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2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic environmental contaminant found in soils and sediments. Because of its exceptionally low water solubility, this compound exists predominantly in the sorbed state in natural environments. Clay minerals, especially expandable smectite clays, are one of the major component geosorbents in soils and sediments that can function as an effective adsorbent for environmental dioxins, including TCDD. In this study, TCDD was intercalated in the smectite clay saponite by an incipient wetness method. The primary goal of this study was to intercalate TCDD in natural K-saponite clay and evaluate its immunotoxic effects in vivo. The relative bioavailability of TCDD was evaluated by comparing the metabolic activity of TCDD administered in the adsorbed state as an intercalate in saponite and freely dissolved in corn oil. This comparison revealed nearly identical TCDD-induced suppression of humoral immunity, a well-established and sensitive sequela, in a mammalian (mouse) model. This result suggests that TCDD adsorbed by clays is likely to be available for biouptake and biodistribution in mammals, consistent with previous observations of TCDD in livestock exposed to dioxin-contaminated ball clays that were used as feed additives. Adsorption of TCDD by clay minerals does not appear to mitigate risk associated with TCDD exposure substantially.

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2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), the prototypical aryl hydrocarbon receptor (AhR) ligand, exhibits immune suppression in vivo and in vitro. Suppression of primary humoral immune responses in particular has been well characterized as one of the most sensitive functional immune endpoints in animals treated with TCDD. Previous studies have used purified TCDD to elucidate the mechanisms by which TCDD and dioxin-like compounds (DLC) impair IgM production by B cells, but did not represent the route by which animals and humans are likely to be exposed environmentally. In the studies reported here, mice were treated with TCDD adsorbed onto a well-defined synthetic silica phase of known purity and physical properties, followed by sensitization with sheep erythrocytes to initiate a humoral immune response. We found that surfactant-templated mesoporous forms of amorphous silica provided an ideal combination of purity, dispersibility and textural properties for immobilizing TCDD. TCDD-adsorbed silica distributed to the spleen and liver after oral administration as assessed by induction of cyp1a1 gene expression. Most notably, TCDD delivered in the adsorbed state on amorphous silica and as a solute in corn oil (CO) produced similar suppression of the anti-sheep red blood cell immunoglobulin M antibody forming cell (sRBC IgM AFC) response at equivalent doses of TCDD. These results suggest that TCDD immobilized on silicate particles found in soils distributes to the spleen and suppresses humoral immunity.

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Mesoporous gamma-alumina with precisely controlled mesoporosity is synthesized through the scaffolding of pseudoboehmite nanoparticles in the presence of a nonionic surfactant as the porogen. In the initial step of the synthesis, a colloidal suspension of pseudoboehmite is prepared by peptizing pseudoboehmite in dilute acidic solution. The nanoparticles in the peptizate are then assembled into a scaffold structure using nonionic Tergitol 15-S-7 (C(15)H(33)(OC(2)H(4))(7)OH) as the surfactant porogen. Calcination of the resulting surfactant-containing composites at 500 degrees C removes the surfactant and concomitantly converts the pseudoboehmite crystallites to gamma-alumina through topochemical transformation with the retention of the scaffold structure. Depending on the surfactant to alumina ratio used to form the scaffold structures, the average pore size can be precisely controlled over the range of 3.5-15 nm. Also, the BET surface areas of the scaffold structures are substantially larger in comparison to the gamma-alumina formed from pseudoboehmite at the same calcination temperature in the absence of surfactant (296-321 vs 238 m(2) g(-1)). The substantial improvement in surface area provided by the scaffold structures, together with the ability to provide narrow pore size distributions over a wide range of average pore sizes by simply adjusting the surfactant content, should substantially improve the effectiveness of this oxide as an adsorbent and as a catalyst or catalyst support.

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The synthesis of saponite in the presence of bis(triethoxysilyl)methane (BTESM) as an organosilicon reagent results in the replacement of up to 33.3 % of the oxygen atoms in the tetrahedral sheet by bridging methylene groups. The methylene-functionalized saponites represent a new form of covalently-bonded organoclay that truly is isomorphic with purely inorganic saponite made under equivalent reaction conditions from sodium silicate as the silicon source. The isoelectronic and isolobal relationship between methylene and bridging oxygen centers is essential for methylene saponite formation. Bridging ethylene groups are not incorporated into the Kagome net of the basal surfaces due to a mismatch in bridging group size. The textural properties of the methylene saponites are similar to those for purely inorganic magnesium saponite made under equivalent synthetic conditions in the absence of BTESM. Layer stacking disorders afford large surface areas (~550 to 650 m(2)/g), making the methylene saponites attractive candidates for use as adsorbents and functional fillers for polymer composites.

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The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

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Large-pore mesoporous silica with 3D wormhole framework structures (denoted MSU-J) are prepared through a supramolecular hydrogen-bonding assembly pathway from low-cost sodium silicate as the silica source and commercially available mono- and triamine Jeffamine and Surfonamine surfactants as structure-directing porogens. The calcined mesostructures exhibit large pore sizes (up to 8.2 nm), surface areas (632-1030 m(2)/g) and pore volumes (0.5-2.0 cm(3)/g), depending on the surfactant chain length and synthesis temperature (25-65 °C). The textural properties of these new wormhole mesostructures are comparable to those of hexagonal SBA-15 derivatives and large pore MCM-48. However, unlike the SBA-15 structure type, wherein the 3D pore network is formed by connecting 1D cylindrical mesopores through micropores, MSU-J mesophases have wormhole framework structures containing fully interconnected 3D mesopores that can minimize the diffusion limitations often encountered in adsorption and chemical catalysis. Also, unlike large pore MCM-48, which requires cost-intensive tetraethylorthosilicate as a silica source and the use of a co-surfactant as a pore expander under strong acid conditions, MSU-J mesostructures are assembled from low cost sodium silicate in the presence of a single Jeffamine or Surfonamine porogen at near-neutral pH.

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The surfactant-mediated hydrolysis of ZSM-5 zeolite affords five-membered ring subunits that can be readily incorporated into the framework walls of a hexagonal mesostructured aluminosilicate, denoted MSU-Z. The five-membered ring subunits, which are identifiable by infrared spectroscopy, impart unprecedented acidity to the mesostructure, as judged by cumene cracking activity at 300 degrees C. Most notably, MSU-Z aluminosilicate made through the base hydrolysis of ZSM-5 in the presence of cetyltrimethylammonium ions exhibits a cumene conversion of 73%, which is 6.7-fold higher than the conversion provided by a conventional MCM-41. This approach to stabilizing zeolitic subunits through surfactant-mediated hydrolysis of zeolites appears to be general. The hydrolysis of USY zeolite under analogous hydrolytic conditions also affords zeolitic fragments that boost the acidity of the mesostructure in comparison to equivalent compositions prepared from conventional aluminosilicate precursors.

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Thiol-functionalized mesostructured silica, prepared by direct assembly methods, is an effective trapping agent for the removal of arsenite from water.

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Thiol-functionalized mesostructured silica with anhydrous compositions of (SiO(2))(1)(-)(x)()(LSiO(1.5))(x)(), where L is a mercaptopropyl group and x is the fraction of functionalized framework silicon centers, are effective trapping agents for the removal of mercuric(II) ions from water. In the present work, we investigate the mercury-binding mechanism for representative thiol-functionalized mesostructures by atomic pair distribution function (PDF) analysis of synchrotron X-ray powder diffraction data and by Raman spectroscopy. The mesostructures with wormhole framework structures and compositions corresponding to x = 0.30 and 0.50 were prepared by direct assembly methods in the presence of a structure-directing amine porogen. PDF analyses of five mercury-loaded compositions with Hg/S ratios of 0.50-1.30 provided evidence for the bridging of thiolate sulfur atoms to two metal ion centers and the formation of chain structures on the pore surfaces. We find no evidence for Hg-O bonds and can rule out oxygen coordination of the mercury at greater than the 10% level. The relative intensities of the PDF peaks corresponding to Hg-S and Hg-Hg atomic pairs indicate that the mercury centers cluster on the functionalized surfaces by virtue of thiolate bridging, regardless of the overall mercury loading. However, the Raman results indicate that the complexation of mercury centers by thiolate depends on the mercury loading. At low mercury loadings (Hg/S < or = 0.5), the dominant species is an electrically neutral complex in which mercury most likely is tetrahedrally coordinated to bridging thiolate ligands, as in Hg(SBu(t))(2). At higher loadings (Hg/S 1.0-1.3), mercury complex cations predominate, as evidenced by the presence of charge-balancing anions (nitrate) on the surface. This cationic form of bound mercury is assigned a linear coordination to two bridging thiolate ligands.

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The direct supramolecular assembly of organofunctional mesostructures with a vesicular hierarchical morphology is reported for the first time for (SiO2)1-x(LSiO1.5)x compositions, where L is a mercaptopropyl group and x = 0.10-0.30.

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The proton transfer process mediated by water molecules adsorbed in an aluminosilicate framework has been studied using ab initio molecular dynamics simulations. This investigation has been carried out using a quasi-one-dimensional model simulating the mesoporous aluminosilicate channel structures. The effects of both the water loading and temperature of the system have been considered. At low coverage (one water molecule per acid site), the hydroxonium ion (H(3)O)(+) is found to be a transition state, in agreement with earlier studies on zeolites. At a higher water coverage (two water molecules per acid site), the (H(5)O(2))(+) species and the hydrogen bonded "neutral complex" structure are both found to be stable complexes at finite temperatures. The vibrational frequency spectrum is simulated by performing a Fourier transform of the velocity autocorrelation function (VAF), and the peak positions in the VAF are compared with IR measurements and zero-temperature calculations.

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The density functional theory (DFT) method is used to investigate the structure and bonding of silica and aluminosilicate nanoclusters containing five- and six-membered oxygen rings. The clusters, which are derived from the BEA zeolite structure, are considered as models of the protozeolitic clusters that are incorporated into the pore walls of steam stable aluminosilicate mesostructures assembled from zeolite seeds. Two locally different Brønsted acid sites in the aluminosilicate structure are identified for the adsorption of a water molecule. The sterically more open acid site is favored for water binding. The stability of the aluminosilicate structure in the presence of H2O molecule is studied by breaking an Al-O bond and inserting a water molecule into the five-membered ring structure. We find that an excitation energy at least 18 times larger than the room-temperature thermal energy is needed to break the stable five-membered ring structure, implying a high hydrothermal stability and acidity for this aluminosilicate structure.

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Clay-PEO nanocomposites can have large electrical conductivities that make them potential electrolyte materials for rechargeable lithium batteries, but the origin of these large conductivities, especially for Li-containing materials, is poorly understood. This paper presents X-ray diffraction (XRD), TGA-DTA, and (7)Li and (23)Na NMR data for PEO nanocomposites made with natural (SWy-1) and synthetic (MNTS) montmorillonite clays that provide new insight into interlayer structure. An increase in basal d(001)-spacings demonstrates successful intercalation of PEO in all samples, and X-ray line narrowing shows that this intercalation improves the layer stacking order. The basal spacings of 17.9-19.4 A are consistent with a helical or bilayer structure of PEO in the interlayer. TGA-DTA provides quantitative results for the hydration state of the nanocomposites, demonstrates PEO intercalation, and shows that the composites prepared from the synthetic montmorillonite are less stable than those made with SWy-1. (7)Li NMR shows that the nearest neighbor hydration state of Li(+) is unaffected by PEO intercalation and suggests weak interaction of Li(+) with PEO. (23)Na NMR shows that PEO intercalation results in the conversion of the multiple Na(+) hydration states observed for the pristine clay into inner sphere sites most likely formed through coordination with the basal oxygens of the clay. These differences between lithium and sodium suggested that tighter binding of the Na to the clay may be the origin of the conductivity of Li-montmorillonite-PEO nanocomposites being as much as 2 orders of magnitude larger than those of Na-montmorillonite-PEO nanocomposites. The results confirm the idea that polymer oxygen atoms do not participate in sequestering the exchangeable cations and agree with the jump process for cation migration advanced by Kuppa and Manias (Kuppa, V.; Manias, E. Chem. Mater. 2002, 14, 2171).

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Directly assembled wormhole mesostructures with high level functionalized mercaptan (MP-HMS) have been shown to be effective mercury(II) (Hg2+) trapping agents. Sorption of Hg2+ onto MP-HMS was investigated using X-ray absorption spectroscopy (XAS) to identify the structural coordination of the adsorbed Hg. Samples with different fractions of mercaptan functionalized groups (i.e., x = 0.1 and 0.5) with various Hg/S molar ratios ranging from 0.05 to 1.4 were investigated. XAS analysis indicates that adsorbed Hg first coordination shell is best fitted with an Hg-O path and an Hg-S path. The Hg-S atomic distance (R(Hg-S)) remained relatively constant while the Hg-S coordination numbers (CN) decreased as Hg/S loading increased. For the Hg-O path, both the CN and the R(Hg-O) increased with increasing Hg loading. XAS results suggest that at low Hg loadings, adsorbed Hg2+ forms mostly monodentate sulfur complexes (-S-Hg-OH) with the sulfur functional groups on the MP-HMS surfaces. At high Hg loadings, the Hg coordination environment is consistent with the formation of a double-layer structure of Hg attached to sulfur binding sites (-S-Hg-O-Hg-OH).

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Silica mesostructures with well-expressed hexagonal and wormhole framework structures and up to 50% organo-functionalization of the framework silicon sites have been directly assembled from sodium silicate.

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Mesostructured carbons with graphitic framework walls are conveniently prepared at ambient pressures through the replication of a mesostructured silica template using an aromatic hydrocarbon as the carbon precursor and a catalyst.

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The in-situ graphitization of an as-made, large pore silica mesostructure templated by nonionic Pluronic 123 surfactant micelles provides a low cost pathway to the nanocasting of linear carbon nanotubes.

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