Seeking Solvation: Exploring the Role of Protein Hydration in Silk Gelation

The mechanism by which arthropods (e.g., spiders and many insects) can produce silk fibres from an aqueous protein (fibroin) solution has remained elusive, despite much scientific investigation. In this work, we used several techniques to explore the role of a hydration shell bound to the fibroin in native silk feedstock (NSF) from Bombyx mori silkworms. Small angle X-ray and dynamic light scattering (SAXS and DLS) revealed a coil size (radius of gyration or hydrodynamic radius) around 12 nm, providing considerable scope for hydration. Aggregation in dilute aqueous solution was observed above 65 °C, matching the gelation temperature of more concentrated solutions and suggesting that the strength of interaction with the solvent (i.e., water) was the dominant factor. Infrared (IR) spectroscopy indicated decreasing hydration as the temperature was raised, with similar changes in hydration following gelation by freezing or heating. It was found that the solubility of fibroin in water or aqueous salt solutions could be described well by a relatively simple thermodynamic model for the stability of the protein hydration shell, which suggests that the affected water is enthalpically favoured but entropically penalised, due to its reduced (vibrational or translational) dynamics. Moreover, while the majority of this investigation used fibroin from B. mori, comparisons with published work on silk proteins from other silkworms and spiders, globular proteins and peptide model systems suggest that our findings may be of much wider significance.

Synthesis and characterization of novel thermo- and salt-sensitive amphoteric terpolymers based on acrylamide derivatives

A novel linear amphoteric terpolymers based on neutral monomer — N-isopropylacrylamide (NIPAM), ani- onic monomer — 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS), and cationic mono- mer — (3-acrylamidopropyl) trimethylammonium chloride (APTAC) were synthesized by free-radical polymerization in aqueous solution and characterized by methods of 1H NMR and FTIR spectroscopy, TGA, GPC, Dynamic light scattering (DLS) and zeta-potential. The thermal and salt sensitivity of amphoteric ternary polymers of various compositions, particularly, [NIPAM]:[AMPS]:[APTAC] = 90:2.5:7.5; 90:5:5; 90:7.5:2.5 mol.% were studied in aqueous and aqueous-salt solutions in the temperature range from 25 to 60 C and at the NaCl ionic strength  interval from 10–3 to 1M. It was found that due to hydrophobic/hydrophilic balance, the temperature dependent conformational and phase change of macromolecular chains becomes sensitive to salt addition and allows the fine-tuning of the phase transition. In aqueous and aqueous-salt solutions, the average hydrodynamic size of amphoteric terpolymers is varied from 8 to 300 nm exhibiting bimodal distribution at room temperature. The number average (Mn) and weight average (Mw) molecular weights, polydispersity index (PDI), and zeta-potentials of amphoteric terpolymers in aqueous solu- tions were determined

Mineralization treatment of European oak heartwood with calcium oxalate for improved fire retardancy

Within the focus to apply substances for wood protections, here fire retardants, with low hazardous and low environmental impact is of interest. Additionally, European oak is an attractive species for various interior and exterior applications. However, oak is classified as very heavily treatable and thus impregnation is challenging. However, the focus of this study was to treat European oak with a new fire retardant based on an in-situ calcium oxalate deposition. Thin oak specimens with a thickness of 4 mm were investigated with two various formulations of aqueous salt solutions (potassium oxalate and calcium chloride, and potassium oxalate and calcium acetate) to obtain an in-situ mineralization of calcium oxalate during a two-step impregnation process. The uptake, the distribution, and the penetration of the salts for both applied formulations were investigated. Additionally, fire retardant properties were investigated in a single flame source test. It could be demonstrated that an acceptable degree of treatability was achieved for both applied formulations. The fire retardancy of the so mineralized material was clearly improved. Synergetic effects which might be caused by the reaction side products of the various formulations were found to be neglectable.

Cast-in-situ piles encasements based on oil-bituminous rocks (kirs) in saline soils

A technology of building a pile foundation in saline soils with a protective and load-bearing shell based on bituminous rocks (kirs) is proposed that makes it possible to eliminate water permeability, to increase suffusion resistance and bearing capacity of the soil, as well as durability. The method of extracting natural bitumen from bituminous rocks (kirs) is based on the ability of kirs to self-grind or disintegrate into small parts at elevated temperatures in aqueous salt solutions. The proposed method excludes mechanical grinding and allows reducing the consumption of reagents and improving the quality of extracted natural bitumen. The compositions of the obtained mastics based on natural bitumen are not inferior in their properties to the known compositions of waterproofing cold mastics based on industrial bitumen at a lower cost.

Forces between reactive surfaces

<p>Adhesive and repulsive, nm-range surface forces acting between mineral grains control colloidal stability and mineral aggregation but less is known about how these forces are affected by surface reactivity and to what extent these grain-scale forces can influence various deformation processes in rocks. In this experimental work, we explore and quantify the surface forces acting between dynamic mineral surfaces that undergo recrystallization or are chemically reactive in contact with water or aqueous salt solutions. Our experimental setup consists of the surface forces apparatus (SFA) coupled with the multiple beam interferometry (MBI). This setup can excellently reproduce a typical grain contact geometry with nanometer-thin water films confined between contacting mineral grains over relatively large, micron-sized contact areas. Owing to the use of MBI, both surface growth or dissolution processes can be monitored during force measurements in real-time. As such, SFA can provide information about the links between surface reactivity and adhesive or repulsive surface forces. Using the examples of force measurements between recrystallizing or chemically reactive mineral surfaces such as carbonates, hydroxides, and silicates, we comment on the relationship between the measured surface forces and surface reactivity. We link our findings with the observed changes in mineral phases, surface topographies, or surface roughness. We also comment on how the micron-scale confinement in the SFA affects the growth and dissolution processes in contrast to less confined regions. The magnitude of the forces associated with dynamic mineral surfaces and the potential significance of these forces to macroscopic deformation processes and cohesion in rocks are discussed.</p>