Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.

A hierarchical mesoporous network of zeolite beta with very high micropore as well as mesopore volume was synthesized without the need of a porogen at near 100% yield in the form of easily retrievable micrometer-sized particles. This was achieved by a dense-gel synthesis utilizing steam-assisted conversion (SAC) to induce a burst of nucleation. During the first phase of the synthesis, individual, evenly sized zeolite beta nanoparticles are formed that subsequently condense into a porous network displaying uniform mesopores. The final product consists of hierarchical self-sustaining macroscopic zeolite aggregates assembled from 20 nm crystalline domains of zeolite beta. The small size of the zeolite crystals in the resulting materials gives rise to mesopores with dominant pore sizes of about 13 nm. Large surface areas between 630 and 750 m(2)/g and total pore volumes up to 0.9 mL/g were obtained without sacrificing the microporosity (usually larger than 0.20 mL/g). Crystallization conditions were optimized for different Si/Al ratios between 10 and 33. A complete conversion into hierarchical zeolite beta was achieved in only a few hours at 170-180 °C if the amount of water present during the steam-assisted conversion was adequately adjusted. This dense gel steam conversion process proves to be a highly efficient strategy for fabricating hierarchical zeolite beta networks in a single step.

We present the first direct evidence of non random siting of Ti and Fe in TS-1 and FeS-1, nanoporous metallosilicate selective oxidation catalysts of MFI topology. This was accomplished by using Rietveld analysis of powder neutron diffraction data and exploiting the differences in neutron scattering lengths between Ti or Fe and Si. Previous spectroscopic, X-ray diffraction, and computational approaches have suggested a random substitution of Ti and Fe ions among the 12 crystallographically distinct Si sites in the framework of TS-1 and FeS-1. In contrast, our results indicate that titanium is distributed among only 4 or 5 of the 12 silicon sites with Ti occupying T3, -7, -8, -10, and -12. Of the 2.47 total Ti atoms per unit cell the Ti site occupancies and estimated standard deviation for sample B are as follows: T3 0.30(0.11), T7 0.34(0.14), T8 0.92(0.10), T10 0.41(0.14), and T12 0.50(0.14). In FeS-1 synthesized with 1.5 Fe atoms per unit cell, iron is found only at T8. Several starting models were chosen for initial refinement, and each returned the same specific, nonrandom distribution of Ti in the framework of MFI. We have examined several computational approaches that involve thermodynamic arguments to rationalize the experimental observations, and all have failed to predict the experimentally observed substitution pattern. This suggests that the kinetics of framework formation may play a role in directing the observed metal substitution.

Group 4 phosphides, which are typically prepared at high temperatures (> 800 degrees C) over several days, are synthesized in self-propagating metathesis (exchange) reactions in seconds. These reactions produce cubic forms of zirconium phosphide (ZrP) and hafnium phosphide (HfP) which are normally made at temperatures greater than 1425 degrees C and 1600 degrees C, respectively. To test whether the high temperatures reached in the metathesis reactions are responsible for the formation of the cubic phases, inert salts are added to lower the maximum reaction temperatures. The lower temperature reactions still result in cubic phosphides, although smaller crystallites form. Further experiments with phosphorus addition indicate that the phosphorus content is not responsible for cubic phase formation. Templating is ruled out using lattice mismatched KCl and hexagonal ZnS as additives. Therefore, the direct synthesis of the high-temperature cubic phase in metathesis reactions appears to be caused by nucleation of the metastable cubic form that is then trapped by rapid cooling. Heating the cubic phase of either ZrP or HfP to 1000 degrees C for 18 h, or carrying out metathesis reactions in sealed ampules at 1000 degrees C, results only in the hexagonal phase.

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In the third sentence,``hyperglycaemia'' should have read``hypoglycaemia''. The corrected sentence is: "Here we show that mice carrying a targeted disruption of the cyclic AMP (cAMP) response element binding (CREB) protein gene, or overexpressing a dominant-negative CREB inhibitor, exhibit fasting hypoglycaemia and reduced expression of gluconeogenic enzymes." M

Mosi2 has a very favorable combination of materials properties, including a high melting point (2020°C), high strength at elevated temperatures, and resistance to high temperature oxidation and corrosion. These properties make it a good candidate for a hightemperature structural material; however, it has very poor ductility. A great deal of research has focused on improving the ductility of this alloy through various preparative routes. We have synthesized Mosi2, as well as WSi2, TaSi2, and NbSi2, using rapid solid-state metathesis reactions between a high oxidation state metal halide and an alkaline earth silicide. These reactions take advantage of the large exothermic heat of formation of the alkaline earth halide and can reach temperatures as high as the melting point of the product silicides. In addition, this approach yields crystalline products in seconds. The synthetic technique will be discussed along with characterization results.

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