminate between the Im3m and Pn3m space groups. A major advantage of cryo-transmission electron microscopy is the ability to analyse single particles. This allows the identification of particles present at very low concentrations and the coexistence of particles with different internal self-assembly structures. With this technique we have obtained strong evidence for the presence of two cubic internal self-assembly structures with different space groups within the same dispersion. In addition, we found that cryo-transmission electron microscopy combined with tilting experiments enables the analysis of internal particle morphology, allowing the discussion of mechanisms for hexosome stabilization.
Publisher: Elsevier BV
Date: 12-2021
Publisher: Elsevier BV
Date: 11-2016
Publisher: Elsevier BV
Date: 10-2022
Publisher: Elsevier BV
Date: 05-2019
DOI: 10.1016/J.CARBPOL.2019.02.028
Abstract: The effects of amyloglucosidase digestion on the multi-scale supramolecular structural changes of native corn starch were examined by ultra-small angle neutron scattering (USANS), small angle X-ray scattering (SAXS), particle sizing, and scanning electron microscopy (SEM). Well-defined and spherical pores were formed upon amyloglucosidase digestion as revealed by SEM. The pore polydispersity was determined using USANS by assuming spherical pore morphology with log-normal distribution. Both USANS and SEM measurements demonstrated that the pores become larger and more polydisperse as the digestion time increased. Moreover, SAXS revealed that the lamellar peak area decreased gradually for both thermally and enzymatically treated starches, indicating partial loss of lamellar organisation. Overall, the results demonstrate structural changes occur on multiple length scales upon enzymatic digestion from granular to lamellar with small-angle scattering demonstrated to provide detailed characterization of the resultant microporous structures.
Publisher: Informa UK Limited
Date: 02-04-2016
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1SM05957B
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CP02101E
Abstract: By adding silica nanoparticles to lamellar liquid crystals, their flow and structure can be changed dramatically, indicating new ways to understand particle–membrane interactions.
Publisher: MDPI AG
Date: 14-12-2021
DOI: 10.3390/EN14248438
Abstract: The accessibility of pores to methane has been investigated in Devonian New Albany Shale Formation early-mature (Ro = 0.50%) to post-mature (Ro = 1.40%) s les. A Marcellus Shale Formation s le was included to expand the maturation range to Ro 2.50%. These are organic matter-rich rocks with total organic carbon (TOC) values of 3.4 to 14.4% and porosity values of 2.19 to 6.88%. Contrast matching small-angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques were used to generate porosity-related data before and after pressure cycling under hydrostatic (in a vacuum and at 500 bar of deuterated methane) and uniaxial stress (0 to ca. 350 bar) conditions. Our results showed that the accessible porosity was small for the s les studied, ranging from zero to 2.9%. No correlation between the accessible porosity and TOC or mineralogical composition was revealed, and the most likely explanation for porosity variation was related to the thermal transformation of organic matter and hydrocarbon generation. Pressure caused improvements in accessible porosity for most s les, except the oil window s le (Ro = 0.84%). Our data show that densification of methane occurs in nanopores, generally starting at diameters smaller than 20 nm, and that the distribution of methane density is affected by pressure cycling.
Publisher: American Chemical Society (ACS)
Date: 14-07-2016
DOI: 10.1021/ACS.JPCLETT.6B01173
Abstract: An understanding of the location of peptides, proteins, and other biomolecules within the bicontinuous cubic phase is crucial for understanding and evolving biological and biomedical applications of these hybrid biomolecule-lipid materials, including during in meso crystallization and drug delivery. While theoretical modeling has indicated that proteins and additive lipids might phase separate locally and adopt a preferred location in the cubic phase, this has never been experimentally confirmed. We have demonstrated that perfectly contrast-matched cubic phases in D2O can be studied using small-angle neutron scattering by mixing fully deuterated and hydrogenated lipid at an appropriate ratio. The model transmembrane peptide WALP21 showed no preferential location in the membrane of the diamond cubic phase of phytanoyl monoethanolamide and was not incorporated in the gyroid cubic phase. While deuteration had a small effect on the phase behavior of the cubic phase forming lipids, the changes did not significantly affect our results.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CP41300K
Abstract: A series of chelating hiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These hiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The hiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat hiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat hiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat hiphiles exhibited lamellar structures. The non-complexed hiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the hiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA hiphiles resulted in lamellar crystalline structures for all the neat hiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.
Publisher: Elsevier BV
Date: 2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CP01146D
Abstract: Perfluorocarbon emulsion droplets are interesting colloidal systems with applications in biomedicine. This work describes the use of small- and ultra-small-angle neutron scattering in studying their heat-induced phase transition into microbubbles.
Publisher: American Chemical Society (ACS)
Date: 13-12-2005
DOI: 10.1021/LA052109W
Abstract: In our recent work, we reported on the effect of varying temperature and solubilizing tetradecane (TC) on the structural transitions observed in dispersed particles based on the monolinolein (MLO)-water-TC system. At a given temperature, the addition of TC induces a transition of the internal structure from the bicontinuous cubic phase, Pn3m, to the reversed hexagonal, H2, and to the isotropic liquid phase (water-in-oil (W/O) microemulsions). Our present study focuses on the discovery of a Fd3m phase (reversed discontinuous micellar cubic), which is formed in the MLO-water-TC system at a specific TC/MLO weight ratio. It is situated between the H2 and the isotropic liquid phase (W/O microemulsion). Remarkably, it is not found in the absence of TC by increasing the temperature. The Fd3m structure was investigated in detail by means of small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryo-TEM). The present work proves that the structural transformation in the dispersed particles from H2 (hexosomes) to the W/O microemulsion system (emulsified microemulsion (EME)) is indirect and it occurs gradually via an emulsified intermediate phase. Specifically, in addition to the nanostructured aqueous dispersions described above, we present new TC-loaded aqueous dispersions with a confined intermediate phase, which is a discontinuous micellar cubic phase of the symmetry Fd3m. We denoted this type of emulsified particles as "micellar cubosomes".
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2FD20112G
Abstract: Inverse bicontinuous cubic phases with two aqueous network domains separated by a smooth bilayer are firmly established as equilibrium phases in lipid/water systems. The purpose of this article is to highlight the generalisations of these bicontinuous geometries to polycontinuous geometries, which could be realised as lipid mesophases with three or more network-like aqueous domains separated by a branched bilayer. An analysis of structural homogeneity in terms of bilayer width variations reveals that ordered polycontinuous geometries are likely candidates for lipid mesophase structures, with similar chain packing characteristics to the inverse micellar phases (that once were believed not to exist due to high packing frustration). The average molecular shape required by global geometry to form these multi-network phases is quantified by the surfactant shape parameter, v/(al) we find that it adopts values close to those of the known lipid phases. We specifically analyse the 3etc(187 193) structure of hexagonal symmetry P6(3) /mcm with three aqueous domains, the 3dia(24 220) structure of cubic symmetry I43d composed of three distorted diamond networks, the cubic chiral 4srs(24 208) with cubic symmetry P4232 and the achiral 4srs(5 133) structure of symmetry P42/nbc, each consisting of four intergrown undistorted copies of the srs net (the same net as in the QII(G) gyroid phase). Structural homogeneity is analysed by a medial surface approach assuming that the headgroup interfaces are constant mean curvature surfaces. To facilitate future experimental identification, we provide simulated SAXS scattering patterns that, for the 4srs(24 208) and 3dia(24 220) structures, bear remarkable similarity to those of bicontinuous QII(G)-gyroid and QII(D)-diamond phases, with comparable lattice parameters and only a single peak that cannot be indexed to the well-established structures. While polycontinuous lipid phases have, to date, not been reported, the likelihood of their formation is further indicated by the reported observation of a solid tricontinuous mesoporous silicate structure, termed IBN-9, which formed in the presence of surfactants [Han et al., Nat. Chem., 2009, 1, 123].
Publisher: American Chemical Society (ACS)
Date: 16-09-2016
DOI: 10.1021/ACS.LANGMUIR.6B01735
Abstract: Solutions of extended, flexible cylindrical micelles, often known as wormlike micelles, have great potential as the base for viscoelastic complex fluids in oil recovery, drilling, and lubrication. Here, we study the morphology and nanostructural characteristics of a model wormlike micellar fluid formed from erucyl amidopropyl betaine (EAPB) in water as a function of a erse range of additives relevant to complex fluid formulation. The wormlike micellar dispersions are extremely oleo-responsive, with even as little as 0.1% hydrocarbon oil causing a significant disruption of the network and a decrease in zero-shear viscosity of around 100-fold. Simple salts have little effect on the local structure of the wormlike micelles but result in the formation of fractal networks at larger length scales, whereas even tiny amounts of small organic species such as phenol can cause unexpected phase transitions. When forming mixtures with other surfactants, a vast array of self-assembled structures are formed, from spheres to ellipsoids, lamellae, and vesicles, offering the ultimate sensitivity in designing formulations with specific nanostructural characteristics.
Publisher: Elsevier BV
Date: 04-2023
Publisher: Elsevier BV
Date: 03-2022
Publisher: International Union of Crystallography (IUCr)
Date: 02-2018
DOI: 10.1107/S1600576717016879
Abstract: The double-crystal ultra-small-angle neutron scattering (USANS) diffractometer KOOKABURRA at ANSTO was made available for user experiments in 2014. KOOKABURRA allows the characterization of microstructures covering length scales in the range of 0.1–10 µm. Use of the first- and second-order reflections coming off a doubly curved highly oriented mosaic pyrolytic graphite premonochromator at a fixed Bragg angle, in conjunction with two interchangeable pairs of Si(111) and Si(311) quintuple-reflection channel-cut crystals, permits operation of the instrument at two in idual wavelengths, 4.74 and 2.37 Å. This unique feature among reactor-based USANS instruments allows optimal accommodation of a broad range of s les, both weakly and strongly scattering, in one s le setup. The versatility and capabilities of KOOKABURRA have already resulted in a number of research papers, clearly demonstrating that this instrument has a major impact in the field of large-scale structure determination.
Publisher: Wiley
Date: 13-08-2015
Abstract: Here, a new hiphilic magnetic resonance imaging (MRI) contrast agent, a Gd(III)-chelated diethylenetriaminepentaacetic acid conjugated to two branched alkyl chains via a dopamine spacer, Gd-DTPA-dopamine-bisphytanyl (Gd-DTPA-Dop-Phy), which is readily capable of self-assembling into liposomal nanoassemblies upon dispersion in an aqueous solution, is reported. In vitro relaxivities of the dispersions were found to be much higher than Magnevist, a commercially available contrast agent, at 0.47 T but comparable at 9.40 T. Analysis of variable temperature (17)O NMR transverse relaxation measurements revealed the water exchange of the nanoassemblies to be faster than that previously reported for paramagnetic liposomes. Molecular reorientation dynamics were probed by (1)H NMRD profiles using a classical inner and outer sphere relaxation model and a Lipari-Szabo "model-free" approach. High payloads of Gd(III) ions in the liposomal nanoassemblies made solely from the Gd-DTPA-Dop-Phy hiphiles, in combination with slow molecular reorientation and fast water exchange makes this novel hiphile a suitable candidate to be investigated as an advanced MRI contrast agent.
Publisher: American Chemical Society (ACS)
Date: 10-07-2018
DOI: 10.1021/ACS.LANGMUIR.8B01141
Abstract: The development of protein-based hydrogels for tissue engineering applications is often limited by their mechanical properties. Herein, we present the facile fabrication of tough regenerated silk fibroin (RSF)/graphene oxide (GO) nanocomposite hydrogels by a photochemical cross-linking method. The RSF/GO composite hydrogels demonstrated soft and adhesive properties during initial stages of photocrosslinking (<2 min), which is not observed for the pristine RSF hydrogel, and rendered a tough and nonadhesive hydrogel upon complete cross-linking (10 min). The composite hydrogels exhibited superior tensile mechanical properties, increased β-sheet content, and decreased chain mobility compared to that of the pristine RSF hydrogels. The composite hydrogels demonstrated Young's modulus as high as ∼8 MPa, which is significantly higher than native cartilage (∼1.5 MPa), and tensile toughness as high as ∼2.4 MJ/m
Publisher: Trans Tech Publications, Ltd.
Date: 04-2019
DOI: 10.4028/WWW.SCIENTIFIC.NET/SSP.290.22
Abstract: This paper presents a small angle neutron scattering (SANS) study of a novel porous gehlenite-based ceramic, synthesised from a homogeneous powder mixture of soda-lime-silicate (SLS) glass, α-alumina, calcite and calcium fluoride via solid-state sintering at 1200 °C. The products of sintering at single temperatures from 600 to 1200 °C are examined by X-ray diffraction (XRD). Sintering of the mixture below 1200 °C forms two intermediate phases (Na 2 CaSi 3 O 8 and Ca 4 Si 2 O 7 F 2 ). Nepheline and α-alumina are minor phases in the gehlenite-based ceramic fabricated through sintering at 1200 °C. The microstructure of the gehlenite-based ceramic is investigated using field-emission scanning electron microscopy (FESEM) and SANS at the Australian Centre for Neutron Scattering. This study also evaluated the specific surface area of the gehlenite-based ceramic (~3.0 m 2 cm –3 ) from quantitative analysis of SANS data.
Publisher: Elsevier BV
Date: 07-2019
DOI: 10.1016/J.JCIS.2019.03.068
Abstract: Carbohydrates are appealing non-ionic surfactant head-groups as they are naturally abundant, generally biocompatible and biodegradable, and readily functionalized. Recent work has produced a promising molecular candidate for the formation of viscoelastic worm-like micellar solutions: a tri(ethylene glycol)-linked oleyl-β-D-glucoside surfactant (GlcC18:1) exhibited near ideal Maxwell behavior at low concentrations (2.9 wt%) without additives at room temperature. Here, fourteen surfactants have been synthesized with structural variations based around GlcC18:1. Each contain an oligo(ethylene glycol) linker of varying length (2, 3, 4, 6 EO units) between a carbohydrate head-group (glucose, galactose, mannose, maltose, lactose, cellobiose) and a cis-unsaturated alkyl tail-group (oleyl, linoleyl, erucyl). The aqueous adsorption kinetics and self-assembly of these surfactants was explored using tensiometry and small-angle neutron scattering (SANS), respectively. With SANS we observed the formation of worm-like micelles for four surfactants, and vesicles for two surfactants which exhibited behavior similar to insoluble lipids. We also observed temperature-induced micellar elongation due to dehydration of the oligo(ethylene glycol) linker, resulting in a further three surfactants forming worm-like micelles at 50 °C. Worm-like micellar fluids were further characterized using rheology to reveal two surfactants with vastly superior viscoelastic properties compared to GlcC18:1, with >2 orders of magnitude increase in viscosity and >3 orders of magnitude increase in stress relaxation time. These results provide insight into structure-function relationships for non-ionic surfactants and demonstrate a class of designed hiphiles with a special propensity for forming viscoelastic worm-like micellar solutions at low concentrations.
Publisher: Elsevier BV
Date: 2019
DOI: 10.1016/J.JCIS.2018.08.024
Abstract: We examine the time dependent viscometric behavior of a well-defined system of gelling colloidal silica and how this behavior may be understood from a simple theoretical model which incorporates the microstructure of the gel. The ultra-small angle neutron scattering (USANS) technique is used to interrogate structure during the gelation process. The investigations focused on a system where both particles and interactions are well-defined: 7 nm silica particle acid-treated aqueous solution subjected to a constant applied shear in Couette geometry. Ultra-small angle neutron scattering (USANS) time-dependent scattering intensities were measured at wave vectors, q, in the range, 1.0 × 10 The first recorded direct kinetic measurements of the micron-scale structure in a gelling system. A critical micro-structural feature of the intensity-viscosity time behavior of a gelling colloid subjected to a shear is the cluster size. A viscosity/intensity coupling observed at the time of a viscosity maximum that corresponds to a time-dependent critical stress and speculated to be independent of the wave vector over a wide q-range.
Publisher: Elsevier BV
Date: 04-2022
Publisher: Elsevier BV
Date: 07-2018
DOI: 10.1016/J.IJBIOMAC.2018.03.044
Abstract: Regenerated Bombyx mori silk fibroin (RSF) is a widely recognized protein for biomedical applications however, its hierarchical gel structure is poorly understood. In this paper, the hierarchical structure of photocrosslinked RSF and RSF-based hybrid hydrogel systems: (i) RSF/Rec1-resilin and (ii) RSF oly(N-vinylcaprolactam (PVCL) is reported for the first time using small-angle scattering (SAS) techniques. The structure of RSF in dilute to concentrated solution to fabricated hydrogels were characterized using small angle X-ray scattering (SAXS), small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques. The RSF hydrogel exhibited three distinctive structural characteristics: (i) a Porod region in the length scale of 2 to 3nm due to hydrophobic domains (containing β-sheets) which exhibits sharp interfaces with the amorphous matrix of the hydrogel and the solvent, (ii) a Guinier region in the length scale of 4 to 20nm due to hydrophilic domains (containing turns and random coil), and (iii) a Porod-like region in the length scale of few micrometers due to water pores/channels exhibiting fractal-like characteristics. Addition of Rec1-resilin or PVCL to RSF and subsequent crosslinking systematically increased the nanoscale size of hydrophobic and hydrophilic domains, whereas decreased the homogeneity of pore size distribution in the microscale. The presented results have implications on the fundamental understanding of the structure-property relationship of RSF-based hydrogels.
Publisher: Elsevier BV
Date: 12-2021
Publisher: Elsevier BV
Date: 10-2019
DOI: 10.1016/J.COLSURFB.2019.110362
Abstract: Liposomal formulations have important therapeutic applications in anti-cancer treatments but current formulations suffer from serious side effects, high dosage requirements and prolonged treatment. In this study, PEGylated azide-functionalized liposomes containing drug nanocrystals were investigated with the aim of increasing the drug payload and achieving functionalization for targeted delivery. Liposomes were characterized using cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), small and ultra-small angle neutron scattering (SANS/USANS) and small and wide angle X-ray scattering (SAXS/WAXS). Cryo-TEM experiments revealed the dimensions of the nanocrystal-loaded liposomes and the change of shape from spherical to elongated after the formation of nanocrystals. Results from SANS/USANS experiments confirmed the asymmetric particle shape. SAXS/WAXS experiments confirmed that the crystalline drug only occurred in freeze-thawed s les and correlated with a new unidentified polymorphic form of ciprofloxacin. Using a small molecule dye, dibenzocyclooctyne (DBCO)-cy5, specific conjugation between DBCO groups and surface azide groups on the liposomes was confirmed this indicates the promise of this system for tumour-targeted delivery.
Publisher: American Chemical Society (ACS)
Date: 28-05-2004
DOI: 10.1021/LA0499416
Abstract: Aqueous submicron-sized dispersions of the binary monolinolein/water system, which are stabilized by means of a polymer, internally possess a distinct nanostructure. Taking this as our starting point, we were able to demonstrate for the first time that the internal structure of the dispersed particles can be tuned by temperature in a reversible way. Upon increasing the temperature, the internal structure undergoes a transition from cubic via hexagonal to fluid isotropic, the so-called L2 phase, and vice versa. Intriguingly, in addition to the structural changes in topology, the particles expel (take up) water to (from) the aqueous continuous phase when increasing (decreasing) the temperature in a reversible way. At each temperature, the internal structure of the dispersed particles corresponds very well to the structure observed in nondispersed binary monolinolein with excess water. This agreement is independent of any thermal history (including phase transitions), which proves that the structures in the dispersed particles actually are in thermodynamic equilibrium with the surrounding water phase.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CP01201G
Abstract: Triphilic star-polyphiles are short-chain oligomeric molecules with a radial arrangement of hydrophilic, hydrocarbon and fluorocarbon chains linked to a common centre. They form a number of liquid crystalline structures when mixed with water. In this contribution we focus on a hexagonal liquid crystalline mesophase found in star-polyphiles as compared to the corresponding double-chain surfactant to determine whether the hydrocarbon and fluorocarbon chains are in fact demixed in these star-polyphile systems, or whether both hydrocarbon and fluorocarbon chains are miscible, leading to a single hydrophobic domain, making the star-polyphile effectively hiphilic. We report SANS contrast variation data that are compatible only with the presence of three distinct immiscible domains within this hexagonal mesophase, confirming that these star-polyphile liquid crystals are indeed hydrophilic/oleophilic/fluorophilic 3-phase systems. Quantitative comparison with scattering simulations shows that the experimental data are in very good agreement with an underlying 2D columnar (12.6.4) tiling. As in a conventional hiphilic hexagonal mesophase, the hexagonally packed water channels (dodecagonal prismatic domains) are embedded in a hydrophobic matrix, but that matrix is split into oleophilic hexagonal prismatic domains and fluorophilic quadrangular prismatic domains.
Location: Australia
Start Date: 05-2018
End Date: 05-2022
Amount: $372,716.00
Funder: Australian Research Council
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