SSZ-53 and SSZ-59: two novel extra-large pore zeolites

The syntheses, structure solutions, and physicochemical and catalytic characterizations of the novel zeolites SSZ-53 and SSZ-59 are described. SSZ-53 and SSZ-59 were synthesized under hydrothermal conditions with the [1-(4-fluorophenyl)cyclopentylmethyl]trimethyl ammonium cation and 1-[1-(4-chlorophenyl)cyclopentylmethyl]-1-methyl azocanium cation, respectively, as structure-directing agents. The framework topology of SSZ-53 was solved with the FOCUS method, and the structure of SSZ-59 was determined by model building. Rietveld refinement of synchrotron X-ray powder diffraction data confirms each proposed model. SSZ-53 and SSZ-59 each possess a one-dimensional channel system delimited by 14-membered rings. Results from transmission electron microscopy, electron diffraction, catalytic experiments (spaciousness index and constraint index tests), and argon and hydrocarbon adsorption experiments are consistent with the proposed structures.     

Solid-state supramolecular organization, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides

The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.     

Role of Hydrodynamic Conditions in the Distribution of Anodic Dissolution Rates in Cavity Etching Regions during Electrochemical Micromachining of Partially Insulated Surfaces

Experimental study of the distribution of local rates of electrochemical micromachining in the presence of photoresist masks in various hydrodynamic conditions (macroscopically nonuniform rotating disk electrode, sprayer flow, an electrode placed into a cell with chaotic bulk electrolyte mixing) shows that the maximum etching localization is achieved at the control of the dissolution rate by the mass transport rate (at achieving the anodic limiting current). The localization enhancement as compared to the primary current distribution takes place in the case of a turbulent flow at hydrodynamic conditions where the removal of dissolution products from the undercutting region is hindered. These conditions (electrochemical reaction limited by the ion mass transport rate, high resistance to the mass transport in the undercutting region) are necessary for the localization enhancement using a pulsed anodic–cathodic treatment.     

Rotational and vibrational temperatures of naphthalene in a naphthalene-argon supersonic jet

In the $\text{A}$¹B_2u-$\text{X}$¹A_g system of naphthalene in a supersonic jet, rotational contour calculations show rotational temperatures of 2–60 K for argon carrier gas pressures of 1520-120 Torr. The b_1u vibration v₂₄ shows a high vibrational temperature which corresponds to the seeding temperature for pressures <400 Torr.     

Chemical modification of a viral cage for multivalent presentation

Here we present generalized methods for chemically modifying the surface of a viral protein cage; this exploits the chemistry of native and engineered surface exposed functional groups for multivalent presentation of ligands.     

Hydrolysis of alkyl cyanoacrylate and ethoxycarbonylpropenoylphosphonate polymers

The polymers of ethyl α-cyanopropenoate (widely known as cyanoacrylate) and dimethyl (α-ethoxycarbonyl)propenoylphosphonate have been hydrolyzed and their rates of degradation to formaldehyde have been compared. The phosphate polymer produced much less formaldehyde than the cyanopropenoate polymer as required for an improved surgical adhesive. In a comparative study, the rate of aqueous hydrolysis of a high molecular weight cyanoacrylate polymer differed from a previous report. The nature and the hydrolytic properties of the end groups in the two types of polymer are discussed.     

Models of steroid binding based on the minimum deviation of structurally assigned 13C NMR spectra analysis (MiDSASA)

This paper develops a quantitative k-nearest neighbors modeling technique. The technique is used to demonstrate that a compound's biological binding activity to a receptor can be calculated from the minimum of the square root of the sum of squared deviations (SSSD) of a structurally assigned chemical shift on a template between the unknown compound to be predicted and a set of known compounds with known activities. When building models of biological activity, nonlinear relationships are built into the input training data. If a model is developed by selecting only compounds with minimum structurally assigned chemical shift deviations from the unknown compound, some of the nonlinear relationships can be removed. The smaller the total chemical shift deviation between a compound with known activity and another compound with unknown activity, the more likely it will have similar biological, chemical, and physical properties. This means that a model can be produced without rigorous statistics or neural networks. This technique is similar to structure-activity relationship (SAR) modeling, but instead of relying on substructure fragments to produce a model, this new model is based on minimum chemical shift differences on those substructure fragments. We refer to this method as minimum deviation of structurally assigned spectra analysis (MiDSASA) modeling. Modeling by the minimum deviation concept can be applied to other chemoinformatic data analyses such as metabolite concentrations in metabolic pathways for metabolomics research. A MiDSASA template model for 30 steroids binding the corticosterone binding globulin based on the activity factors of the two nearest compounds had a correlation of 0.88. A MiDSASA template model for 50 steroids binding the aromatse enzyme based on the average activity of the four nearest compounds had a correlation of 0.71.