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Magnesium-based cement is one of the most interesting eco-sustainable alternatives to standard cementitious binders. The reasons for the interest towards this material are twofold: (i) its production process, using magnesium silicates, brine or seawater, dramatically reduces CO2 emissions with respect to Portland cement production, and (ii) it is very well suited to applications in radioactive waste encapsulation. In spite of its potential, assessment of the structural properties of its binder phase (magnesium silicate hydrate or M–S–H) is far from complete, especially because of its amorphous character. In this work, a comprehensive structural characterization of M–S–H was obtained using a multi-technique approach, including a detailed solid-state NMR investigation and, in particular, for the first time, quantitative 29Si solid-state NMR data. M–S–H was prepared through room-temperature hydration of highly reactive MgO and silica fume and was monitored for 28 days. The results clearly evidenced the presence in M–S–H of “chrysotile-like” and “talc-like” sub-nanometric domains, which are approximately in a 1 : 1 molar ratio after long-time hydration. Both these kinds of domains have a high degree of condensation, corresponding to the presence of a small amount of silanols in the tetrahedral sheets. The decisive improvement obtained in the knowledge of M–S–H structure paves the way for tailoring the macroscopic properties of eco-sustainable cements by means of a bottom-up approach. [ABSTRACT FROM AUTHOR]

Concrete is the world's most widely used building material. However, the production of CaO-based cements generates large amounts of anthropogenic emissions of CO2. Among different strategies to reduce CO2 emissions, newly developed MgO-based cements, though currently suffering from inferior mechanical properties, are some of the most promising and attractive options. By combining wide- and small-angle X-ray scattering and electron microscopy, we identified differences in the multiscale structure of the two main binding phases: the calcium-silicate-hydrate (C-S-H) gel for CaO-based cements and the magnesium-silicate-hydrate (M-S-H) gel for MgO-based cements. We found the primary unit at the nanoscale level of C-S-H to be a multilayer disk-like globule, whereas for M-S-H it is a spherical globule. These prominent differences result in diverse microstructures, leading to disparities in mechanical properties and durability for the associated cements. Modulating the M-S-H structure and enhancing the compatibility between C-S-H and M-S-H will be the key to improve the robustness of eco-friendly MgO-based binders. [ABSTRACT FROM AUTHOR]

Different metal substituted (Y, Sn and Ce) MCM-41 materials were synthesized and detemplated by a low temperature surfactant removal methodology. All metal substituted materials showed an increase in the d[sub 100] lattice parameter compared to the parent MCM-41 matrices. The increase depends on both the metal type and amount that is successfully incorporated by direct conventional hydrothermal synthesis. The metal modified MCM-41 materials were detemplated by an ultrasound assisted (US) ion-exchange process using methanol as the solvent (NH[sub 4]NO[sub 3]/US/MeOH). The effect of the ultrasound amplitude, extraction time and salt concentration were explored, and optimal values were determined for Y -- MCM-41 detemplation (40 mM of NH[sub 4]NO[sub 3], 60% of US amplitude and 15 min of adiabatic treatment). The removal percentage achieved with these values was in the following order: Y (97.7%) > Ce (94.4%) > Sn (92.1%) > Si (90.3%). Several techniques (SAXS, FTIR, TGA, 1[sub H] MAS, 29[sub Si] HPDEC MAS NMR and N[sub 2] physisorption) demonstrated that the mesoporous materials keep their hexagonal structure and high surface area after the NH[sub 4]NO[sub 3]/US/MeOH surfactant extraction. Moreover, the thermal shrinkage of the structure was reduced in the following order: Si (0.6%) < Sn (4%) < Ce (5%) < Y (9%) < calcined samples (from 9 to 15%). The surfactant recovered was successfully recycled in a consecutive microwave assisted hydrothermal synthesis cycle (MW-HT). The synergy of different strategies (MW-HT synthesis, NH[sub 4]NO[sub 3]/ US/MeOH surfactant removal and surfactant recovery) produces considerable time, energy and cost abatement, environmental impact reduction and promising scale up projections in the eco-friendly synthesis of MCM-41 materials. [ABSTRACT FROM AUTHOR]

In this work, bovine serum albumin (BSA) and Aspergillus sp. laccase (LC) were encapsulated in situ within two lanthanide-based MOFs (TbBTC and GdBTC) through a green one-pot synthesis (almost neutral aqueous solution, T = 25 °C, and atmospheric pressure) in about 1 h. Pristine MOFs and protein-encapsulated MOFs were characterized through wide angle X-ray scattering, scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared and Raman spectroscopies. The location of immobilized BSA molecules, used as a model protein, was investigated through small angle X-ray scattering. BSA occurs both on the inner and on the outer surface of the MOFs. LC@TbBTC, and LC@GdBTC samples were also characterized in terms of specific activity, kinetic parameters, and storage stability both in water and acetate buffer. The specific activity of LC@TbBTC was almost twice that of LC@GdBTC (10.8 μmol min -1 mg -1 vs. 6.6 μmol min -1 mg -1 ). Both biocatalysts showed similar storage stabilities retaining ∼60% of their initial activity after 7 days and ∼20% after 21 days. LC@TbBTC dispersed in acetate buffer exhibited a higher storage stability than LC@GdBTC. Additionally, terbium-based MOFs showed interesting luminescent properties. Together, these findings suggest that TbBTC and GdBTC are promising supports for the in situ immobilization of proteins and enzymes.

Calcium silicate hydrate (C-S-H) is the main binding product of ordinary Portland concrete (OPC). Unfortunately, OPC production generates ∼5% of all anthropomorphic CO2. Among the most promising green alternatives, magnesium silicate hydrate (M-S-H) is a colloidal gel equivalent to C-S-H which exhibits weaker mechanical properties. Here we investigated the effect of the inclusion of aluminosilicate nanoclays (HNTs) on the microstructure of the silicate hydrate gels as a strategy to ultimately improve their mechanical properties. The microstructure of C-S-H and M-S-H gels synthesized with and without carboxylic or polycarboxylic functionalised HNTs (HNT-COOH, HNT-PAA) was investigated by a multi-technique approach including small- and wide-angle X-ray scattering (SWAXS) and scanning electron microscopy (SEM). The results indicate that, during C-S-H formation in solution, HNTs decrease the size of the disk-like globules with little influence on the spacing of calcium silicate layers. In the case of M-S-H, the presence of functionalised HNTs has a reduced effect on the hydrate structure as a result of the weaker interaction of the carboxylic moieties with Mg2+ ions. SEM investigation on the synthesized composites shows that HNT-PAA are better included in the hydration products. Moreover, in the proximity of the PAA functionalised surfaces, less extended aggregates are formed. The morphology at the micron scale for M-S-H and C-S-H with HNT-COOH is conserved.

The impact of high energy crosslinking on the network structure of gelatin hydrogels was investigated in comparison to physically entangled gels by small-angle X-ray scattering (SAXS). Physically entangled gelatin of increasing concentration exhibited a nearly constant correlation length of several nanometers. These gels had scattering behavior close to that of polymer coils swollen in a good solvent, as evidenced by the Porod exponent of 1.8. The mass fractal dimension decreased towards 1, indicating increased formation of semiflexible gelatin triple helices and rod-like structures as a function of the gelatin concentration. In contrast, electron irradiation lead to a decrease in the correlation length at doses above 20 kGy. Covalent crosslinking induced by electron irradiation lead to increased branching and formation of globular structures, as observed by a steady increase of both the Porod exponent and mass fractal dimension. Furthermore, the network mesh size systematically decreased from approximately 45 nm to under 20 nm with both additional physical and chemical crosslinking. These mesh sizes as obtained by SAXS were used to estimate the network shear modulus using several polymer models and were compared to macroscopic rheology measurements. Finally, SEM images of freeze-dried samples revealed changes in the microstructure of the irradiated hydrogels. Overall, fundamental differences in the network structures stemming from the crosslinking method were observed across a wide range of length scales.

The phase behavior of a mixture of a typical insect pheromone (olean) and a phospholipid (DOPC)/water dispersion is extensively explored through SAXS, NMR and DSC experiments. The results mimic those obtained with anaesthetics in phospholipid/water systems. They also mimic the behavior and microstructure of ternary mixtures of a membrane mimetic, bilayer-forming double chained surfactants, oils and water. Taken together with recent models for conduction of the nervous impulse, all hint at lipid involvement and the underlying unity in mechanisms of pheromone, anaesthetic and hydrophobic drugs, where a local phase change in the lipid membrane architecture may be at least partly involved in the transmission of the signal.

The structure and rheology behaviour of gels produced by water dispersions of a vitamin C-derived surfactant (ascorbyl-6-O-dodecanoate) were investigated by means of SAXS and rheology experiments for the first time. The gel state is formed upon heating and is due to an anisotropic expansion of the tightly compact lamellar structure. The phase transition involves primarily the melting of the alkyl chains and a significant increment in the interlamellar water layer. In particular, our results show that in the gel the hydrophobic chains are in a liquid-like state, as in the core of a micelle, while the head groups release their acidic proton, become negatively charged and determine the onset of strong electrostatic interactions between facing lamellae. The full hydration of the anionic head groups and the uptake of a significant amount of water increase the interlamellar thickness and stabilise the gel structure. Rheology and SAXS measurements together provide an updated picture for the gel state. Moreover, for the first time we show the presence of a concentration threshold, above which the self-assembled aggregates interact more strongly and deplete some of the water that is retained in the interlamellar region.

Magnesium-based cement is one of the most interesting eco-sustainable alternatives to standard cementitious binders. The reasons for the interest towards this material are twofold: (i) its production process, using magnesium silicates, brine or seawater, dramatically reduces CO2 emissions with respect to Portland cement production, and (ii) it is very well suited to applications in radioactive waste encapsulation. In spite of its potential, assessment of the structural properties of its binder phase (magnesium silicate hydrate or M-S-H) is far from complete, especially because of its amorphous character. In this work, a comprehensive structural characterization of M-S-H was obtained using a multi-technique approach, including a detailed solid-state NMR investigation and, in particular, for the first time, quantitative (29)Si solid-state NMR data. M-S-H was prepared through room-temperature hydration of highly reactive MgO and silica fume and was monitored for 28 days. The results clearly evidenced the presence in M-S-H of "chrysotile-like" and "talc-like" sub-nanometric domains, which are approximately in a 1 : 1 molar ratio after long-time hydration. Both these kinds of domains have a high degree of condensation, corresponding to the presence of a small amount of silanols in the tetrahedral sheets. The decisive improvement obtained in the knowledge of M-S-H structure paves the way for tailoring the macroscopic properties of eco-sustainable cements by means of a bottom-up approach.

High resolution inelastic X-ray scattering (IXS) experiments show that the "phonon energy softening" and "phonon population enhancement" observed in a hydrated native protein when increasing the temperature from 200 K to physiological temperature are not directly related to the protein structure. Such phenomena were also observed in a denatured sample without a defined tertiary structure and with a limited residual secondary structure. However, in a dry sample, such "softening" is strongly suppressed. These facts suggest that the above-mentioned protein "softening" phenomenon is water-induced. In addition, increasing the hydration level can also induce "phonon energy softening" at room temperature, but not at 200 K. This change may be due to a qualitative difference in the dynamics of hydration water at 200 K and at room temperature.