Bone is a fascinating biomaterial composed mostly of type-I collagen fibers as an organic phase, apatite as an inorganic phase, and water molecules residing at the interfaces between these phases. They are hierarchically organized with minor constituents such as non-collagenous proteins, citrate ions and glycosaminoglycans into a composite structure that is mechanically durable yet contains enough porosity to accommodate cells and blood vessels. The nanometer scale organization of the collagen fibrous structure and the mineral constituents in bone were recently extensively scrutinized.
View Article and Find Full Text PDFDetails of apatite formation and development in bone below the nanometer scale remain enigmatic. Regulation of mineralization was shown to be governed by the activity of non-collagenous proteins with many bone diseases stemming from improper activity of these proteins. Apatite crystal growth inhibition or enhancement is thought to involve direct interaction of these proteins with exposed faces of apatite crystals.
View Article and Find Full Text PDFOne of the many challenges in the study of chiral nanosurfaces and nanofilms is the design of accurate and controlled nanoscale films with enantioselective activity. Controlled design of chiral nanofilms creates the opportunity to develop chiral materials with nanostructured architecture. Molecular layer deposition (MLD) is an advanced surface-engineering strategy for the preparation of hybrid inorganic-organic thin films, with a desired embedded property; in our study this is chirality.
View Article and Find Full Text PDFNa MAS NMR spectroscopy of the smectite mineral hectorite acquired at temperatures from -120 °C to 40 °C in combination with the results from computational molecular dynamics (MD) simulations show the presence of complex dynamical processes in the interlayer galleries that depend significantly on their hydration state. The results indicate that site exchange occurs within individual interlayers that contain coexisting 1 and 2 water layer hydrates in different places. We suggest that the observed dynamical averaging may be due to motion of water volumes comparable to the dripplons recently proposed to occur in hydrated graphene interlayers (Yoshida , 2018, , 1496).
View Article and Find Full Text PDFMotivated by the potential usefulness of polyethylene glycol (PEG)/Li salt mixtures in several industrial applications, we investigated the structure and dynamics of PEG/LiClO mixtures in D O and its mixtures with CD CN and DMSO-d , in a series of PEG-based polymers with a wide variation in their molecular weights. H NMR chemical shifts, T /T relaxation rates, pulsed-field gradient NMR diffusion experiments, and 2D HOESY NMR studies have been performed to understand the structural and dynamical aspects of these mixtures. Increasing the temperature of the medium results in a significant perturbation in the H-bonded structure of PEG in its PEG/LiClO /D O mixtures as observed from the increase in chemical shifts.
View Article and Find Full Text PDFDistinct microheterogeneity has been observed in the [OMIM]Br-H2 O system, which is interestingly perturbed by the addition of Li(+) salts, indicating unusual diffusivity of [OMIM]Br and H2 O molecules. However, the diffusional dynamics of water clusters show contrasting salting behavior at higher concentrations of Li(+) salts, following the classical salting phenomenon in lower amounts. In contrast, the existing microheterogeneity in the [BMIM]Br-H2 O system is weak enough to show any perturbation caused by the Li(+) salts on the NMR time scale.
View Article and Find Full Text PDFWe present our studies on the physicochemical properties of water confined in Dibutylimidazolium bis(trifluoromethanesulfonylimide) ([C4C4im][NTf2]) reverse micelles through the NMR relaxation measurements that provide us an understanding of microviscosity and pH in the confined condition. We present experimental results on phase behavior, diffusion, structural characteristics and pH in aqueous ionic liquid-confined media. The ternary phase diagram was constructed by the cloud point measurements and the microheterogeneous regions were detected by the measurement of bulk viscosity and diffusion coefficients of K4[Fe(CN)6] inside the homogeneous microemulsion systems through the cyclic voltammetric (CV) measurements.
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