Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state 1 H, 13 C, 29 Si, and 27 Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications. S accharide molecules and their interactions with inorganic oxide surfaces play crucial roles in a variety of natural and synthetic processes, including biomineralization, biomolecule synthesis, bone resorption, heterogeneous catalysis, corrosion inhibition, and cement hydration. For example, mono-and oligosaccharides are thought to control the morphologies and structures of carbonate skeletons in marine organisms through sitespecific binding to the mineral phases (1, 2). Interactions of simple organic molecules with aluminosilicate surfaces and exchangeable cations in clays have been hypothesized to be key factors in abiotic syntheses of organic molecules (3). For example, sugar-silicate complexes have been shown to stabilize the abiotic formation of biologically important sugars, such as ribose (4). Similar interactions are thought to promote the adhesion of marine organisms at hydrated inorganic surfaces (5). Biofuels can be produced when polysaccharides are converted to monosaccharides and lower molecular weight alkenes at aluminosilicate zeolite surfaces by heterogeneous reactions in the presence of water (6). Saccharides have also been found to inhibit the corrosion of me...
The compositions and molecular structures of anhydrous and hydrated cements are established by using advanced solid-state nuclear magnetic resonance (NMR) spectroscopy methods to distinguish among different molecular species and changes that occur as a result of cement hydration and setting. One- and two-dimensional (2D) solid-state (29)Si and (27)Al magic-angle spinning NMR methodologies, including T(1)-relaxation-time- and chemical-shift-anisotropy-filtered measurements and the use of very high magnetic fields (19 T), allow resonances from different silicate and aluminate moieties to be resolved and assigned in complicated spectra. Single-pulse (29)Si and (27)Al NMR spectra are correlated with X-ray fluorescence results to quantify the different crystalline and disordered silicate and aluminate species in anhydrous and hydrated cements. 2D (29)Si{(1)H} and (27)Al{(1)H} heteronuclear correlation NMR spectra of hydrated cements establish interactions between water and hydroxyl moieties with distinct (27)Al and (29)Si species. The use of a (29)Si T(1)-filter allows anhydrous and hydrated silicate species associated with iron-containing components in the cements to be distinguished, showing that they segregate from calcium silicate and aluminate components during hydration. The different compositions of white Portland and gray oilwell cements are shown to have distinct molecular characteristics that are correlated with their hydration behaviors.
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