Cluster formation during aging of colloid-polymer dispersions and re-entrant rheological behavior at interfaces and the microscale

We report the dynamics of aqueous dispersions of the disk-shaped colloidal clay laponite® with poly(ethylene oxide) (PEO) chains of moderate molecular weight, explored via angle-dependent dynamic light scattering (DLS), bulk rheology, passive microrheology, and interfacial rheology. The PEO chains adsorb onto the laponite® surfaces, causing interesting dynamic behavior, including transitions from arrested states to liquid states as the concentration and molecular weight of PEO is increased. This re-entrant behavior has been attributed to formation of particle clusters induced free PEO chains. Our DLS results are consistent with a slow diffusive dynamic process, suggesting the formation of large particle clusters, in samples at aging times \u3c 75 days (Figure 1). By contrast to behavior observed in laponite® dispersions with a non-adsorbing polymer, poly(acrylic acid) (PAA), diffusion coefficients of these clusters in the laponite®-PEO systems continue to decrease with aging time until samples reach an arrested state. Finally, interfacial rheology and passive microrheology also show some evidence of re-entrant behavior, although the polymer concentrations at which this occurs do not exactly correspond to the conditions under which re-entrant behavior is observed in bulk rheology Please click Additional Files below to see the full abstract

The triphenylmethane dye brilliant blue G is only moderately effective at inhibiting amyloid formation by human amylin or at disaggregating amylin amyloid fibrils, but interferes with amyloid assays; Implications for inhibitor design.

The development of inhibitors of islet amyloid formation is important as pancreatic amyloid deposition contributes to type-2 diabetes and islet transplant failure. The Alzheimer's Aβ peptide and human amylin (h-amylin), the polypeptide responsible for amyloid formation in type-2 diabetes, share common physio-chemical features and some inhibitors of Aβ also inhibit amyloid formation by h-amylin and vice versa. Thus, a popular and potentially useful strategy to find lead compounds for anti-amylin amyloid agents is to examine compounds that have effects on Aβ amyloid formation. The triphenylmethane dye, brilliant blue G (BBG, Sodium;3-[[4-[(E)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-N-ethyl-3-methylanilino]methyl]benzenesulfonate) has been shown to modulate Aβ amyloid formation and inhibit Aβ induced toxicity. However, the effects of BBG on h-amylin have not been examined, although other triphenylmethane derivatives inhibit h-amylin amyloid formation. The compound has only a modest impact on h-amylin amyloid formation unless it is added in significant excess. BBG also remodels preformed h-amylin amyloid fibrils if added in excess, however BBG has no significant effect on h-amylin induced toxicity towards cultured β-cells or cultured CHO-T cells except at high concentrations. BBG is shown to interfere with standard thioflavin-T assays of h-amylin amyloid formation and disaggregation, highlighting the difficulty of interpreting such experiments in the absence of other measurements. BBG also interferes with ANS based assays of h-amylin amyloid formation. The work highlights the differences between inhibition of Aβ and h-amylin amyloid formation, illustrates the limitation of using Aβ inhibitors as leads for h-amylin amyloid inhibitors, and reinforces the difficulties in interpreting dye binding assays of amyloid formation

Large-area alginate/PEO-PPO-PEO hydrogels with thermoreversible rheology at physiological temperatures

Alginate hydrogels have shown great promise for applications in wound dressings, drug delivery, and tissue engineering. Here, we report the fabrication, rheological properties, and dynamics of a multicomponent hydrogel consisting of alginate and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers, and the achievement of thick, castable gels with tunable, thermoreversible behavior at physiological temperatures (Figure 1). PEO-PPO-PEO triblock copolymers can form temperature-sensitive hydrogels that exist as liquids at low temperatures and soft solids at high temperatures. In this work, we have employed PEO-PPO-PEO triblock copolymers to impart thermoresponsive properties to alginate hydrogels in the form of a multicomponent hydrogel. These systems can transition between a weak gel and a stiff gel, with a corresponding increase in the viscoelastic moduli of approximately two orders of magnitude as temperature is increased. The temperatures corresponding to the upper and lower boundaries of the stiff gel region, as well as the storage modulus at physiological temperatures (e.g., 36 – 40 C), can be controlled through the PEO-PPO- PEO concentration. Additionally, we explore the properties of these materials under compression and large deformations, and describe how alginate and F127 concentration can be used to control the fracture stress and strain. Finally, we compare the results from bulk rheology to the structure and dynamics of the gels measured via small-angle X-ray scattering (SAXS) and X-ray photon correlation spectroscopy (XPCS) experiments. Please click Additional Files below to see the full abstract

Evidence of stratification in binary colloidal films from microbeam X-ray scattering: Toward optimizing the evaporative assembly processes for coatings

Colloidal films have many important applications where a layered configuration is desirable, including flexible electronics, anti-reflective coatings, and anti-microbial paints. We report stratification during evaporative film formation in binary colloidal dispersion, probed using a novel microbeam small-angle X-ray scattering (SAXS) technique. To our knowledge, SAXS approaches have not been used to experimentally obtain quantitative data of concentration profiles in multicomponent colloidal films. We measured the local scattering of a film at different vertical locations using a microfocused X-ray beam and determined particle concentrations at different film depths using a linear combination analysis of the mixed film and pure film scattering data. Using small particle size ratios ranging from 2.55 to 1.25, we experimentally observed and quantify three distinct stratification configurations: inverted small on- top, large-on-top, and no stratification. Our results show some agreement with a previously proposed stratification state diagram, although there are some limitations. Experimental verification of these stratification phenomena is critical to fully understanding the physics of particle movement and structure development during film formation, which is crucial for optimizing evaporative assembly processes for coatings.Financial support for this work was provided by the National Science Foundation through award CBET-1335787 and a Department of Education Graduate Assistance in Areas of National Need (GAANN) fellowship for A. J. C., Award P200A160163. This research used beamline 11-BM, CMS, of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704

Can softer junctions lead to stiffer gels? Understanding the role of stereochemistry in associative polymer gels

The ability to create synthetic materials that mimic the structural and mechanical properties of soft biological tissues remains a significant challenge. In this presentation, we focus on creating stiff hydrogels and novel nanoscale and microscale structure by engineering crystalline domains into associative hydrogels of poly(lactic acid)-poly(ethylene oxide)-poly(lactic acid) (PLA-PEO-PLA) triblock copolymers. In aqueous media, these materials form associative gels of micelles with PLA cores that serve as network junctions. We extend previous studies from our group and others by varying the stereochemistry of the PLA block to create polymers with PLA blocks with ratios of L/D lactide units varying from 100/0 to 50/50. We had previously found that the 100/0 systems (triblocks with poly(L-lactide) blocks) formed gels with nanoscale crystalline domains, and these gels displayed a high value of the elastic modulus which was strongly dependent on PLA block length. Interestingly, our most recent results show that the storage modulus of these gels does not vary monotonically with L/D ratio. Rather, systems at intermediate L/D values are stiffer than the 100/0 systems, displaying higher storage moduli in spite of the fact that the PLA domains are expected to have a lower degree of crystallinity than in the 100/0 systems. Small-angle neutron scattering (SANS) results also indicate that the strongest interactions between micelles occurs for systems with intermediate L/D ratios, and ultra-small angle neutron scattering (USANS) shows evidence of larger structures in these gels, reminiscent of the hierarchical structures observed in biological gels. Collectively, our work shows that stereochemistry can be used in unexpected ways to access novel structures and properties in relatively simple synthetic polymers, giving insight into new routes for creating complex soft materials

Softer Junctions Can Result In Stiffer Gels: Associative Polymer Gels With Crystalline And Semicrystalline Domains

The ability to create synthetic materials that mimic the structural and mechanical properties of soft biological tissues remains a significant challenge. In this presentation, we discuss rheology and structural studies of poly(lactide)-poly(ethylene oxide)-poly(lactide) (PLA-PEO-PLA) triblock copolymer gels with various ratios of L-lactide and D-lactide in the PLA blocks (Figure 1). These materials form associative micellar gels in water, and previous work has shown that stereoregular triblocks with a L/D ratio of 100/0 form much stiffer gels than triblocks with a 50/50 L/D ratio. Our systems display an unexpected maximum in the storage modulus, G’, of the hydrogels at intermediate L/D ratio. The impact of stereochemistry on the rheology is very striking; gels with an L/D ratio of 85/15 have storage moduli that are ~1-2 orders of magnitude higher than hydrogels with L/D ratios of 100/0. No stereocomplexation is observed in the gels, although PLLA crystals are found for gels with L/D ratios of 95/5 and 90/10, and SANS results show a decrease in the intermicellar spacing for intermediate L/D ratios. We expect the dominant contribution to the elasticity of the gels to be intermicellar brdging chains and attribute the rheology to a competition between an increase in the time for PLA endblocks to pull out of micelles as the L/D ratio is increased and PLLA crystallization occurs, and a decrease in the number of bridging chains for micelles with crystalline PLA domains, as formation of bridges may be hindered by crowded crystalline PLA domains. Ultra-small angle neutron scattering (USANS) and confocal microscopy shows evidence of larger structures in these gels, reminiscent of the hierarchical structures observed in biological gels. These results provide a new strategy for controlling the rheology of PLA-based hydrogels for potential applications in biomaterials, as well as fundamental insights into how intermicellar interactions can be tuned via stereochemistry. Collectively, our work shows that stereochemistry can be used in unexpected ways to access novel structures and properties in relatively simple synthetic polymers, giving insight into new routes for creating complex soft materials. Please click Additional Files below to see the full abstract

Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils

This University of Massachusetts, Amherst project, "Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils" started on 1st February 2009 and finished on August 31st 2011. The project consisted following tasks: Task 1.0: Char Removal by Membrane Separation Technology The presence of char particles in the bio-oil causes problems in storage and end-use. Currently there is no well-established technology to remove char particles less than 10 micron in size. This study focused on the application of a liquid-phase microfiltration process to remove char particles from bio-oil down to slightly sub-micron levels. Tubular ceramic membranes of nominal pore sizes 0.5 and 0.8 ÃÂõm were employed to carry out the microfiltration, which was conducted in the cross-flow mode at temperatures ranging from 38 to 45 C and at three different trans-membrane pressures varying from 1 to 3 bars. The results demonstrated the removal of the major quantity of char particles with a significant reduction in overall ash content of the bio-oil. The results clearly showed that the cake formation mechanism of fouling is predominant in this process. Task 2.0 Acid Removal by Membrane Separation Technology The feasibility of removing small organic acids from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration (NF) and reverse osmosis (RO) membranes was studied. Experiments were carried out with a single solute solutions of acetic acid and glucose, binary solute solutions containing both acetic acid and glucose, and a model aqueous fraction of bio-oil (AFBO). Retention factors above 90% for glucose and below 0% for acetic acid were observed at feed pressures near 40 bar for single and binary solutions, so that their separation in the model AFBO was expected to be feasible. However, all of the membranes were irreversibly damaged when experiments were conducted with the model AFBO due to the presence of guaiacol in the feed solution. Experiments with model AFBO excluding guaiacol were also conducted. NF membranes showed retention factors of glucose greater than 80% and of acetic acid less than 15% when operated at transmembrane pressures near 60 bar. Task 3.0 Acid Removal by Catalytic Processing It was found that the TAN reduction in bio-oil was very difficult using low temperature hydrogenation in flow and batch reactors. Acetic acid is very resilient to hydrogenation and we could only achieve about 16% conversion for acetic acid. Although it was observed that acetic acid was not responsible for instability of aqueous fraction of bio-oil during ageing studies (described in task 5). The bimetallic catalyst PtRe/ceria-zirconia was found to be best catalyst because its ability to convert the acid functionality with low conversion to gas phase carbon. Hydrogenation of the whole bio-oil was carried out at 125ÃÂðC, 1450 psi over Ru/C catalyst in a flow reactor. Again, negligible acetic acid conversion was obtained in low temperature hydrogenation. Hydrogenation experiments with whole bio-oil were difficult to perform because of difficulty to pumping the high viscosity oil and reactor clogging. Task 4.0 Acid Removal using Ion Exchange Resins DOWEX M43 resin was used to carry out the neutralization of bio-oil using a packed bed column. The pH of the bio-oil increased from 2.43 to 3.7. The GC analysis of the samples showed that acetic acid was removed from the bio-oil during the neutralization and recovered in the methanol washing. But it was concluded that process would not be economical at large scale as it is extremely difficult to regenerate the resin once the bio-oil is passed over it. Task 5.0 Characterization of Upgraded Bio-oils We investigated the viscosity, microstructure, and chemical composition of bio-oils prepared by a fast pyrolysis approach, upon aging these fuels at 90ÃÂúC for periods of several days. Our results suggest that the viscosity increase is not correlated with the acids or char present in the bio-oils. The viscosity increase is due to formation of high molecular weight polymeric species over time. Our work also suggests that hydrogenation of the samples is beneficial in eliminating the viscosity increase. Task 6.0 Commercialization Assessment Renewable Oil International LLC (ROI) was responsible for Task 6.0, ÃÂÃÂCommercialization Assessment.ÃÂàAs part of this effort ROI focused on methods to reduce char carryover in the vapor stream from the fast pyrolysis reactor and residence time of the vapor in the reactor. Changes were made in the bio-oil recovery methodology and a reactor sweep gas used to reduce vapor residence time. Cyclones were placed in the vapor stream to reduce char particulate carryover. Microfiltration of the bio-oil was also researched to remove char particulate from the bio-oil. The capital cost for these improvements would be less than 2% of the total plant capital cost

Gel Point Determination of Biopolymer Based Semi-IPN Hydrogels

Water-based semi-IPNs (Interpenetrating Polymer Networks) were prepared by mixing two biopolymers, alginate and hydrophobically modified ethylhydroxy ethyl cellulose (HMEHEC), followed by crosslinking the alginate by in-situ release of calcium ions. By altering two different parameters, molecular weight of HMEHEC and calcium crosslinker concentration, we were able to fine tune the rheological properties of the semi-IPNs. Rheological studies in the linear viscoelastic region indicate storage moduli comparable to soft tissue for hydrogels having 90 wt% water. The system is found to be stable over a prolonged period of time, i.e. no phase separation is observed. Uniformity of the structure is confirmed by monotonic behavior of the intensity-q slope in SAXS and SANS over the entire length scale