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...
Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low-surface-area materials, notably for compositions that are industrially relevant.
The properties of thermally reversible organogels in which the gelators consist of a phosphonic acid monoester, phosphonic acid, or phosphoric acid monoester and a ferric salt are probed by IR and NMR spectroscopies, optical microscopy, X-ray diffraction, rheology, and light and small-angle neutron scattering (SANS) techniques. This is one of a small number of two-component molecular gelator systems in which gelation can be induced isothermally. The data indicate that complexation between the phosphonate moieties and Fe(III) is accompanied by their in situ polymerization to form self-assembled fibrillar networks that encapsulate and immobilize macroscopically the organic liquid component. From SANS measurements, the cross-sectional radii of the cyclindrical fibers are ca. 15 A. The efficiencies of the gelators (based on the diversity of the liquids gelated, the minimum concentration of gelator required to make a gel at room temperature, and the temporal and thermal stabilities of the gels) have been determined. With a common ferric salt and liquid component, phosphonic acid monoesters are generally more efficient than phosphinic acids or phosphoric acid esters. Of the phosphonic acid monoesters, monophosphonates are better gelator components than bisphosphonates, and introduction of an omega-hydroxy group on the alkyl chain directly attached to phosphorus reduces significantly gelation ability. Several of the gels are stable for very long periods at room temperature. When heated, they revert to sols over wide temperature ranges. The structures of the gelator complexes and the mechanism of their formation and transformation to gels in selected liquids are examined as well.
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