Crystal structure of zeolite MCM-68: a new three-dimensional framework with large pores

The crystal structure of the aluminosilicate MCM-68 was solved from synchrotron powder diffraction data by the program FOCUS. The unit cell framework contains Si100.6Al11.4O224. This material crystallizes in space group P42/mnm, where, after Rietveld refinement, a=18.286(1) A and c=20.208(2) A. A three-dimensional framework is found that contains continuous 12-ring channels and two orthogonal, intersecting, undulating 10-ring channels. Rietveld refinement of the model coordinates optimizes the framework geometry, to match the observed intensity profile by Rwp=0.1371, R(F2)=0.1411. It is not possible to determine the location of approximately 0.84 K+ cations remaining in the unit cell after the material is steamed and then dehydrated. The framework model also successfully predicts observed electron diffraction data in two projections, and the tetragonal projection can be determined independently from these data by direct methods. The calculated density of the framework structure is 1.66 g/cm3, and the T-site framework density is 16.6 T/1000 A3.     

Zn adsorption on Pd(111): ZnO and PdZn alloy formation

The adsorption and thermal desorption of Zn and ZnO on Pd(111) was studied in the temperature range between 300 and 1300 K with TDS, LEED, and CO adsorption measurements. At temperatures below 400 K, multilayer growth of Zn metal on the Pd(111) surface takes place. At a coverage of 0.75 ML of Zn, a p(2 x 2)-3Zn LEED structure is observed. Increasing the coverage to 3 ML results in a (1 x 1) LEED pattern arising from an ordered Zn multilayer on Pd(111). Thermal desorption of the Zn multilayer state leads to two distinct Zn desorption peaks: a low-temperature desorption peak (400-650 K) arising from upper Zn layers and a second peak (800-1300 K) originating from the residual 1 ML Zn overlayer, which is more strongly bound to the Pd(111) surface and blocks CO adsorption completely. Above 650 K, this Zn adlayer diffuses into the subsurface region and the surface is depleted in Zn, as can be deduced from an increased amount of CO adsorption sites. Deposition of >3 ML of Zn at 750 K leads to the formation of a well-ordered Pd-Zn alloy exhibiting a (6 x 4 square root 3/3)rect. LEED structure. CO adsorption measurements on this surface alloy indicate a high Pd surface concentration and a strong reduction of the CO adsorption energy. Deposition of Zn at T > 373 K in 10(-6) mbar of O2 leads to the formation of an epitaxial (6 x 6) ZnO overlayer on Pd(111). Dissociative desorption of ZnO from this overlayer occurs quantitatively both with respect to Zn and O2 above 750 K, providing a reliable calibration for both ZnO, Zn, and oxygen coverage.     

Continuous Bundles of C*-Algebras with Discontinuous Tensor Products

For each non-exact C*-algebra A and infinite compact Hausdorffspace X there exists a continuous bundle B of C*-algebras onX such that the minimal tensor product bundle AB is discontinuous.The bundle B can be chosen to be unital with constant simplefibre. When X is metrizable, B can also be chosen to be separable.As a corollary, a C*-algebra A is exact if and only if A Bis continuous for all unital continuous C*-bundles B on a giveninfinite compact Hausdorff base space. The key to proving theseresults is showing that for a non-exact C*-algebra A there existsa separable unital continuous C*-bundle B on [0,1] such thatA B is continuous on [0,1] and discontinuous at 1, a counter-intuitiveresult. For a non-exact C*-algebra A and separable C*-bundleB on [0,1], the set of points of discontinuity of A B in [0,1]can be of positive Lebesgue measure, and even of measure 1.2000 Mathematics Subject Classification 46L06 (primary), 46L35(secondary).     

Hyper-Raman scattering from vitreous boron oxide: coherent enhancement of the boson peak

Hyper-Raman scattering spectra of vitreous B(2)O(3) are compared to Raman scattering ones. Particular attention is given to the low-frequency boson peak which relates to out-of-plane rigid librations of planar structural units, mostly boroxols. While the Raman strength can be accounted for by the motions of single units, the hyper-Raman signal exhibits a unequaled enhancement due to coherent librations of several boroxols. This important distinction is explained by the different symmetry properties of the polarizability and hyperpolarizability tensors of the structural units.     

Highly diastereoselective Diels-Alder cycloadditions of 9R-(1-methoxyethyl)anthracene with p-benzoquinone

Diels-Alder cycloadditions of p-benzoquinone with 9R-(1-methoxyethyl)anthracene provides a 60:40 ratio of cycloadducts when heated at reflux in xylene. Mechanistic studies to explore the origins of this selectivity have shown that at lower temperatures the kinetic product predominates, giving a 96:4 ratio of cycloadducts.     

ChemMatrix, a poly(ethylene glycol)-based support for the solid-phase synthesis of complex peptides

CM (ChemMatrix) resin is a new, totally poly(ethylene glycol) (PEG)-based resin, made exclusively from primary ether bonds and, therefore, highly chemically stable. It exhibits good loading and is user-friendly because of its free-flowing form upon drying. It performs excellently for the preparation of hydrophobic, highly structured, and poly-Arg peptides, as compared to polystyrene (PS) resins. In the most striking example, stepwise solid-phase assembly of the highly complex beta-amyloid (1-42) peptide resulted in a crude material of 91% purity. In contrast, literature procedures using PS or PEG-PS-based resins for this peptide required convergent approaches, additional time-consuming steps, or both. In addition to the difficulties of its synthesis, characterization of the beta-amyloid (1-42) peptide as a monomer is also a challenge, and methods for characterization by HPLC and MALDI-TOF have also been developed.     

Products of the triplet excited state produced in the radiolysis of liquid benzene

The radiation chemical yields of the products derived from the triplet excited state produced in the radiolysis of liquid benzene with gamma-rays, 10 MeV 4He ions, and 10 MeV 12C ions have been determined. Iodine scavenging techniques have been used to examine the formation and role of radicals, especially the H atom and phenyl radical. For all irradiation types examined here, the increase in hydrogen iodide yields with increasing iodine concentration matches the increase in iodobenzene yields. This agreement suggests that the benzene triplet excited state is the common precursor for the H atom and the phenyl radical. Pulse radiolysis studies in liquid benzene have determined the rate coefficients for the reactions of phenyl radicals with iodine and with the solvent benzene to be 9.3 x 10(9) M(-1) s(-1) and 3.1 x 10(5) M(-1) s(-1), respectively. Direct measurements of polymer formation, which refers to trimers (C18) and higher order compounds (>C18), in liquid benzene radiolysis using gamma-rays, 4He ions, and 12C ions at relatively high doses have been performed using gel permeation chromatography. The yields of trimers increase from gamma-rays to 12C ions due to the increased importance of intratrack radical-radical reactions that can be scavenged by the radical scavenging reactions of iodine. On the other hand, the >C18 product yields decrease from gamma-rays to 12C ions. The structure of the polymer consists of a partly saturated ring as determined by infrared and gas chromatography/mass spectrometry studies. A schematic representation for the radiolytic decomposition of the benzene triplet excited state is presented.     

Cavity ring-down spectroscopy of the torsional motions of 1,4-bis(phenylethynyl)benzene

The torsional motions of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB), a prototype molecular wire, were studied using cavity ring-down spectroscopy in the first UV absorption band (316-321 nm). The torsional spectrum of 1,4-bis(phenylethynyl)-2,3,5,6-tetradeuteriobenzene was also recorded in the gas phase. Both spectra were successfully simulated using simple cosine potentials to describe the torsional motions. The ground-state barrier to rotation was estimated to be 220-235 cm(-1), which is similar to that of diphenylacetylene (tolane). Complementary DFT calculations were found to overestimate the torsional barrier.     

Polynuclear cyanoruthenate chromophores based on hexaaza-triphenylene containing up to twelve cyanides: photophysical and structural properties

The complexes [Ru(CN)4(HAT)]2-, [{Ru(CN)4}2(mu2-HAT)]4- and [{Ru(CN)4}3(mu3-HAT)]6- (HAT = hexaaza-triphenylene) contain four, eight and twelve externally-directed cyanide ligands, respectively; they show strongly solvatochromic and intense MLCT absorptions, and [3]6- forms a high-dimensionality cyanide-bridged coordination network with Nd(III), in which Ru --> Nd energy transfer results in sensitised near-IR luminescence.